Electronic Supplementarymaterial (ESM) For

Journal of Molecular Modeling

Electronic SupplementaryMaterial (ESM) for

Theoretical analyses of iron(III)-protoporphyrin-IX versus 4-methoxyacetophenone thiosemicarbazone binding via DFT-D3, MEP, QTAIM, NCI, ELF and LOL studies

Nyiang Kennet Nkungli1 and Julius Numbonui Ghogomu1,*

1Laboratory of Noxious Chemistry and Environmental Engineering, Department of Chemistry, Faculty of Science, University of Dschang, P.O. Box 67, Dschang, Cameroon

*Correspondence:

1. Technical computational details

1.1 ORCA input file structures

1.1.1 Geometry optimization/frequency calculations on MAPTSC

! RKS B3LYP D3BJ Opt NumFreq def2-TZVP def2-TZVP/J RIJCOSX PAL4

! Grid4 FinalGrid5 GridX4 TightSCF

! NormalPrint

! COSMO(WATER)

%maxcore 750

%scf

MaxIter 300

CNVDIIS 1

CNVSOSCF 1

end

* xyz 0 1

xyz coordinates of thione/thiol tautomers of MAPTSC

*

1.1.2 Single-point calculations on neutral and ionic forms of MAPTSC: method 1

! aB3LYP D3BJ ma-def2-TZVP def2-TZVP/JRIJCOSX PAL4

! Grid4 FinalGrid5 GridX4 TightSCF

! NormalPrint

! COSMO(WATER)

%maxcore 750

%scf

MaxIter 300

CNVDIIS 1

CNVSOSCF 1

end

%output

Print[P_Hirshfeld] 1

print[p_mos] true

print[p_basis] 5

end

* xyz bc

xyz coordinates of neutral or ionic forms of thione/thiol tautomers of MAPTSC

*

Where: a = RKS, bc ≡ 0 1 for the neutral molecule;a = UKS, b c ≡ 1 2 for the cationic species and a = UKS, b c ≡ -1 2 for the anionic species

1.1.3 Single-point calculations on neutral and ionic forms of MAPTSC: method 2

! aB3LYP D3BJ PWPB95 ma-def2-TZVPP def2-TZVP/JRIJCOSX PAL4

! Grid4 FinalGrid5 GridX4 TightSCF

! NormalPrint

! COSMO(WATER)

%maxcore 750

%scf

MaxIter 300

CNVDIIS 1

CNVSOSCF 1

end

%output

Print[P_Hirshfeld] 1

print[p_mos] true

print[p_basis] 5

end

* xyz b c

xyz coordinates of neutral or ionic forms of thione/thiol tautomers of MAPTSC

*

Where: a = RKS, b c ≡ 0 1 for the neutral molecule; a = UKS, b c ≡ 1 2 for the cationic species and a = UKS, b c ≡ -1 2 for the anionic species

1.1.4 Geometry optimization/frequency calculations on Fe(III)PPIX and the Fe(III)PPIX⎼MAPTSC complexes

! UKS RI BP86 D3BJ Opt NumFreq def2-SVP def2-SVP/J PAL6

! Grid4 FinalGrid5 TightSCF

! NormalPrint

! COSMO(WATER)

%maxcore 550

%scf

MaxIter 500

CNVDIIS 1

CNVSOSCF 1

end

* xyz 1 2

xyz coordinates of Fe newGTO "def2-TZVP" end

xyz coordinates of the rest of the elements in Fe(III)PPIX and Fe(III)PPIX⎼MAPTSC complexes

*

Note that the oxidation state of Fe is +3 but the overall charge onFe(III)PPIX and on each Fe(III)PPIX⎼MAPTSC complex is 1becauseProtoporphyrin-IX (PPIX) undergoes deprotonation with the loss of 2H+ ions as it coordinates with Fe(III).

1.1.5 Single-point calculations onFe(III)PPIX and the Fe(III)PPIX⎼MAPTSC complexes

! UKS B3LYP D3BJ def2-TZVP def2-TZVP/JRIJCOSXPAL6

! Grid4 FinalGrid5 GridX4 TightSCF

! NormalPrint

! COSMO(WATER)

%maxcore 550

%scf

MaxIter 500

CNVDIIS 1

CNVSOSCF 1

end

* xyz 1 2

xyz coordinates of Fe(III)PPIX and Fe(III)PPIX⎼MAPTSC complexes

*

1.1.6 Single-point calculations, along with gCP correction at RIJCOSX-B3LYP-D3BJ/def2-TZVP level

! UKS B3LYP D3BJ def2-TZVP def2-TZVP/J RIJCOSX GCP(DFT/TZ) PAL6

! Grid4 FinalGrid5 GridX4 TightSCF

! NormalPrint

! COSMO(WATER)

%maxcore 550

%scf

MaxIter 500

CNVDIIS 1

CNVSOSCF 1

end

* xyz 1 2 (xyz 01 for MAPTSCtautomers)

xyz coordinates of Fe(III)PPIX, MAPTSCtautomers and Fe(III)PPIX⎼MAPTSC complexes

*

1.1.7 Single-point calculations, along with gCP correction at RI-BP86-D3BJ/def2-TZVP level

! UKS B3LYP D3BJ def2-TZVP def2-TZVP/J RI GCP(DFT/TZ) PAL6

! Grid4 FinalGrid5 GridX4 TightSCF

! NormalPrint

! COSMO(WATER)

%maxcore 550

%scf

MaxIter 500

CNVDIIS 1

CNVSOSCF 1

end

* xyz 1 2 (xyz 01 for MAPTSCtautomers)

xyz coordinates of Fe(III)PPIX, MAPTSCtautomers and Fe(III)PPIX⎼MAPTSC complexes

*

1.2 The approach utilized to locate the global minima

In an attempt to locate the global minima, the Fe(III)PPX (free heme) was first optimized at a lower level of theory, RI-BP86/def2-SV(P). Then three models of each complex, obtained by appending the ligand (L1 or L2) on Fe(III)PPX in three different orientations as shown in the diagram below, were pre-optimized at RI-BP86/def2-SV(P). It is worth noting that in the diagram, the arrow head points in the direction of the terminal NH2 group of the thiosemicarbazone moiety of each ligand. Since the Fe(III)PPX molecule is somewhat symmetrical, several other orientations of the ligand will result in structures similar to those obtained from the orientations considered.

After pre-optimization, we selected the most stable of the three models (i.e., the model with the lowest energy) for further optimization at RI-BP86-D3(BJ)/def2-SVP /[def2-TZVP for Fe(III)] level. For each complex, the most stable model was that obtained from orientation (1) of the ligand. In this model, a hydrogen bond was formed between one propionate side chain of Fe(III)PPIX and the thiosemicarbazone moiety of each ligand. This hydrogen bond interaction is probably the main feature that accounts for the model’s extra stability.

Fig. S1: Schematic representation of the initial guesses that were pre-optimized in effort to locate the global minima

1.3 AIMAll and Multiwfn input files

MOLDEN input files generated by ORCA 3.0.3(using the utility:orca_2mkl BaseName -molden)were standardized,and then standard WFN files appropriate forthe AIMAll and Multiwfn programswere generated by the molden2aim utility.All MOLDEN input files used here were generated from GBW files obtained from the single-point calculations described in section 1.1.5above.

2. Cartesian coordinates ofatoms in the optimized geometries of Fe(III)PPIX and Fe(III)PPIX⎼MAPTSC complexes

ESM Table S2Optimized atomic coordinates ofFe(III)PPIX

75

Fe -0.06293583994993 -1.38909149502228 0.13288846984415

N 0.51530408471962 0.48926874760127 0.11965264983935

C 1.72994746193919 1.00189190910227 0.52997682637438

C 0.64081955586533 2.80145962204439 -0.35588587042469

C -0.17422262724953 1.59713543663272 -0.39537888644197

C 3.06121117109116 3.22048399862050 0.58880932954947

C 0.10095432247813 4.11110757259053 -0.86892899008176

C 1.00964845520817 5.33777557502016 -0.83821733148342

C 1.30696356650748 5.83905563184181 0.56013551019408

C 2.71966915565519 0.27679220425713 1.18571419825524

C 2.66753807011108 -1.09749032144538 1.39212770668410

C 3.75392899379075 -1.88205425927637 1.98242452918920

N 1.68284275945027 -1.92594502817855 0.88599905549654

C 2.17420664216578 -3.22330527807963 1.05839884865944

C 3.45853422333831 -3.22140582224000 1.71195016115094

C 4.91466775027388 -1.39408949631959 2.70805701204052

C 4.99875245484951 -0.24964273149764 3.43334231438205

C 4.24570810807587 -4.43907019142363 2.07323165943517

C 1.51678532899690 -4.38420414344637 0.65879699151210

C 0.22139968691944 -4.40722935809928 0.15996220696692

N -0.57703075948378 -3.29592178029193 -0.02142548473615

C -1.83566317132982 -3.80811233602657 -0.36787518241346

C -1.82699405966782 -5.24137682191636 -0.45388127436229

C -0.51511671087888 -5.64053813596880 -0.14198098063950

C -2.99162136496687 -6.10435095521291 -0.80801039960455

C 0.07718754469573 -6.95627818986949 -0.08483691212860

C -0.51786751273362 -8.14602947266509 -0.38309242216677

C -2.97742213423296 -3.02800625025477 -0.58838866898928

C -2.98709976431444 -1.64887124501019 -0.63226624744853

N -1.85463097028267 -0.83301592081498 -0.46963567836900

C -2.29945542271784 0.43193135812416 -0.78092017702250

C -3.73004591596492 0.44614534327066 -1.09970582347156

C -4.16500934077841 -0.86260895276909 -0.97852528369545

C -5.50736129454913 -1.49121340221494 -1.19821155006123

C -4.41517115554561 1.73195573807093 -1.46907278532841

C -5.90318329001460 1.69867538962838 -1.80838141733032

C -6.21914821170115 0.93667271143776 -3.07903506043336

C -1.49485050281582 1.57303457453907 -0.80816278897927

O 0.70300003438343 5.50917511414813 1.56998906298769

O 2.32211355747136 6.73026349955858 0.56486441705611

H 2.44202215831120 7.03998754590978 1.49208372114754

O -5.39677469125530 0.58818862159234 -3.91324483203225

O -7.54211986539731 0.69527625964799 -3.19937126586129

H -7.68316819949630 0.22887084506195 -4.05528968519101

H -1.94730828988101 2.51391705086958 -1.14201246266736

C 1.84134181691707 2.43077228939994 0.23003103695077

H 3.62257719604542 0.80816012122098 1.50716843955811

H 5.79238590560933 -2.06414267666290 2.69448872784700

H 4.14309467106156 0.43055521274888 3.56576575292718

H 5.93245410358594 0.01391672487315 3.95330219798591

H 2.04305559060855 -5.33638934409317 0.79889818403034

H 1.13350331499340 -6.99198228370303 0.22769350813414

H -1.56099837630611 -8.23040910757712 -0.71542332592155

H 0.05656117837545 -9.08107763794925 -0.30019271252904

H -3.92014691767846 -3.55296185378302 -0.78538482329746

H 4.34609488696407 -5.12731101423618 1.20946663522917

H 3.75220134909233 -5.00953426500407 2.88857890218904

H 5.26275590018276 -4.17701595113511 2.41968405721700

H 3.98438213278461 2.64323758840151 0.38284590058195

H 3.06554307497442 3.46503340212477 1.67257515519873

H 3.14199001440246 4.16861580551135 0.03403959076409

H -6.33571520058724 -0.77008914745510 -1.10962918847560

H -5.69700420720819 -2.29460741346199 -0.45952047640517

H -5.56835240801537 -1.95102795120974 -2.20706212253077

H -3.91968392117477 -5.52169986922427 -0.94895871109618

H -3.18207009440152 -6.85942004961355 -0.01698470624734

H -2.80114343415255 -6.66118371283448 -1.74990959899109

H -3.87130201024253 2.16875796241669 -2.33513988871140

H -4.26683043021532 2.45535167095931 -0.63842228055302

H -6.25669730297995 2.73952234453336 -1.97374221836576

H -6.52661970613196 1.31493769378648 -0.97662204785738

H -0.81890238915605 4.35163737104424 -0.29297775914997

H -0.23640071913380 3.96128698300120 -1.91625688928087

H 0.50022991847080 6.17458724367986 -1.36382631042218

H 1.95706207222559 5.18650670271495 -1.39287223817963

ESM Table S3Optimized atomic coordinates ofFe(III)PPIX-L1

103

Fe 0.76695489642718 -1.84851848628773 -0.94013033363173

N 0.46005989483006 -0.30560004628084 0.28071712994011

C 0.42448600653318 1.04450596024009 -0.04593894837995

C 0.18472037633781 1.00662445578781 2.21297024378803

C 0.31351552050121 -0.33530349808519 1.66182506059081

C 0.10826062574578 3.36384712357864 1.12426532593276

C -0.02315340815383 1.33296228170923 3.66259133467592

C 1.29049892102687 1.56553819950005 4.46258938799835

C 2.20192941923031 0.36879747975634 4.42267884850666

C 0.54541520937646 1.55908127218646 -1.32802038916165

C 0.76981001294608 0.79127144020360 -2.46381669002511

C 1.08458181934799 1.34714421674188 -3.77390170164613

N 0.88596278361992 -0.59401865716001 -2.46942118475236

C 1.34701348374848 -0.91073622702331 -3.74619898006574

C 1.50886429892538 0.27489358969132 -4.55743614828692

C 1.01468315679204 2.74081983230557 -4.20039818466738

C 0.16611653182484 3.69872813185134 -3.75526235481337

C 1.97435906683071 0.28781239526022 -5.97820854441172

C 1.55705672131514 -2.19833676318502 -4.23035287963652

C 1.23692695824683 -3.35817773233623 -3.53657896316879

N 0.77258051490521 -3.37783150503534 -2.23149134190967

C 0.50520267926666 -4.71590803474929 -1.96574545374906

C 0.76956353288226 -5.55235628360872 -3.12380351943618

C 1.25558440367420 -4.70203571478855 -4.11525589983675

C 0.57008745193279 -7.03167935399224 -3.18865682390662

C 1.70517324204285 -4.99111157116806 -5.46962810620233

C 1.56563293071380 -6.14872219019270 -6.16394111227312

C 0.08903865695329 -5.20283920294942 -0.73070580320404

C -0.03722015040047 -4.43780120842886 0.42203285501608

N 0.15647020445862 -3.05941750278338 0.50104725873300

C 0.07785843570215 -2.76845798250812 1.85878918346146

C -0.19562953202663 -3.96069510773000 2.63675392444474

C -0.29872722698476 -5.00630249219104 1.73135694308410

C -0.60127914097493 -6.44569115452835 2.00260196990379

C -0.40908431468245 -4.00044472901314 4.12118131987717

C -1.88203053635653 -3.74149770119400 4.54323039063872

C -2.30866999896325 -2.32786413276042 4.21441109154281

C 0.20069389333454 -1.49716553158845 2.41110228456524

O 3.14021596591699 0.22846701026577 3.63488692109553

O 1.86114074641832 -0.57560014785693 5.31298041565292

H 2.49699647171443 -1.32444144176318 5.24273841942578

O -1.96093994376839 -1.33672907258625 4.84630374898071

O -3.07417929124497 -2.25887839870238 3.10723719003774

H -3.26830512712543 -1.30754874595807 2.93848069688949

H 0.11362221778224 -1.39951978295783 3.49989172575931

C 0.24252820049654 1.87423973744432 1.13728776014408

H 0.53159669250072 2.64917955424909 -1.44285433508604

H 1.72180377428149 3.01436472652214 -5.00411750506636

H -0.61645386268341 3.49604296415948 -3.00755352085919

H 0.21348310966742 4.72037455560237 -4.16262770711465

H 1.92852070195570 -2.29421378156287 -5.25846438125651

H 2.22402374870822 -4.16183383096581 -5.98093282715631

H 1.04579920221237 -7.02981557160072 -5.76256702112348

H 1.96991430134076 -6.23181484785697 -7.18459256853091

H -0.09091363162441 -6.28219406679022 -0.64065561665983

H 2.90915481238264 -0.29584994593961 -6.10404774297670

H 2.16533024649833 1.31798013478385 -6.33327452968709

H 1.21795029704699 -0.16152909938681 -6.65686188262762

H -0.77911641958964 3.68631262489403 0.53992671198113

H 0.99310585025122 3.84994263508443 0.66284414970047

H 0.00364718454227 3.76826630685570 2.14894583609520

H -0.68934212849078 -6.64058974365834 3.08822765625050

H 0.18985208279417 -7.11337359469264 1.60234225200674

H -1.55551545910189 -6.75506147359515 1.52655042294200

H 0.36227557187416 -7.47169955352116 -2.19549578789111

H 1.46883167044403 -7.53483671362178 -3.60266094977984

H -0.28030898503670 -7.29748087762587 -3.85295642632690

H 0.24525903492202 -3.26457321830781 4.63263802142070

H -0.11812858241050 -4.99591929048862 4.51128871554112

H -1.96652380415742 -3.86932789448094 5.64037371587704

H -2.55280662766129 -4.46641654063822 4.04455395361737

H -0.61783260553105 0.53606308651019 4.15450482252048

H -0.61875426582036 2.26336559704316 3.75042688408460

H 1.03476297636537 1.79366068876523 5.51541625655845

H 1.84497103572319 2.42254986032465 4.04039509123465

S 2.87936660344804 -2.26212286699635 -0.72473813669974

C 3.30014760154363 -1.29001469222583 0.69246882248129

N 3.32956549101489 -1.87667635301105 1.88328816094935

H 3.05424661540612 -2.85835923569015 1.94905470379201

H 3.47960133836663 -1.31346883891127 2.74374675040512

N 3.62054162248292 0.01137775382003 0.57663889884718

H 3.84154517719758 0.54553687868254 1.43832058125957

N 3.64691289620647 0.59130546916840 -0.65751708531030

C 3.97693564768926 1.84752237668797 -0.77006794221707

C 4.01415587378770 2.37132646345966 -2.17911251703598

H 3.77401222694256 1.56037347950730 -2.88958324983096

H 3.27635965676266 3.19190482356709 -2.30324251134912

H 5.00951818511929 2.79256965078717 -2.42914271327396

C 4.30357950435522 2.77784396243346 0.33956680617578

C 5.38632007753131 3.67918629146366 0.20790223692047

C 5.72643425470337 4.57756166708592 1.22705575967762

C 4.96091801626897 4.61083026193508 2.41533785026512

C 3.86199033667624 3.73151679674132 2.55266418013581

C 3.54326440431846 2.83010430479827 1.53721850182946

H 2.66119067063918 2.18506030834446 1.66353160964855

H 3.26634388016342 3.78764555850154 3.47539334238137

H 5.99646196413197 3.67039747479710 -0.70690260999119

H 6.58469288159078 5.24753061865007 1.08613707053247

O 5.19618466371040 5.44269153661814 3.45816890130588

C 6.29086935844669 6.35909056697408 3.36776843500301

H 6.15950850862463 7.06131331723841 2.51737324191450

H 7.25729032040086 5.82315885588823 3.25629258203433

H 6.29445971994761 6.92727815249449 4.31493857494153

ESM Table S4Optimized atomic coordinates of Fe(III)PPIX-L2[in which L2 is N2-bound to Fe(III)]

103

Fe -0.04123041343392 -1.52009901454977 -0.38881814024136

N 0.48143608372275 0.37471794549345 -0.10493272674674

C 1.78139121800642 0.82012572543901 0.08128614052939

C 0.59487769878638 2.71017312746756 -0.35776416545297

C -0.24617920751785 1.52152517941936 -0.39867380943870

C 3.18580636228048 2.98857013738260 0.03677025876666

C 0.01009029217090 4.07574679980441 -0.60398284341916

C 0.93800305175585 5.28754863267552 -0.56518031287510

C 1.52024744162938 5.56338441299848 0.80563842648454

C 2.83845542473932 0.02735618776781 0.51558371871138

C 2.70493129426788 -1.30100920777954 0.90100714059535

C 3.73541232474086 -2.08151405027926 1.58719556063002

N 1.58241834587539 -2.06933552001113 0.64829941947857

C 1.88915239661179 -3.33185418359646 1.14258760297002

C 3.21498145304757 -3.36461972496929 1.72748756261521

C 5.04485580284341 -1.63504621542689 2.05253844532846

C 5.40436947454070 -0.39653619591647 2.46861212756184

C 3.84146053047944 -4.56597228275888 2.35988288175345

C 1.07183920510106 -4.44802748112058 1.03757397218684

C -0.12968593906841 -4.47653101411606 0.34193690717783

N -0.72668298201239 -3.37069476350432 -0.25462537878240

C -1.85077229985481 -3.88055828173790 -0.90551838263097

C -1.95271396149908 -5.31188500446735 -0.74264632782222

C -0.89325717720143 -5.68785653452791 0.08872943782155

C -2.97105980107691 -6.19194687342498 -1.38836527636446

C -0.52471432601466 -6.99805563002164 0.60063710973288

C -1.26974833884630 -8.13119919923128 0.58584384320413

C -2.81390353850551 -3.10199775696001 -1.54359609269017

C -2.84912781400698 -1.71397196577967 -1.49433414515226

N -1.86043800806404 -0.91646188607855 -0.91966475407762

C -2.31969988430561 0.38349500143051 -1.07006576757127

C -3.61734315602023 0.41034301580425 -1.72578350920311

C -3.94144921605531 -0.90487142480089 -2.01273401086297

C -5.14894872593701 -1.43958365879682 -2.71468446601049

C -4.37116675553017 1.64227139382936 -2.12995965248489

C -4.04252611141851 2.11561964843210 -3.57696649660635

C -2.65592687242020 2.69094207989203 -3.72803154611973

C -1.58126011688221 1.52866246129299 -0.78358917486868

O 1.11259526053101 5.08504796442236 1.85349510961371

O 2.54979291646534 6.43574254537016 0.74311080974340

H 2.85894394488675 6.59722191013657 1.66414666096102

O -1.67038469468497 2.09180333986171 -4.16221905571786

O -2.58046705999430 3.97024223026055 -3.32563367844735

H -1.66259853625794 4.28905258241586 -3.48935088945680

H -2.05971239403924 2.50038089154257 -0.96003023078153

C 1.88227920925942 2.26177269265688 -0.10279261158465

H 3.82032801885534 0.49845605981369 0.63554309726375

H 5.81161300974976 -2.42987195900694 2.09536276076746

H 4.69112614664474 0.43971525466858 2.53144060497374

H 6.43541967929857 -0.19698706536783 2.79919388082762

H 1.44276396826716 -5.38671874756278 1.46662084146063

H 0.47684406992442 -7.06293221468756 1.05790973160012

H -2.28753135431862 -8.17294841414659 0.17424612471908

H -0.86557394204228 -9.06350581320832 1.00887559978050

H -3.64854956865422 -3.61709204562170 -2.03668465679731

H 3.82957509146191 -5.43792862815755 1.67299933639199

H 3.29717493179013 -4.87416389681037 3.27779563451062

H 4.89262248395626 -4.37387739995512 2.64549623240950

H 4.00598538923272 2.42091754027590 -0.44634127372080

H 3.46218032610153 3.11735046526890 1.10484214577510

H 3.17400222252679 3.98923094424196 -0.42434073469774

H -5.87754793027720 -0.63608926543113 -2.93358262272982

H -5.66690617363160 -2.20932184956869 -2.10555978740464

H -4.87862467055210 -1.92049915916518 -3.67847816722231

H -3.51154872609027 -5.67556207723559 -2.20393868422533

H -3.72968647836969 -6.55373463541781 -0.66139776145920

H -2.47631799025863 -7.08845479181638 -1.81655507278686

H -4.19814712366823 2.47444998979534 -1.41821736599658

H -5.45947589711590 1.43546081841649 -2.10068193145114

H -4.76926202075090 2.89933677786025 -3.86813109634338

H -4.13603859531136 1.26672164133785 -4.28004450085266

H -0.80975270436480 4.23954627549686 0.12811500867798

H -0.48690887614913 4.06606018231254 -1.59678016170334

H 0.35875239424058 6.19485772956377 -0.84349973659576

H 1.75313367706065 5.22782003313276 -1.31323683121134

S 1.61335591852146 0.73811711630500 -3.39811939677320

C 0.39571208796295 -0.46434161430057 -2.96142029816212

N -0.81820536158552 -0.43346736136967 -3.48792465202131

H -1.47742510586813 -1.17351574079509 -3.22064259952521

H -1.20416023210505 0.43114778234077 -3.92420058914040

N 0.78273519798699 -1.48093924101194 -2.13202602276292

H 0.69640925491075 1.55110814520705 -4.01161190134764

N 2.16514205409901 -1.59200576445448 -2.16878510801856

C 2.72388555387240 -2.77178127357169 -2.10213977049231

C 4.22258658718722 -2.73577858465051 -1.95048884486892

H 4.58062275909593 -1.69525676222536 -2.04977275346618

H 4.50778318642775 -3.09724638486567 -0.93987876595280

H 4.72638162120444 -3.38842759513253 -2.69079397733843

C 2.04922975472884 -4.08164901786823 -2.18874656248095

C 2.67806760495557 -5.23985955877426 -1.67135093645834

C 2.10351418016452 -6.51068589348044 -1.79059673520177

C 0.87703477682967 -6.65935443862472 -2.47824416794015

C 0.25008164463264 -5.51807219790349 -3.03160582271518

C 0.81680991794332 -4.25827494716430 -2.87570834415564

H 0.30570439261970 -3.39158560497160 -3.30932731965911

H -0.69531464828800 -5.64781332594394 -3.57682759603618

H 3.63169033682502 -5.14898742639885 -1.13264823161455

H 2.61315277315064 -7.37566688313830 -1.34718885676291

O 0.23473977840595 -7.83715601778252 -2.65781695456281

C 0.84839852128710 -9.03276079718360 -2.16966659475955

H 0.97336215976128 -8.99794006283933 -1.06816179437811

H 1.83460768144295 -9.20099924965525 -2.65175413417519

H 0.16372146518088 -9.85860386471228 -2.43217161364589

ESM Table S5Optimized atomiccoordinates of Fe(III)PPIX-L2[in which L2 isS5-bound to Fe(III)]

102

Fe 0.90053672649323 -1.83665075215809 -0.86722788651448

N 0.81004115887650 -0.31789573792328 0.42045527075468

C 0.98171192358724 1.03386884527500 0.15091406596058

C 0.66780984612926 0.95444170874456 2.39674116592645

C 0.62778749674239 -0.37319562650913 1.79727128423896

C 0.93217411696772 3.33356220386496 1.39435211616913

C 0.45040292907599 1.25813342423350 3.85074513060604

C 1.75750751609154 1.31492741733450 4.68787079841432

C 2.51176330888898 0.01052693091992 4.67480004659297

C 1.15788082552429 1.58220975993114 -1.10913434045011

C 1.17386472547378 0.85347771218819 -2.29220328168834

C 1.43295558487415 1.43241460527900 -3.60579051169861

N 1.06882176833612 -0.52927496662815 -2.36747317690320

C 1.34167143764445 -0.83712796416106 -3.69814849004898

C 1.58520479751453 0.35639375234533 -4.47794072185295

C 1.53970461972440 2.84168509768905 -3.97004241782624

C 0.95248745491171 3.90887550211874 -3.37504324203635

C 1.88269264097926 0.38004765991853 -5.94375649677274

C 1.35565558989121 -2.11621384030042 -4.24530468725929

C 1.03591606150889 -3.27579205007297 -3.55183226830934

N 0.71173734970142 -3.31761435118505 -2.20544575408903

C 0.41728982785162 -4.65325161310838 -1.95180144089159

C 0.53668869825601 -5.46501377225145 -3.15049556025802

C 0.93557753120656 -4.60028058309125 -4.16712415160453

C 0.29290352758911 -6.93789012010579 -3.22809102787523

C 1.22033315469517 -4.86533579457233 -5.57037429402665

C 0.91185884701526 -5.97573802978285 -6.28740112663131

C 0.06002776352506 -5.15928883591388 -0.70636530525113

C -0.01229872587859 -4.41477012950128 0.46401623625349

N 0.24357163245291 -3.04899626841832 0.56867000647605

C 0.15374909241383 -2.77727444002618 1.92848591489099

C -0.19395487554888 -3.96708367511611 2.68242695177929

C -0.31392541764096 -4.99481258292857 1.76046839516827

C -0.67778113884047 -6.42601544531128 2.00256920408040

C -0.44746289532585 -4.01608247699773 4.16031024794689

C -1.91247355035498 -3.67540963340620 4.55225966620541

C -2.24935396325432 -2.23535831301642 4.23330637201416

C 0.35922943081833 -1.53070636223888 2.50981483920933

O 3.53941019222110 -0.20332100929592 4.03885600199920

O 1.91721857986515 -0.94107249455459 5.42727786416325

H 2.46605769212200 -1.75659888410667 5.37059637933965

O -1.88100046738199 -1.27433290678837 4.89822696123239

O -2.96267288640739 -2.10794846922142 3.09560277253289

H -3.09259043021144 -1.14454769777263 2.93463241319256

H 0.25601964112357 -1.44787404057818 3.59791522856584

C 0.89038121481765 1.83981846668965 1.36155137671983

H 1.32801573774812 2.66293588628695 -1.17047227820750

H 2.15729330369581 3.03682204143446 -4.86545507413778

H 0.26768753517414 3.80987796400493 -2.51900781432737

H 1.12375589934453 4.92591782337884 -3.76016810547306

H 1.59631710904695 -2.20208573029978 -5.31278065799169

H 1.75230499619119 -4.05833667115830 -6.10402571917450

H 0.35646682305611 -6.82529455200642 -5.86519742167311

H 1.20286006904264 -6.04863390332412 -7.34681299425454

H -0.15811893781855 -6.23305950559877 -0.63434603972274

H 2.70753853265522 -0.31560643637629 -6.20210282012795

H 2.17424736843088 1.39200099749647 -6.28307018703498

H 1.00057609826592 0.07097623146923 -6.54473682993363

H 0.03688329890170 3.77163388787299 0.90226317367621

H 1.82121185656864 3.72673315015919 0.86273936998255

H 0.96990855287945 3.71649820720952 2.43125099716878

H -0.77161137493260 -6.63978357390733 3.08446420654108

H 0.08219506407103 -7.11961161661924 1.58604285171757

H -1.64614194700766 -6.68580589342575 1.52468323748979

H 0.27058920959369 -7.41113268768468 -2.22819864465975

H 1.08432335957437 -7.43843079486757 -3.82367907925165

H -0.67493637288903 -7.16859076156601 -3.72420474137927

H 0.23441876148047 -3.32694569683542 4.69985818245346

H -0.22678841949125 -5.03257628796206 4.54277637456395

H -2.03144136956318 -3.81171813591775 5.64520561201622

H -2.61165646611014 -4.35355946464133 4.02719259029792

H -0.24581254453894 0.52059454814216 4.30040941844327

H -0.03914072600622 2.24774690784282 3.95134452739824

H 1.50285015415230 1.57097548456874 5.73611474335277

H 2.42994293218859 2.09085290715381 4.28071672397337

S 2.97343967399357 -2.37493651307660 -0.75098385622878

C 3.63928688463650 -1.49200186407972 0.67751431133726

N 3.54477222057401 -2.14419135104036 1.87205889599629

H 2.84927868474911 -2.89037789049221 1.92580402549238

H 3.67086212787619 -1.57086653941477 2.72218873655348

N 4.24183289686064 -0.33306327660809 0.59662839369026

N 4.35206885873372 0.18193334980142 -0.65998484711031

C 4.41196444910707 1.48016911751064 -0.83018491086065

C 4.61162734768870 1.88891009377648 -2.27231662011319

H 4.63322495193533 0.97953139215625 -2.89860736115763

H 3.78588432736655 2.53515084399358 -2.63291495070046

H 5.55632967936308 2.45621320396945 -2.41448457219960

C 4.30694782614291 2.55215219478728 0.18900011375952

C 4.31455566929244 3.90805867114684 -0.23162511871832

C 4.25621760627232 4.97899094939004 0.67234184354453

C 4.19997683530059 4.71842073049591 2.05847682288784

C 4.19136433258866 3.37602249516126 2.50113979165047

C 4.22517782037794 2.31823057113464 1.59314619005656

H 4.18483928141410 1.28469379641924 1.95744277842782

H 4.14425532994899 3.18563206635700 3.58389872763451

H 4.36093228475901 4.15045697100821 -1.30176417701134

H 4.25442994634362 6.00662498212655 0.28533412442426

O 4.14070293394688 5.67573032078071 3.02271035985796

C 4.12015685920192 7.04425310779833 2.61654987689459

H 3.23538576357112 7.26616604659460 1.98172657413090

H 5.04291988911588 7.31798503382587 2.06102441051598

H 4.06252666106947 7.64210295215881 3.54401630707523

Fig. S6:The optimized geometry of Fe(III)PPIX⎼L2(where L2 is S5-bound to the Fe(III) center of Fe(III)PPIX). The H-bond between the NH2 group in L2 and the C=O group in one propionate side chain of Fe(III)PPIX is shown as a red dashed line

3. Harmonic vibrational frequenciesforFe(III)PPIX and Fe(III)PPIX⎼MAPTSC complexes

ESM Table S7IR frequencies for Fe(III)PPIX

The first frequency considered to be a vibration is 11

The total number of vibrations considered is 214

Mode freq (cm**-1) T**2 TX TY TZ

------

11: 36.95 0.933261 (-0.108034 0.939420 -0.197686)

12: 43.51 1.160514 (0.526545 0.277159 -0.898024)

13: 50.63 5.806300 (0.832253 -2.082444 0.881523)

14: 52.40 1.033622 (0.719737 -0.677493 -0.237916)

15: 55.61 1.792582 (1.002636 0.041935 -0.886310)

16: 68.24 2.412001 (-0.402003 1.359962 -0.633166)

17: 69.12 1.514290 (-0.505198 0.204213 1.103341)

18: 82.74 0.528967 (0.433725 -0.463893 -0.354475)

19: 84.06 2.137768 (-1.194981 -0.027108 -0.842053)

20: 96.96 0.366101 (0.265296 -0.206565 0.503041)

21: 107.36 4.993336 (1.805408 0.918980 0.943033)

22: 112.48 1.929962 (-1.329959 -0.086175 0.392104)

23: 113.89 0.735253 (-0.545714 -0.655329 0.089410)

24: 121.54 0.401801 (-0.629923 0.055201 0.044166)

25: 131.35 1.330302 (1.070672 0.230697 -0.361583)

26: 135.62 0.541209 (-0.544102 -0.223269 -0.441942)

27: 144.23 1.015715 (-0.880369 -0.411451 -0.267159)

28: 159.90 0.789500 (-0.554409 -0.628531 -0.295094)

29: 165.20 1.659831 (-0.790278 -0.706496 -0.732226)

30: 176.51 5.260709 (0.654513 0.432421 2.155304)

31: 182.69 11.707556 (-2.038843 -2.125136 -1.741974)

32: 192.73 3.537819 (-0.878647 -0.627832 1.540008)

33: 202.66 0.510579 (-0.593084 -0.389754 -0.083197)

34: 208.42 3.097636 (1.094669 1.378141 0.007936)

35: 222.60 3.940044 (-1.229750 -1.509772 -0.385159)

36: 227.24 33.952531 (2.843020 3.255904 3.907538)

37: 234.81 1.348926 (-0.852490 -0.766731 -0.185232)

38: 240.81 1.324328 (-0.515150 -0.568811 -0.857556)

39: 244.70 1.958921 (0.488043 0.895723 0.958340)

40: 255.09 2.809987 (-1.045819 0.116265 1.304888)

41: 269.15 8.064629 (2.373637 1.556014 -0.096427)

42: 276.76 3.419731 (-0.823551 -1.610975 0.382431)

43: 294.39 0.655886 (-0.116140 0.771067 -0.218753)

44: 301.06 10.145576 (2.611132 1.777515 -0.409884)

45: 304.36 11.454631 (0.762085 -2.566462 -2.070538)

46: 309.46 5.138592 (-0.927100 0.647595 -1.964612)

47: 312.77 8.980873 (-2.671036 0.909284 -1.009772)

48: 320.25 40.275655 (2.801774 4.449060 3.554095)

49: 325.20 21.674532 (-3.476583 -0.864851 2.973203)

50: 333.78 1.297208 (0.940445 0.036142 -0.641455)

51: 336.15 1.661822 (0.951853 0.846592 0.197689)

52: 337.90 4.211702 (-1.306061 0.624739 1.454513)

53: 353.83 20.211522 (-3.705195 0.562798 -2.483206)

54: 366.85 20.926674 (0.047398 4.553546 0.435486)

55: 375.31 2.054551 (-1.414482 -0.032920 -0.229579)

56: 392.92 1.874644 (0.977803 -0.630092 0.722170)

57: 410.88 6.400525 (1.150401 -2.159991 0.641514)

58: 448.77 4.270935 (1.547902 -1.273308 0.503608)

59: 454.24 6.150288 (-1.996438 1.127889 -0.944664)

60: 462.16 0.621004 (0.764831 -0.142683 0.125215)

61: 478.27 85.236034 (-7.428872 -4.256297 -3.454249)

62: 496.67 1.342383 (0.228469 -1.095168 -0.301315)

63: 507.34 2.431199 (0.411054 1.488432 -0.216345)

64: 509.50 9.570509 (-1.948040 2.400643 0.112076)

65: 510.77 27.524395 (2.062006 4.650557 -1.282516)

66: 524.14 53.887777 (-3.558536 6.017234 -2.239975)

67: 536.39 55.069993 (4.530712 4.885378 3.267372)

68: 574.41 11.477968 (-1.934431 2.743206 -0.459096)

69: 578.82 16.153217 ( -2.026060 -2.199587 -2.685166)

70: 599.35 9.571572 (-2.500120 -1.589620 -0.891112)

71: 600.85 28.336055 (-4.562237 -0.305711 -2.725543)

72: 610.85 5.888804 (-1.854537 0.598639 1.446073)

73: 630.30 7.733318 (-0.431788 -1.646616 -2.198984)

74: 633.20 3.084231 (1.055992 0.073182 1.401341)

75: 639.95 117.504289 (5.178247 -8.729757 3.805443)

76: 654.32 18.283923 (-2.584907 -2.306689 2.506266)

77: 663.54 109.267618 (3.124133 -9.632549 2.592570)

78: 666.78 44.761895 (-1.196400 6.553992 -0.612953)

79: 680.19 4.790089 (1.127539 -1.488058 1.142116)

80: 684.00 2.802049 (-1.168367 -0.134549 -1.191161)

81: 687.07 7.376632 (-1.171321 2.354260 -0.679777)

82: 697.22 3.886299 (-0.650626 1.529913 1.059411)

83: 711.22 1.411004 (-1.161466 0.046812 -0.244560)

84: 713.07 2.290326 (-0.640601 0.469774 -1.288126)

85: 714.87 1.791338 (0.299929 1.098885 -0.702731)

86: 719.44 21.532648 (-1.831554 -4.250715 0.330883)

87: 725.99 20.566225 (-2.029848 0.101247 -4.054095)

88: 740.64 22.797839 (-2.329758 4.129668 -0.562058)

89: 749.31 19.277359 (0.048563 -3.966318 -1.882372)

90: 750.79 70.989042 (4.599199 6.862147 1.657511)

91: 756.93 8.406146 (0.363401 -0.578179 -2.817764)

92: 773.72 6.962311 (-2.393018 -0.903297 -0.647941)

93: 787.73 0.194325 (0.091098 -0.430995 -0.016405)

94: 790.49 11.053969 (-2.943318 -1.545831 0.035428)

95: 794.79 79.636006 (3.067418 4.459905 7.094801)

96: 807.13 1.397997 (-0.334217 -0.456790 -1.038094)

97: 840.36 61.610397 (4.196708 0.594237 -6.606430)

98: 844.16 8.567787 (-1.491862 2.503738 0.270982)

99: 852.06 30.812373 (-3.554850 0.080366 4.262506)

100: 854.25 0.028256 (0.076321 -0.149225 0.012775)

101: 894.92 22.428275 (-1.868355 4.267654 0.851264)

102: 900.29 11.469824 (-2.190561 1.754958 -1.895097)

103: 909.53 59.254601 (-2.615900 -0.348550 7.231195)

104: 911.36 70.380221 (-1.859581 2.272660 -7.858575)

105: 922.25 59.906799 (2.071084 7.449474 0.350351)

106: 936.99 42.628481 (3.959138 4.342318 2.845695)

107: 938.41 13.493020 (2.814326 -2.258161 -0.687966)

108: 942.84 20.347905 (-2.995328 3.040818 -1.459226)

109: 946.20 28.215473 (-0.995354 -5.190293 0.534415)

110: 963.89 101.130469 (0.536797 9.700495 2.596673)

111: 970.67 45.891930 (0.589734 -5.675076 3.652075)

112: 972.19 75.355431 (-5.968781 5.266271 -3.463449)

113: 975.12 127.597462 (6.947679 2.644542 8.504918)

114: 986.13 3.615955 (-0.522290 0.489945 1.761568)

115: 990.62 22.528387 (2.305496 3.935935 1.312056)

116: 993.06 3.463331 (0.567613 0.619727 1.660447)

117: 996.86 22.292133 (4.045553 0.334566 2.411162)

118: 997.95 22.103718 (1.030968 4.298239 1.601862)

119: 1017.87 98.403037 (0.154121 9.828524 -1.333944)

120: 1028.80 115.398493 (-8.895284 -2.452797 -5.500564)

121: 1040.45 10.763114 (-2.568005 0.116844 -2.038336)

122: 1042.93 8.937309 (2.366278 0.507592 1.755103)

123: 1056.95 368.624045 (11.379245 12.986191 8.396169)

124: 1065.38 55.331666 (-6.631764 3.266888 -0.823906)

125: 1077.63 83.424188 (-1.877167 -8.787350 -1.637958)

126: 1082.16 311.748609 (-15.931888 -4.590748 -6.070304)

127: 1096.41 98.194625 (5.682026 -6.473296 4.899556)

128: 1109.19 196.624712 (11.291727 6.447742 5.248642)

129: 1113.40 275.553601 (-10.894900 -12.412036 -1.672157)

130: 1115.12 399.283510 (19.239401 1.926495 5.041584)

131: 1118.91 54.359897 (0.679510 7.175485 -1.552606)

132: 1130.55 9.373180 (-2.518745 -1.628994 0.612765)

133: 1148.68 676.828631 (18.912711 15.270711 9.270566)

134: 1155.67 123.364964 (-9.796465 -1.316641 -5.065639)

135: 1162.52 37.118749 (-4.766069 -3.599513 -1.202848)

136: 1167.05 46.026223 (6.259383 0.675852 2.527761)

137: 1206.39 19.716090 (2.667457 0.603141 3.498140)

138: 1223.46 0.641213 (0.496801 0.479181 0.405940)

139: 1227.48 26.344525 (-1.790595 -4.796669 -0.360914)

140: 1236.56 45.551736 (4.154560 4.087784 3.403144)

141: 1245.55 98.500626 (7.212951 4.999196 4.634869)

142: 1246.84 59.124253 (2.093206 -7.345576 0.886145)

143: 1261.67 76.508829 (6.227384 -4.587488 4.084539)

144: 1266.49 25.132082 (-3.923499 1.994247 -2.400254)

145: 1267.77 18.973649 (0.678756 -4.236283 -0.752891)

146: 1269.41 50.961622 (-4.908221 -3.334875 -3.968576)

147: 1288.63 239.555992 (1.035555 15.400227 1.147439)

148: 1293.72 9.351465 (-0.168507 -2.852924 -1.088070)

149: 1302.35 65.416277 (4.291158 6.847620 0.335174)

150: 1319.24 219.818561 (-10.742003 -7.622499 -6.806280)

151: 1328.56 70.682005 (4.097390 6.673128 3.059864)

152: 1333.61 65.453178 (3.897092 6.794037 2.026553)

153: 1335.33 35.400183 (-1.295566 5.459213 -1.979566)

154: 1339.32 87.984422 (2.195642 -9.046707 -1.149203)

155: 1345.45 181.112566 (4.260839 12.489593 2.639674)

156: 1349.43 236.067652 (-9.897120 -11.639078 -1.626816)

157: 1356.98 60.927988 (3.176412 -4.544463 5.494201)

158: 1360.26 45.664555 (2.875496 -6.113138 0.160073)

159: 1361.04 20.445838 (3.325112 3.035345 0.419701)

160: 1362.34 32.471328 (0.932971 -0.373658 -5.609035)

161: 1364.55 31.945949 (2.581939 -4.286781 -2.627366)

162: 1370.07 5.491564 (-0.364211 -1.446440 -1.807408)

163: 1376.67 15.536288 (-3.205424 -1.672676 -1.569617)

164: 1377.06 127.180480 (-8.315009 -3.983026 -6.494352)

165: 1381.11 19.905921 (0.865826 0.412254 -4.357329)

166: 1387.02 52.512970 (-3.169561 -6.486601 -0.625191)

167: 1387.28 41.933897 (0.003114 5.531170 3.367498)

168: 1388.63 80.472387 (-6.416709 -2.818024 -5.599730)

169: 1394.25 12.450099 (1.164748 -3.114764 -1.179707)

170: 1396.66 24.112205 (2.716261 4.001007 0.852100)

171: 1398.46 23.002485 (-0.795643 4.568690 1.223318)

172: 1408.68 2.589301 (-0.567989 0.345004 -1.465490)

173: 1415.09 39.102397 (-3.960173 -0.653250 4.795070)

174: 1416.80 107.939302 (-0.069477 9.462661 4.288651)

175: 1419.46 102.177840 (-6.852659 -6.907533 -2.739507)

176: 1422.75 244.388041 (9.643609 10.055507 7.090530)

177: 1457.39 1811.363445 (2.213709 -42.502430 -0.079728)

178: 1486.25 14.120286 (-1.918741 1.826156 -2.665309)

179: 1498.96 394.288642 (-18.123477 -4.690170 -6.620463)

180: 1510.80 20.440366 (-2.441121 3.770809 -0.512142)

181: 1518.12 450.975204 (14.789397 12.887854 8.133399)

182: 1528.46 120.896774 (9.125684 -1.508740 5.944945)

183: 1572.65 74.113178 (-6.983813 -2.927126 -4.095298)

184: 1576.92 286.772353 (-16.022761 -3.490758 -4.225883)

185: 1587.57 488.201602 (5.050368 21.236411 3.422022)

186: 1595.90 27.391120 (4.411723 1.783006 2.179154)

187: 1608.74 116.744033 (7.618251 -6.072609 4.672227)

188: 1619.14 41.370598 (5.004652 3.734442 1.542076)

189: 1622.91 203.821079 (12.951781 0.640765 5.971755)

190: 1672.85 66.378846 (7.402614 0.867309 3.290581)

191: 1756.57 408.786026 (-15.925576 4.025301 11.788088)

192: 1758.48 409.950134 (-11.998164 -7.285100 14.591830)

193: 2958.23 13.229717 (-3.065553 -1.897465 -0.481383)

194: 2962.78 30.537718 (3.919546 3.685989 1.260303)

195: 2964.54 22.531870 (-4.027092 1.500619 -2.015576)

196: 2964.82 28.178563 (3.730877 -3.295335 1.843878)

197: 2969.00 13.461114 (3.279614 0.158447 1.637114)

198: 2972.65 43.739563 (5.710006 3.047121 1.360314)

199: 2984.20 16.782726 (0.915203 3.989615 -0.167637)

200: 2985.72 18.265366 (3.720594 -1.254838 1.687580)

201: 2998.76 4.244435 (-0.941770 0.501065 1.762509)

202: 3008.13 7.544476 (0.631918 0.928604 -2.506562)

203: 3031.42 4.185368 (0.113257 -0.803055 -1.878202)

204: 3037.58 9.804052 (2.737002 -0.678063 -1.361287)

205: 3039.87 4.317976 (-1.830988 0.329987 0.925509)

206: 3040.62 13.071740 (3.224465 0.580965 -1.528739)

207: 3041.40 4.808387 (1.485824 0.438266 -1.551978)

208: 3045.83 7.098063 (1.594519 0.862104 -1.952524)

209: 3074.08 28.094526 (4.908362 -1.492002 1.332833)

210: 3076.49 29.918805 (-4.518632 -1.354464 -2.768789)

211: 3077.74 19.454539 (3.629931 1.462396 2.034586)

212: 3082.60 34.192239 (5.138940 2.537058 1.160547)

213: 3092.67 3.240507 (-1.643737 0.507705 -0.529974)

214: 3096.81 145.641461 (0.182562 -12.043619 -0.747911)

215: 3112.93 10.040169 (2.841288 -1.393206 0.161944)

216: 3117.90 9.644083 (-0.880956 -2.902994 0.663795)

217: 3148.31 8.392506 (2.499732 1.463821 0.032809)

218: 3150.11 1.705946 (-0.289292 -1.272827 -0.046554)

219: 3159.74 0.355523 (-0.407750 0.399379 -0.172511)

220: 3160.35 0.282614 (0.036960 -0.526468 0.063872)

221: 3176.17 7.856610 (-2.631902 0.029864 -0.963749)

222: 3200.12 4.297799 (1.603269 1.205205 0.524222)

223: 3589.59 137.823165 (5.894415 4.996890 8.837994)

224: 3590.08 126.835698 (3.197527 5.803096 9.106898)

ESM Table S8IR frequencies forFe(III)PPIX-L1

The first frequency considered to be a vibration is 12

The total number of vibrations considered is 297

Mode freq (cm**-1) T**2 TX TY TZ

------

12: 37.44 0.385506 ( 0.445353 -0.418336 -0.110278)

13: 42.38 1.370545 ( -0.503654 0.722228 0.771533)

14: 45.32 0.468697 ( 0.287028 -0.433782 0.445135)

15: 48.00 0.723667 ( 0.067721 0.704634 -0.471775)

16: 51.74 4.127001 ( -1.877327 0.185566 0.753797)

17: 54.36 0.209095 ( 0.348735 -0.280842 -0.092770)

18: 60.69 2.605142 ( 0.371838 -0.010002 -1.570598)

19: 67.34 2.997266 ( -1.270011 -1.143884 0.275443)

20: 71.87 2.734854 ( -1.530542 0.288444 0.555962)

21: 78.23 1.687778 ( -0.349105 -0.591430 -1.102776)

22: 80.35 2.637773 ( 0.635718 -0.139146 1.488044)

23: 84.98 3.387588 ( 1.362539 -0.274527 -1.206528)

24: 86.92 0.927004 ( -0.171741 -0.424689 0.846846)

25: 89.75 2.135937 ( 0.359582 -1.394453 -0.249274)

26: 91.53 4.408424 ( 0.016576 0.783367 -1.947944)

27: 95.54 5.782037 ( 0.516396 2.160469 -0.920730)

28: 103.54 0.350004 ( 0.329725 0.490793 0.020178)

29: 108.89 2.961951 ( -1.260595 0.712154 0.930424)

30: 112.36 3.774006 ( 1.721129 -0.887588 -0.154625)

31: 121.47 4.096233 ( -0.567361 1.650945 -1.024068)

32: 125.86 1.234332 ( -0.134404 1.096506 0.118082)

33: 128.00 13.141727 ( 3.528928 0.576752 -0.596448)

34: 130.95 0.787979 ( -0.276450 0.670849 0.511387)

35: 138.44 3.731197 ( -0.447026 0.002776 1.879190)

36: 145.77 5.731323 ( 1.070070 1.660230 1.352741)

37: 149.14 4.021195 ( 0.477735 1.922560 0.311006)

38: 155.23 2.264960 ( 1.110108 -1.001983 -0.169266)

39: 158.61 1.473880 ( 0.249970 -0.609780 -1.019589)

40: 168.77 2.493597 ( -1.494044 -0.103548 0.500708)

41: 171.58 0.528214 ( 0.416652 -0.165208 -0.572120)

42: 176.74 5.234149 ( -2.031866 0.119301 -1.044719)

43: 182.60 5.818975 ( 0.732565 -1.518065 -1.725630)

44: 185.32 1.543525 ( -0.051417 -0.608422 -1.081991)

45: 187.82 0.232514 ( 0.464272 0.085110 -0.098598)

46: 191.92 0.336143 ( -0.292961 -0.458140 0.201059)

47: 200.43 21.372187 ( 0.526329 3.394134 3.094353)

48: 201.98 1.801616 ( 0.746015 -0.633734 -0.918400)

49: 210.48 0.870607 ( 0.814931 -0.421714 -0.169267)

50: 224.23 1.052818 ( -0.351669 -0.718337 -0.642759)

51: 225.89 2.452554 ( -0.954610 -1.194614 -0.337891)

52: 229.86 0.308939 ( 0.248094 0.143306 0.476290)

53: 247.89 2.174007 ( 0.003376 1.264023 0.759106)

54: 251.78 0.148930 ( -0.319628 -0.101869 0.190763)

55: 262.17 0.570187 ( 0.145531 0.041885 -0.739765)

56: 265.70 0.562989 ( 0.044621 0.569162 -0.486880)

57: 268.10 3.547367 ( -0.871972 0.238149 -1.652367)

58: 278.85 2.181271 ( 0.351816 -1.432926 0.064953)

59: 289.22 20.764372 ( -0.872437 -3.731124 -2.466158)

60: 295.02 0.641185 ( 0.109070 0.788513 0.086811)

61: 303.22 3.922346 ( 1.553507 -1.077337 0.590176)

62: 305.37 2.398881 ( -0.065246 0.033766 1.547089)

63: 318.40 2.067176 ( 1.189942 0.792206 -0.153696)

64: 321.32 12.649591 ( -0.956993 1.602891 -3.027292)

65: 322.24 2.198701 ( 0.020927 1.464551 -0.230985)

66: 325.12 11.886016 ( -0.277717 0.480816 3.402603)

67: 328.29 11.815894 ( -2.430902 -2.340338 0.655308)

68: 333.32 2.162361 ( 1.151992 0.727890 0.552676)

69: 336.73 4.902603 ( 2.195145 -0.173929 -0.231716)

70: 340.57 7.547070 ( 2.742355 -0.060857 0.151177)

71: 346.22 36.145790 ( 5.771525 1.590663 0.552343)

72: 366.30 1.344111 ( -0.986668 -0.064704 0.605319)

73: 385.92 14.542990 ( 3.750577 0.052774 -0.688026)

74: 391.38 4.762432 ( 1.847146 -0.607946 -0.990397)

75: 398.36 14.748584 ( 1.410176 0.401335 -3.549495)

76: 407.10 2.912139 ( -1.572760 -0.414743 -0.516289)

77: 413.62 1.623337 ( 0.498270 -0.606938 1.003339)

78: 415.34 14.886085 ( 1.657622 2.969216 1.822671)

79: 420.51 0.746680 ( -0.514553 -0.463295 -0.516984)

80: 424.57 17.133155 ( -2.171757 -0.221496 -3.516755)

81: 427.61 2.238006 ( -0.468819 -0.947140 1.058840)

82: 442.71 41.294146 ( -0.786458 6.221735 -1.402012)

83: 472.77 0.858341 ( 0.416848 0.676638 -0.476171)

84: 480.20 2.557735 ( -0.249610 1.293884 -0.906252)

85: 484.32 36.492880 ( -4.975449 2.164102 -2.656021)

86: 497.14 258.622292 ( 13.299872 -8.325487 3.524481)

87: 498.30 2.038984 ( -0.386661 -0.310240 -1.339115)

88: 509.01 17.212624 ( 0.392068 -3.004512 2.834046)

89: 515.63 11.293457 ( 1.387459 -0.846247 -2.941476)

90: 529.92 5.952942 ( 1.070776 0.763450 2.055122)

91: 537.70 13.593198 ( 2.603544 -2.231587 1.354539)

92: 555.30 43.931220 ( 5.663969 -2.774516 2.037827)

93: 557.33 37.678141 ( 5.301557 0.356540 3.073193)

94: 563.33 44.688914 ( -1.847287 5.167650 -3.817308)

95: 572.18 27.496766 ( 3.010478 -3.587773 2.358320)

96: 575.29 24.641053 ( -0.926691 3.001832 3.843345)

97: 580.12 21.764328 ( 2.340140 -3.673462 -1.671451)

98: 582.36 1.452992 ( 0.726948 -0.160010 -0.948122)

99: 597.42 10.568322 ( 3.038688 0.637166 -0.963698)

100: 599.34 34.354396 ( 0.878611 3.867600 4.315566)

101: 618.29 70.705224 ( 0.688725 2.818141 7.892336)

102: 625.75 65.117679 ( 7.674713 2.432468 0.547318)

103: 627.60 74.524936 ( 7.968385 3.294198 -0.421947)

104: 629.21 14.275940 ( 2.450079 0.006918 -2.876283)

105: 632.38 75.153413 ( 0.753662 -2.089191 -8.379779)

106: 640.68 10.009852 ( -1.531914 -2.766070 0.109327)

107: 654.42 10.123687 ( 0.456876 2.371299 -2.071688)

108: 674.39 6.611001 ( -1.122185 0.471519 2.264812)

109: 686.67 100.028888 ( -6.947747 -6.276287 -3.516521)

110: 691.15 4.865729 ( -0.885497 1.875148 0.751961)

111: 692.97 12.310532 ( 1.568653 2.326765 2.106187)

112: 698.70 28.273510 ( 1.802712 -5.001984 0.062389)

113: 705.25 77.913105 ( -4.181893 4.304853 6.472489)

114: 707.16 110.213664 ( 6.378688 0.307168 -8.332566)

115: 707.43 60.450595 ( 5.067296 5.044396 3.054042)

116: 710.88 35.261867 ( -2.687973 -4.313799 -3.070473)

117: 716.70 55.810862 ( 7.329659 -0.660066 -1.285020)

118: 720.86 67.708611 ( 1.593556 -3.497494 7.275763)

119: 723.32 41.421655 ( 2.789144 -5.067938 2.821051)

120: 727.53 11.919602 ( 1.072660 -0.631145 -3.220351)

121: 730.16 25.326976 ( -1.879522 -4.215246 -2.006508)

122: 736.92 105.844839 ( 9.489054 -2.019154 3.424281)

123: 739.81 63.941178 ( 6.839289 -3.981079 -1.147307)

124: 742.69 18.465332 ( -3.958749 -0.036395 -1.671022)

125: 749.88 16.209582 ( -0.562723 0.442499 -3.961959)

126: 756.26 4.769372 ( 1.896519 0.008150 1.082830)

127: 759.89 5.773676 ( 1.991122 -0.243581 1.322792)

128: 778.29 29.317222 ( -0.816034 5.073882 -1.705001)

129: 782.40 33.515896 ( -1.783901 1.198464 5.375619)

130: 792.26 10.151473 ( -1.906066 2.093348 1.461601)

131: 803.69 16.095430 ( -3.529212 1.326756 -1.371061)

132: 807.78 14.231899 ( 1.698323 -0.593726 3.315884)

133: 816.07 11.091340 ( 0.212742 0.557905 3.276404)

134: 818.68 3.165209 ( -1.315491 -1.063634 -0.550794)

135: 831.26 55.585445 ( 2.996135 -5.817116 3.573482)

136: 854.48 39.703525 ( -6.007934 0.701247 -1.765363)

137: 859.15 24.949955 ( -4.279448 -0.529030 -2.521192)

138: 861.37 7.496808 ( 2.587037 -0.110789 -0.889818)

139: 870.86 29.889460 ( -4.911769 -1.902596 1.464279)

140: 881.59 61.287770 ( 6.863556 -2.480867 2.832784)

141: 897.09 50.933655 ( 4.039307 0.064816 5.883320)

142: 907.98 37.322479 ( 2.260698 4.585061 -3.344987)

143: 912.72 7.643978 ( 0.558427 2.311062 1.411074)

144: 924.47 7.209818 ( 0.377968 1.094909 -2.422423)

145: 938.37 39.579738 ( 0.566412 -0.104653 -6.264819)

146: 941.62 13.772423 ( -0.593276 0.495627 3.629711)

147: 943.07 29.419287 ( 1.171730 2.773656 -4.511449)

148: 946.62 55.114732 ( -1.627069 6.012409 4.039593)

149: 949.19 42.908236 ( -0.023947 6.514256 0.687116)

150: 962.76 1.090427 ( -0.402267 0.679900 0.682894)

151: 968.37 38.493245 ( 0.641664 2.574154 -5.608498)

152: 977.31 7.722297 ( 1.293971 0.612446 -2.381774)

153: 979.88 2.810732 ( 0.290103 -0.617198 1.531548)

154: 981.98 68.866830 ( -1.530580 -4.411423 -6.860284)

155: 983.99 13.218840 ( 2.632563 -2.402699 0.717977)

156: 985.17 3.807850 ( -1.818188 -0.696891 0.127997)

157: 988.23 12.685500 ( -0.173534 -3.404595 -1.031561)

158: 989.23 19.362490 ( -4.084580 1.601766 0.336216)

159: 990.76 6.509234 ( -2.153236 1.312704 -0.386804)

160: 991.50 11.310421 ( -1.192020 2.696054 1.618890)

161: 995.70 17.896454 ( 0.035937 0.465035 -4.204629)

162: 998.17 7.075421 ( 1.007490 -1.266923 -2.110756)

163: 1000.19 8.319510 ( 1.266024 0.996221 2.392538)

164: 1001.99 44.048886 ( -0.777384 5.530118 -3.586412)

165: 1025.19 21.295575 ( 0.633665 -1.909264 4.153162)

166: 1029.28 121.513461 ( -7.103602 -8.196633 -1.966595)

167: 1031.74 18.419736 ( 3.126051 -1.655231 -2.430586)

168: 1033.35 29.002996 ( -3.071186 -2.712840 -3.494469)

169: 1055.33 33.740841 ( 2.360766 4.455711 -2.883447)

170: 1081.09 143.960712 ( -2.980883 4.477460 10.725083)

171: 1084.66 6.558876 ( 0.292344 2.255157 1.177997)

172: 1101.44 52.661539 ( -3.653213 -4.276640 -4.585403)

173: 1104.16 35.233607 ( -4.501282 -2.847968 -2.619379)

174: 1108.44 40.675461 ( -1.988179 -5.824257 1.673510)

175: 1110.38 33.001350 ( 1.986762 -2.865951 -4.565134)

176: 1110.95 254.371250 ( -5.833365 8.964733 -11.831173)

177: 1115.24 72.942498 ( 1.162553 -1.989120 8.224012)

178: 1121.75 103.133138 ( -1.532803 -2.370195 9.755297)

179: 1123.83 0.723555 ( -0.400486 0.606100 -0.442501)

180: 1126.52 84.195142 ( 3.607687 5.363316 -6.512647)

181: 1140.11 35.451956 ( 3.218162 -3.931134 -3.105089)

182: 1143.97 32.144344 ( 0.806134 -4.901938 2.732306)

183: 1158.10 147.040638 ( 5.236419 9.931728 4.580539)

184: 1158.96 2.291087 ( -0.090156 -1.470019 0.349289)

185: 1159.13 2.810460 ( 1.317645 -0.773990 -0.689356)

186: 1169.91 29.459434 ( -4.447569 1.541004 -2.702568)

187: 1173.40 31.020418 ( 5.333162 1.094024 1.175120)

188: 1181.30 71.083159 ( 1.695920 -7.247012 3.960787)

189: 1186.22 58.525526 ( -2.775974 4.404044 -5.605702)

190: 1191.22 43.743400 ( -1.439987 -6.385792 0.944191)

191: 1237.10 24.457243 ( -0.088034 -4.315572 -2.413571)

192: 1249.48 29.533252 ( 2.050680 3.712327 -3.398028)

193: 1253.38 133.727363 ( 0.832008 -7.118910 -9.075034)

194: 1266.43 16.373689 ( 1.535109 3.347665 1.676386)

195: 1268.33 135.966057 ( -4.606729 -8.966070 -5.861203)

196: 1270.93 15.914172 ( 1.042453 -1.216994 3.653271)

197: 1277.60 88.514293 ( -2.143589 -5.915256 -6.994931)

198: 1278.36 604.517616 ( 10.401489 18.348204 12.636062)

199: 1281.73 21.011774 ( 0.007595 -4.041239 -2.163354)

200: 1286.36 15.069524 ( 1.087749 2.110146 3.071418)

201: 1287.32 54.159275 ( -1.913570 -4.713662 -5.317793)

202: 1290.00 21.013544 ( 0.865567 0.653260 -4.453941)

203: 1296.45 51.788141 ( 1.550048 -7.020946 -0.302995)

204: 1321.99 22.649719 ( 1.491646 4.428242 0.902986)

205: 1326.57 128.868705 ( -5.278447 -4.102334 -9.174833)

206: 1329.12 0.835544 ( -0.789141 0.428296 -0.171357)

207: 1330.87 1.910428 ( -0.330901 -0.331425 1.300419)

208: 1333.62 10.812803 ( 0.167804 -2.432102 2.206700)

209: 1339.90 20.805943 ( -0.883569 -3.302725 -3.019479)

210: 1347.00 67.196077 ( 2.557790 -1.163105 7.700712)

211: 1349.04 23.384317 ( -2.519516 -3.737395 -1.751638)

212: 1350.64 83.157707 ( -6.921611 2.802140 -5.234216)

213: 1355.52 43.932540 ( 0.176914 -6.625720 -0.032718)

214: 1358.56 22.871567 ( -0.528193 4.753118 -0.021190)

215: 1360.50 7.975063 ( 2.665671 -0.553718 0.750104)

216: 1362.16 23.430840 ( 2.445184 -3.798960 1.737763)

217: 1364.82 70.096803 ( 2.249982 8.052344 -0.440614)

218: 1367.35 24.052013 ( -0.113223 -4.900831 0.145092)

219: 1377.46 143.300842 ( -9.222993 -4.358863 -6.263988)

220: 1383.53 9.916756 ( -1.854084 2.470976 0.611068)

221: 1384.04 20.736768 ( 4.480033 -0.742770 0.338184)

222: 1386.28 32.679655 ( 5.252503 1.742797 -1.433013)

223: 1388.31 8.811876 ( 1.992962 2.113829 -0.609675)

224: 1389.23 27.635050 ( 2.917162 -3.552684 -2.550226)

225: 1389.84 29.076795 ( -3.519151 2.883976 -2.893968)

226: 1392.05 10.131617 ( -1.109570 1.774735 -2.398080)

227: 1394.01 43.319229 ( -1.689294 6.309382 -0.810686)

228: 1396.82 3.505648 ( 0.788149 -1.433800 0.910322)

229: 1397.56 10.020909 ( 1.856844 2.348639 -1.028072)

230: 1398.63 26.705007 ( 0.946861 -4.676016 1.985784)

231: 1401.81 14.460901 ( 2.367659 2.942090 -0.446322)

232: 1402.66 18.099828 ( 3.081441 -1.861197 2.267267)

233: 1406.73 83.962295 ( 4.071201 2.493827 -7.821026)

234: 1409.60 15.183282 ( 1.143317 3.519205 1.221188)

235: 1410.96 99.483221 ( -1.915297 -6.537922 -7.284945)

236: 1413.74 8.595247 ( 1.205389 2.493706 0.961099)

237: 1417.78 50.732490 ( 1.961381 -4.382223 -5.261330)

238: 1419.56 53.318414 ( 1.688714 -0.604450 7.078227)

239: 1422.79 33.711919 ( 4.282384 3.261551 -2.176096)

240: 1426.46 1.175135 ( 0.678460 0.248729 0.808061)

241: 1431.78 4.970211 ( -1.112210 -1.861713 -0.516937)

242: 1490.06 11.058150 ( -1.352372 -1.864272 2.398694)

243: 1502.95 220.191701 ( -5.578335 -10.743037 -8.582601)

244: 1505.11 4.470582 ( 0.456938 0.370819 -2.030833)

245: 1507.98 31.969266 ( -1.313269 -4.546386 3.094345)

246: 1523.65 41.285030 ( -6.247129 -1.488475 -0.207023)

247: 1536.88 4.965939 ( 0.162909 0.678458 2.116387)

248: 1547.80 23.573245 ( -0.980140 -0.903415 4.668663)

249: 1564.16 34.376064 ( -0.476263 4.963120 3.084911)

250: 1565.39 43.174732 ( -0.591078 4.822269 4.423922)

251: 1577.45 25.883726 ( -1.904905 -0.785791 4.651623)

252: 1596.96 10.113512 ( 1.716562 1.534009 2.194024)

253: 1608.43 1.734752 ( 0.827272 1.024867 0.004398)

254: 1611.01 1121.140915 ( 10.505161 31.766123 -1.302269)

255: 1617.67 429.665373 ( -0.368586 8.325575 -18.979313)

256: 1624.77 45.147810 ( -0.299688 4.313931 5.142762)

257: 1626.86 24.370778 ( 0.560246 -4.859867 0.662267)

258: 1631.22 12.503575 ( 0.194623 2.720126 -2.250914)

259: 1635.74 38.041287 ( -2.087049 3.092831 4.911202)

260: 1642.70 2.100530 ( 1.380349 -0.192013 0.397867)

261: 1684.34 2.787490 ( -0.035890 0.624810 1.547842)

262: 1710.08 554.865158 (-15.766956 -1.679817 17.419715)

263: 1740.13 432.222467 ( 7.008187 15.223049 12.303112)

264: 2946.07 90.103335 ( -6.618875 -6.663956 -1.373141)

265: 2954.80 37.106276 ( 1.157005 5.972969 0.302088)

266: 2958.33 58.571489 ( -0.778799 7.574557 0.768798)

267: 2959.79 51.784531 ( -1.719389 -0.350120 6.978943)

268: 2960.82 37.004912 ( -1.785300 -5.726353 1.013163)

269: 2964.19 11.736541 ( 1.470539 2.644361 -1.606676)

270: 2983.89 40.816835 ( -2.493640 2.047898 -5.514047)

271: 2986.14 14.032781 ( -1.173840 3.199283 1.555464)

272: 3004.11 15.952437 ( 2.471828 1.390380 -2.812356)

273: 3015.79 627.203562 ( -4.620244 19.704576 14.750817)

274: 3023.10 6.566274 ( -2.271393 0.786558 -0.887905)

275: 3028.42 9.469168 ( 3.068763 -0.227707 -0.002979)

276: 3031.05 6.823819 ( 2.315166 0.572316 1.065964)

277: 3031.43 9.364749 ( -2.627460 1.488868 -0.494447)

278: 3032.63 30.797339 ( 3.787604 -2.882852 2.853167)

279: 3037.84 15.154073 ( -1.233834 -3.318322 1.618784)

280: 3039.31 4.528218 ( -1.976888 -0.013309 0.787371)

281: 3041.70 9.496260 ( -1.890737 0.983529 2.225768)

282: 3064.67 34.815277 ( 1.918321 3.446234 -4.388484)

283: 3065.82 75.691791 ( 1.132190 -5.319099 -6.790959)

284: 3068.59 19.064382 ( 1.299499 2.921601 -2.973202)

285: 3068.67 28.561344 ( 1.296455 1.977028 -4.792902)

286: 3070.83 13.642838 ( 0.487387 -3.605373 0.637634)

287: 3072.83 8.045482 ( -0.863282 -1.937939 -1.882716)

288: 3073.23 3.335535 ( 0.180499 -1.046919 1.485569)

289: 3073.98 65.859321 ( -3.064013 -0.345521 7.506781)

290: 3084.45 8.709587 ( -0.737389 0.501567 2.813232)

291: 3095.03 5.116310 ( 0.273857 -0.085492 2.243658)

292: 3096.00 30.791266 ( 0.123595 4.154886 3.675991)

293: 3097.57 2014.316623 ( -6.645238 33.407068 29.225421)

294: 3102.63 14.348438 ( 3.614680 -0.112641 -1.126872)

295: 3123.96 4.321830 ( 0.906674 1.188916 -1.444386)

296: 3125.19 6.836035 ( -1.163844 1.600875 1.708420)

297: 3139.50 0.601195 ( 0.318214 0.681929 -0.186837)

298: 3145.12 10.644749 ( 1.141444 -0.110625 -3.054442)

299: 3146.25 15.988003 ( 0.886298 -0.443844 -3.873691)

300: 3148.70 12.106850 ( -0.864365 -3.238336 -0.934294)

301: 3154.10 0.518140 ( -0.052814 -0.294112 0.654865)

302: 3171.11 14.609727 ( -0.829024 -3.073923 2.115052)

303: 3183.91 4.046271 ( -1.078565 -1.160889 1.239074)

304: 3211.86 744.706382 ( -1.904958 0.457296 27.218898)

305: 3287.22 350.361761 ( -5.167696 -12.847399 -12.593689)

306: 3557.91 299.974572 ( -2.690479 -17.097528 -0.640637)

307: 3582.05 109.435939 ( -4.937020 8.995032 -2.037444)

308: 3591.92 137.600061 ( 5.619771 -9.247941 4.527010)

ESM Table S9IR frequencies forFe(III)PPIX-L2[in which L2 is N2-bound to Fe(III)]

The first frequency considered to be a vibration is 10

The total number of vibrations considered is 299

Mode freq (cm**-1) T**2 TX TY TZ

------

10: 35.04 0.317901 ( -0.349552 0.393080 0.202983)

11: 42.75 1.452950 ( -0.578557 -0.547695 0.904573)

12: 46.21 0.925208 ( 0.035414 0.768087 0.577925)

13: 49.09 1.216654 ( -0.343725 0.028372 1.047713)

14: 54.87 4.057328 ( 1.107815 -1.676913 0.134301)

15: 57.58 0.536812 ( 0.276920 -0.256743 0.627861)

16: 59.63 0.820780 ( -0.614828 -0.629315 -0.216169)

17: 65.05 2.913555 ( 0.792471 -1.309998 0.754619)

18: 67.50 1.738666 ( -1.171855 0.152494 0.584951)

19: 73.14 0.859559 ( 0.462521 -0.803173 0.023373)

20: 76.26 0.088144 ( -0.258569 -0.121598 -0.080622)

21: 80.60 1.606415 ( -0.355439 0.499486 -1.109321)

22: 83.72 1.890851 ( 0.890118 -0.799680 0.677535)

23: 88.94 0.741942 ( -0.754929 -0.179968 -0.373678)

24: 89.85 1.076344 ( -0.344250 0.030470 -0.978216)

25: 92.52 0.752512 ( -0.505580 0.701063 -0.073561)

26: 100.62 3.024878 ( -0.675396 -1.456665 -0.668465)

27: 101.74 1.234402 ( 0.929962 0.437586 0.422010)

28: 108.75 4.831153 ( -1.765304 0.747818 1.075000)

29: 110.90 2.660273 ( -1.461559 0.681249 -0.244984)

30: 113.78 1.905245 ( 0.941366 0.147799 0.998614)

31: 116.17 3.104443 ( -1.002209 -0.765992 -1.230153)

32: 123.44 2.426025 ( 0.987646 -0.730919 -0.957256)

33: 131.92 2.362605 ( -1.052241 -0.429509 -1.034851)

34: 140.78 0.839466 ( 0.486745 -0.742746 -0.225551)

35: 147.38 2.806861 ( 0.726866 -1.450980 -0.416154)

36: 153.54 6.567246 ( -1.583677 -0.335575 1.986606)

37: 156.46 3.487557 ( -0.744890 1.530807 -0.767676)

38: 163.82 1.376551 ( 0.808689 -0.849703 0.024039)

39: 167.25 0.194638 ( 0.163661 -0.242674 -0.330094)

40: 168.71 0.247194 ( -0.115114 0.475823 0.086808)

41: 180.84 2.694719 ( 1.533567 -0.548287 -0.205604)

42: 185.65 1.879680 ( -0.799937 1.113139 0.026492)

43: 189.63 0.760493 ( 0.239423 0.397948 0.738111)

44: 191.79 1.867751 ( 0.775546 -0.426047 -1.041520)

45: 204.27 11.461597 ( -1.637022 2.564756 -1.484515)

46: 210.41 2.834895 ( 1.670204 -0.209947 -0.035171)

47: 212.01 1.987143 ( -0.939304 0.786968 -0.696802)

48: 220.66 7.371559 ( -0.451665 -2.581072 -0.711072)

49: 222.34 1.501446 ( 1.032491 0.553275 -0.359579)

50: 224.34 1.503890 ( 0.013062 -0.816210 -0.915161)

51: 235.03 3.365794 ( 0.026655 0.381741 1.794257)

52: 237.11 5.250762 ( 0.623574 -1.877727 -1.155881)

53: 247.66 1.159332 ( 0.390097 0.492804 -0.874242)

54: 256.92 0.624151 ( -0.428783 -0.437702 -0.498711)

55: 266.79 3.618876 ( 1.005519 0.725801 -1.442574)

56: 269.34 1.547129 ( 1.110931 -0.352460 0.434435)

57: 277.80 1.194594 ( -0.556318 -0.322423 0.883825)

58: 281.62 6.708806 ( -0.404611 2.554166 0.146065)

59: 288.75 13.406006 ( 0.686651 -0.194649 -3.591188)

60: 296.73 8.019794 ( -1.273618 -1.754797 1.821642)

61: 298.63 10.249380 ( 1.147834 2.346641 -1.850712)

62: 301.85 12.441365 ( -1.456433 -1.041309 3.039053)

63: 308.53 10.455322 ( -0.402501 3.203777 -0.170671)

64: 318.83 7.514143 ( -0.438189 2.461597 1.123687)

65: 324.59 7.537329 ( -1.078396 2.517167 -0.195608)

66: 331.90 7.477642 ( 2.448909 0.218469 -1.196979)

67: 333.20 12.847058 ( -0.182371 1.803212 -3.092285)

68: 334.12 1.985286 ( -1.142025 0.166966 -0.808200)

69: 344.70 2.556183 ( -1.331049 0.340276 0.817743)

70: 354.74 3.912017 ( -0.238607 -0.496875 -1.899526)

71: 361.47 33.234981 ( 0.155769 4.979235 -2.901368)

72: 370.83 38.309648 ( 1.610364 1.959095 -5.646089)

73: 373.14 3.792295 ( -0.716568 0.783732 1.632357)

74: 386.21 14.000872 ( -0.995153 3.580614 -0.435601)

75: 396.12 3.241103 ( 0.443284 -0.981400 -1.442725)

76: 402.13 2.000033 ( -1.231670 0.467660 0.514117)

77: 411.53 61.185438 ( 2.955670 -1.243449 -7.134654)

78: 416.60 1.554083 ( -0.018548 -0.796256 0.959018)

79: 416.92 9.107833 ( -0.250699 1.536806 2.585190)

80: 428.53 1.958348 ( 0.020147 -0.646397 1.241013)

81: 428.89 6.390028 ( -1.345806 2.127246 -0.231647)

82: 461.79 2.245054 ( -0.436162 -0.727783 1.234969)

83: 463.55 14.882569 ( -2.497646 -1.540703 -2.504110)

84: 466.13 6.999861 ( 0.797943 2.350977 -0.914361)

85: 479.63 18.607069 ( 2.918813 1.959347 2.499712)

86: 491.27 42.688941 ( -1.039227 3.811416 5.204042)

87: 497.13 3.063855 ( -1.028939 -1.324679 -0.500366)

88: 504.98 5.088170 ( -0.318646 -1.778127 -1.350888)

89: 509.76 21.825428 ( 4.354016 -1.641578 -0.416171)

90: 518.17 10.108633 ( -0.337132 2.462723 -1.982416)

91: 522.95 60.229422 ( 0.604231 7.708070 0.670812)

92: 537.95 16.761548 ( -0.338823 3.040378 -2.720817)

93: 554.42 24.888092 ( 0.742307 2.650139 -4.160990)

94: 562.12 69.134917 ( 2.596518 7.851529 -0.864004)

95: 568.46 8.457100 ( 0.647452 0.410077 2.805306)

96: 576.28 1.374463 ( 0.003662 -0.598221 1.008257)

97: 578.96 14.913183 ( 2.604874 2.703778 0.904099)

98: 596.81 16.167858 ( -3.532907 -1.814981 0.626315)

99: 599.05 15.130233 ( 3.230061 1.683616 -1.364689)

100: 603.18 53.387276 ( 3.680711 -2.120156 5.945131)

101: 604.74 73.470092 ( -4.717121 -4.618463 -5.467053)

102: 621.47 4.941211 ( 1.122972 -1.528523 -1.159207)

103: 624.92 152.108686 ( -4.619318 4.245860 -10.618063)

104: 628.61 37.024334 ( 2.162094 1.980031 5.331900)

105: 638.94 4.822149 ( -1.750423 1.132005 0.690457)

106: 640.41 75.239375 ( -2.441919 7.213739 4.151912)

107: 646.12 187.488849 ( 3.142533 -1.402832 13.253128)

108: 663.04 78.624952 ( -5.832546 6.612830 0.936398)

109: 671.88 2.589710 ( -1.130234 -1.112919 0.271461)

110: 682.18 1.581406 ( -1.225148 0.252644 -0.128804)

111: 685.58 2.774814 ( -0.001005 -1.536233 0.644051)

112: 692.13 48.317121 ( 3.127030 6.124481 1.014661)

113: 695.33 51.877090 ( 4.018268 -4.273255 4.179702)

114: 703.60 9.697090 ( 0.177842 -0.533715 3.062778)

115: 705.55 87.880178 ( -0.609944 3.082708 -8.832047)

116: 707.46 54.822294 ( -6.053891 -0.311112 4.251576)

117: 711.78 31.879864 ( -0.647413 5.497185 -1.114307)

118: 716.08 19.394683 ( -2.409909 -2.808668 -2.387134)

119: 717.03 92.787874 ( -1.497032 7.919846 -5.274732)

120: 719.47 64.959951 ( 6.555809 3.844406 2.683629)

121: 730.60 19.269465 ( -2.412716 -3.063061 -2.016414)

122: 732.07 7.805931 ( 0.955645 1.353509 -2.249597)

123: 737.03 14.356859 ( 3.580790 -1.147629 0.466634)

124: 739.99 240.904324 ( -2.697873 -1.418320 15.218875)

125: 747.97 3.794618 ( -0.348204 -1.101384 -1.568543)

126: 753.53 5.073225 ( 0.644103 2.157401 -0.063084)

127: 757.05 12.784625 ( -0.887510 -1.252831 3.229143)

128: 779.06 31.950720 ( 0.155736 -5.478185 -1.384182)

129: 788.66 22.225684 ( -3.390727 2.613875 -1.973908)

130: 789.12 8.328077 ( 2.720486 0.914387 -0.301543)

131: 796.46 26.179715 ( -3.601384 -2.372279 -2.753550)

132: 801.28 28.089822 ( 0.797814 3.952846 3.439233)

133: 812.41 5.770665 ( -0.775710 -2.041539 -1.000528)

134: 816.47 9.488275 ( 1.477390 1.112693 2.463231)

135: 823.64 127.463041 ( -3.777078 5.560981 9.070403)

136: 851.73 39.537708 ( 1.122549 1.102174 -6.087923)

137: 855.46 20.704223 ( 2.382731 -1.491389 -3.578068)

138: 858.74 19.972054 ( 1.489630 -1.513659 -3.932161)

139: 861.78 8.661050 ( -0.298805 -1.353375 2.596178)

140: 884.67 80.049672 ( -4.315708 -1.895095 7.604798)

141: 892.00 42.066467 ( -0.133533 -1.474960 6.314517)

142: 898.21 1.609260 ( -1.213980 0.275209 0.244485)

143: 909.18 36.496341 ( -4.985426 -0.209832 -3.405560)

144: 927.01 6.012134 ( 2.195806 0.931525 0.568183)

145: 930.48 44.769428 ( 4.123927 -3.916503 3.524721)

146: 935.08 3.783272 ( 1.332478 -0.637192 -1.265607)

147: 936.71 6.424556 ( -2.326990 0.530098 0.853620)

148: 942.34 35.237181 ( 4.889470 2.772734 1.908457)

149: 945.42 14.579178 ( 1.020297 -3.349629 1.522550)

150: 947.56 64.482402 ( 0.692194 -7.881826 1.371161)

151: 958.35 2.441594 ( 0.057810 1.377243 0.735836)

152: 967.78 107.432926 ( 2.775683 8.298824 -5.555000)

153: 968.97 49.258869 ( 5.291778 -3.197013 3.321907)

154: 975.98 15.548170 ( -1.618749 -1.406850 3.308866)

155: 981.03 41.817663 ( 0.325698 3.263801 -5.573077)

156: 982.75 4.783996 ( -1.241693 -1.799820 0.053317)

157: 984.09 2.874509 ( -0.365494 -1.442778 -0.811982)

158: 988.62 10.477809 ( -0.452522 -3.204708 -0.053678)

159: 989.27 52.866388 ( 3.840501 5.879002 1.885279)

160: 991.97 7.847705 ( 2.271942 0.895839 -1.372392)

161: 994.26 29.145836 ( 3.509206 3.178109 2.594404)

162: 994.75 5.068856 ( 1.438156 -1.669582 0.461583)

163: 999.76 22.168824 ( -3.012128 -3.578720 0.537282)

164: 1000.88 8.509791 ( -2.421275 -0.674878 -1.480459)

165: 1016.92 89.307243 ( -2.628857 -6.755568 6.062892)

166: 1024.25 21.016721 ( 3.639804 0.070615 2.786317)

167: 1027.17 24.284342 ( 3.151779 -3.174472 2.067210)

168: 1032.05 122.739121 ( 3.197870 -10.484919 1.605994)

169: 1042.16 7.757196 ( 1.256680 2.474402 0.235135)

170: 1061.67 120.375390 ( 1.604059 -10.796466 1.112969)

171: 1066.16 64.647478 ( -1.056362 0.785430 7.931877)

172: 1080.01 65.350419 ( -3.764364 6.449665 -3.095448)

173: 1096.63 13.644904 ( -1.510636 2.673683 -2.052876)

174: 1098.10 33.712552 ( 2.862020 0.441983 5.032499)

175: 1102.87 213.523614 ( 6.627149 12.924496 1.600599)

176: 1106.74 6.650689 ( -0.674247 -1.284378 -2.132241)

177: 1112.80 371.643728 ( 13.311590 13.815225 1.893377)

178: 1115.21 35.118504 ( -2.494507 5.336117 -0.649461)

179: 1119.84 0.667288 ( -0.339958 0.659581 -0.341570)

180: 1121.58 210.235152 ( 4.782184 -13.540187 2.007289)

181: 1125.28 67.544882 ( -0.164899 -8.194572 -0.605536)

182: 1129.96 20.033259 ( -0.503957 -1.274988 4.260715)

183: 1143.89 7.144813 ( -1.626234 -1.652090 1.330705)

184: 1151.13 209.047806 ( -0.413104 -14.304311 -2.064907)

185: 1157.77 12.380126 ( 0.151111 3.457579 0.634383)

186: 1159.22 6.546482 ( -1.385646 2.146458 -0.138508)

187: 1165.98 26.159055 ( 5.057500 0.041801 0.760920)

188: 1173.31 1.134998 ( -0.826734 0.670662 0.041495)

189: 1179.16 84.340572 ( 3.364718 8.103886 2.710401)

190: 1181.81 51.610359 ( 2.686799 6.608985 -0.844264)

191: 1217.72 15.946444 ( 2.819452 0.269489 2.815050)

192: 1234.55 3.064343 ( 0.372071 1.690651 -0.260008)

193: 1242.15 27.362357 ( 1.109811 4.929479 1.353112)

194: 1249.18 114.791697 ( 8.195278 -5.835698 3.684255)

195: 1266.12 38.386027 ( 0.127045 5.222526 3.330932)

196: 1266.79 38.295300 ( -2.640472 0.780713 5.541994)

197: 1269.61 27.515672 ( -3.378281 1.473548 -3.732499)

198: 1270.29 73.277520 ( 1.462131 -7.481239 -3.894965)

199: 1274.33 7.759297 ( -1.833105 -2.007718 -0.606704)

200: 1276.31 1069.865191 ( 8.689593 30.805952 -6.734204)

201: 1281.12 23.947714 ( 0.389246 4.737010 1.164878)

202: 1285.45 1.359406 ( 1.047388 0.469304 0.205274)

203: 1289.81 45.009622 ( -0.033587 -5.553270 3.764265)

204: 1292.33 185.238126 ( -4.651882 -3.280302 12.362756)

205: 1308.00 44.948481 ( 6.466892 0.697548 1.625181)

206: 1324.36 55.044455 ( 5.399384 1.784136 4.765287)

207: 1326.16 21.568320 ( 3.388966 2.085471 2.394586)

208: 1329.69 4.892387 ( 1.678789 -1.440030 -0.019156)

209: 1332.46 2.408874 ( -1.093497 1.093889 -0.128626)

210: 1337.52 19.454987 ( 3.133684 -2.257386 2.130544)

211: 1344.07 23.811310 ( -1.416809 4.465406 -1.365324)

212: 1345.42 63.154889 ( -3.806514 -6.974963 -0.123395)

213: 1356.69 67.137279 ( 1.755506 7.728581 -2.079546)

214: 1357.62 21.327225 ( -1.360165 -4.366883 0.638363)

215: 1358.54 33.416177 ( 4.460163 3.466431 1.227593)

216: 1360.65 29.955695 ( 4.828788 -1.396532 2.165226)

217: 1361.37 20.610871 ( -3.062490 3.055943 -1.375950)

218: 1364.77 24.828842 ( 1.066234 1.410258 -4.658665)

219: 1364.98 2.954460 ( 0.514644 1.303739 -0.994920)

220: 1372.14 11.012946 ( 1.716284 2.734372 0.768456)

221: 1378.45 53.426550 ( -0.611990 -7.133236 -1.472739)

222: 1379.24 55.381420 ( -5.498801 -1.711402 -4.713355)

223: 1388.56 10.913737 ( -0.359096 0.035369 3.283829)

224: 1389.15 34.420769 ( 1.905279 -3.311427 -4.452542)

225: 1389.26 3.299834 ( 1.395990 0.157844 -1.151578)

226: 1390.49 77.073461 ( 6.359850 6.024279 0.577783)

227: 1390.65 14.816636 ( 0.825924 -1.432670 -3.475909)

228: 1393.03 9.003480 ( 2.145775 1.215446 1.709333)

229: 1396.21 24.043704 ( 4.575222 1.679675 -0.538279)

230: 1397.67 2.739103 ( 1.415085 0.143844 -0.846137)

231: 1400.45 95.373739 ( -3.827128 -8.089891 -3.909028)

232: 1402.14 40.837129 ( 1.185785 5.034255 3.753308)

233: 1404.03 31.379544 ( -4.336359 2.092647 -2.862929)

234: 1406.33 7.252391 ( -2.078673 -1.137080 1.280061)

235: 1410.82 4.617493 ( 0.201403 0.327929 2.114094)

236: 1413.38 32.269784 ( -0.119455 5.679382 -0.011796)

237: 1417.46 21.318755 ( 3.473971 -0.348079 -3.021444)

238: 1417.91 26.324427 ( 2.452018 4.293756 -1.369559)

239: 1418.81 12.567767 ( 2.719544 -0.667834 -2.173901)

240: 1428.12 29.239349 ( -4.089983 0.896908 -3.421541)

241: 1435.18 51.750381 ( 1.921810 6.563738 2.230330)

242: 1486.94 189.651742 ( 1.119951 -0.074852 13.725591)

243: 1490.00 20.631556 ( -0.859420 0.491952 -4.432938)

244: 1499.77 184.253613 ( 1.331931 13.496823 -0.561552)

245: 1502.88 23.357238 ( 0.274523 -4.626857 1.368968)

246: 1507.29 46.150614 ( 4.178345 4.587709 2.764955)

247: 1537.02 16.441252 ( 3.881627 0.093149 1.168568)

248: 1544.17 10.864072 ( -2.542404 -0.763190 -1.953918)

249: 1555.64 265.633450 ( 2.048789 15.161936 5.617083)

250: 1562.50 2.825496 ( -0.504832 -1.512685 -0.531436)

251: 1578.02 90.466862 ( -3.094717 -8.210047 -3.672155)

252: 1579.93 190.067132 ( -2.628800 11.400579 7.292691)

253: 1592.57 12.274684 ( -1.223846 -3.163219 -0.878029)

254: 1604.94 532.324008 ( 12.366218 -17.597002 8.351417)

255: 1605.88 25.267208 ( -3.812295 2.571728 -2.029736)

256: 1620.46 174.030746 ( -9.936074 -7.308930 -4.678111)

257: 1623.96 58.681467 ( 0.497764 7.637587 -0.317747)

258: 1626.15 38.166851 ( -5.236254 -1.495862 -2.917343)

259: 1633.03 17.793707 ( -3.889639 -0.439632 -1.571985)

260: 1642.32 14.344421 ( -2.107275 -2.779912 -1.475094)

261: 1680.42 0.893075 ( 0.256938 0.218390 -0.882815)

262: 1706.72 718.815457 ( 18.503145 -18.519896 -5.784679)

263: 1759.53 399.983858 ( -8.987917 -9.207425 15.310928)

264: 2540.96 14.405614 ( 3.087300 -1.908323 1.110176)

265: 2952.93 131.879830 ( -3.895771 10.802798 0.048487)

266: 2954.71 54.672880 ( -5.094035 -5.151174 -1.479561)

267: 2958.38 51.212397 ( -3.102050 5.584608 -3.225188)

268: 2960.47 57.333840 ( -6.690197 -1.043938 -3.388997)

269: 2966.44 34.399273 ( 4.289267 -2.757944 2.897448)

270: 2967.68 19.156498 ( 3.338792 -2.660866 -0.963723)

271: 2968.14 36.271424 ( 5.133171 2.804695 1.433758)

272: 2983.34 22.838547 ( 0.938040 4.679773 0.241568)

273: 2992.93 52.438562 ( -5.748971 4.205027 1.306002)

274: 3006.12 27.436678 ( 0.279281 -2.808261 4.412749)

275: 3006.89 15.290076 ( 1.934130 -2.254700 2.542743)

276: 3025.81 7.029295 ( -0.846077 -1.301710 2.149186)

277: 3026.59 9.931235 ( -1.078153 1.431949 2.591977)

278: 3031.37 8.728589 ( -1.912308 -0.476058 2.201144)

279: 3039.10 7.596988 ( -2.120081 0.254558 1.742826)

280: 3041.39 10.224807 ( -2.313301 0.099402 2.205349)

281: 3043.68 24.603770 ( 2.116286 -1.254040 -4.307260)

282: 3044.19 11.523414 ( -2.816044 -0.230021 -1.881595)

283: 3047.07 10.847493 ( -2.859926 0.288906 1.607747)

284: 3061.96 26.441312 ( -4.644784 1.652263 -1.461958)

285: 3068.04 18.335139 ( 3.036975 -2.800884 1.125598)

286: 3068.51 13.347695 ( -2.504805 -0.234178 -2.649303)

287: 3073.36 19.953138 ( 3.995261 0.346969 1.967394)

288: 3074.33 3.412741 ( 1.387590 0.401784 1.151479)

289: 3077.04 10.538690 ( -0.892409 3.035369 0.727207)

290: 3078.80 18.297589 ( 2.688152 -2.564949 2.119544)

291: 3088.82 21.128493 ( 0.294005 -4.410838 1.259588)

292: 3095.23 11.737047 ( 0.095038 -3.360659 -0.658775)

293: 3097.18 14.510452 ( -2.105065 -2.924248 -1.236092)

294: 3113.93 6.554790 ( 0.002156 -2.375307 0.955353)

295: 3126.21 3.745263 ( -1.457017 -1.273065 -0.040895)

296: 3129.18 3.362979 ( -0.693060 1.651104 -0.395603)

297: 3140.86 60.028531 ( 4.138330 -5.471531 3.600708)

298: 3141.24 5.385466 ( 1.684234 -1.357446 0.840335)

299: 3143.89 1848.486748 ( 23.986971 -31.169617 17.365683)

300: 3149.00 1.530637 ( 0.966826 -0.718257 -0.282827)

301: 3149.47 3.237923 ( -0.675149 -1.584349 -0.521474)

302: 3160.63 2.258792 ( 1.286440 0.008084 0.777046)

303: 3164.21 6.346622 ( 1.243095 -1.851352 1.172107)

304: 3171.25 20.123747 ( -4.297976 0.104073 -1.280749)

305: 3187.89 4.167944 ( -1.325530 1.259676 -0.907817)

306: 3455.67 194.962686 ( 2.473083 10.824734 -8.465913)

307: 3584.72 124.167322 ( -7.834494 -7.847794 1.095513)

308: 3589.03 143.824188 ( -5.757179 -4.743231 -9.390465)

ESM Table S10IR frequencies forFe(III)PPIX-L2[in which L2 is S5-bound to Fe(III)]

The first frequency considered to be a vibration is 11

The total number of vibrations considered is 295

Mode freq (cm**-1) T**2 TX TY TZ

------

11: 35.54 0.144415 ( -0.038954 -0.289834 0.242680)

12: 40.47 0.855240 ( -0.144183 -0.529062 0.744678)

13: 44.36 0.628118 ( -0.428171 0.455135 0.487483)

14: 47.38 4.796279 ( 0.094482 1.385897 1.693116)

15: 53.06 2.448020 ( 1.141435 -0.671319 0.833352)

16: 53.43 4.497916 ( -2.104001 0.129531 0.233058)

17: 55.14 0.998619 ( -0.383179 0.471241 0.793552)

18: 61.57 1.172991 ( 0.380186 -0.396188 0.933534)

19: 64.89 2.099369 ( -0.875167 0.407288 1.080541)

20: 74.02 2.370221 ( -0.374991 0.572534 -1.379061)

21: 79.34 0.706189 ( -0.617128 -0.568552 -0.045724)

22: 81.62 0.294645 ( -0.514456 0.164162 0.055053)

23: 84.39 0.242370 ( -0.425385 -0.007379 0.247717)

24: 85.69 3.965748 ( 1.232470 0.284212 -1.538177)

25: 90.20 6.601143 ( -0.961493 0.554065 2.317259)

26: 92.60 4.151624 ( 1.968319 -0.500715 -0.163179)

27: 100.16 0.773007 ( 0.845382 0.132513 0.201933)

28: 106.16 4.289868 ( -0.260017 1.194866 1.671692)

29: 109.70 6.554576 ( -0.013544 -1.773175 -1.846685)

30: 119.91 2.950367 ( -0.692982 -0.109643 1.567840)

31: 124.70 9.067094 ( -1.193862 -2.744999 0.326752)

32: 130.42 4.148055 ( -0.977094 1.774104 0.214231)

33: 132.81 2.301577 ( -0.015983 -1.118971 1.024316)

34: 136.49 7.616975 ( 1.773936 -1.991719 -0.709353)

35: 140.25 4.456415 ( -0.796244 -1.135223 1.591753)

36: 148.01 5.423852 ( 0.782759 1.807445 1.242691)

37: 150.37 0.588602 ( 0.227111 -0.644591 -0.348604)

38: 160.71 1.903652 ( -0.214068 1.336676 -0.266689)

39: 162.93 2.762263 ( -0.223961 1.554942 -0.542456)

40: 170.77 0.380230 ( -0.209655 -0.456493 0.357616)

41: 176.81 6.457459 ( -2.378368 0.858339 0.253137)

42: 184.47 1.001426 ( 0.244329 0.889024 0.389057)

43: 185.88 1.363759 ( -0.697112 0.485254 0.801451)

44: 188.45 0.106012 ( -0.167579 -0.271303 -0.065755)

45: 200.69 2.148524 ( -0.123550 -1.118270 -0.939538)

46: 202.02 1.762529 ( -0.738036 0.530556 0.967648)

47: 208.25 3.058527 ( -0.446167 1.635529 0.429543)

48: 212.27 10.754256 ( -2.798181 1.526794 -0.770285)

49: 224.13 1.568826 ( -0.958943 0.777018 -0.213302)

50: 228.77 0.474268 ( 0.429329 0.211139 -0.495343)

51: 232.16 0.306490 ( -0.365843 -0.035791 -0.413967)

52: 246.28 0.626765 ( -0.724447 0.270358 -0.169847)

53: 250.62 1.917427 ( 0.824942 1.105135 -0.124795)

54: 251.91 0.702676 ( -0.077357 -0.083605 0.830483)

55: 262.11 0.772205 ( 0.057002 -0.651452 0.586998)

56: 267.62 2.071319 ( -0.294296 -1.271479 0.606670)

57: 279.45 1.805321 ( -0.190192 1.307288 -0.245246)

58: 294.82 1.652107 ( 0.474178 0.814787 0.873719)

59: 296.09 4.899346 ( -1.276891 -1.747160 -0.465112)

60: 296.49 15.036641 ( -0.415359 -1.728841 -3.446045)

61: 303.65 5.874277 ( 0.475398 -1.693081 -1.667858)

62: 305.87 1.453310 ( -0.123980 1.059704 -0.561218)

63: 316.23 8.594698 ( 0.108205 -1.642009 2.426272)

64: 319.70 11.391519 ( -0.221451 -1.851643 2.813165)

65: 324.61 1.388835 ( 0.125819 1.116972 0.354088)

66: 326.22 3.216889 ( 0.564864 1.648349 -0.425163)

67: 328.48 5.531715 ( 1.947497 0.159422 -1.309028)

68: 334.25 1.908769 ( 1.358599 -0.098463 -0.230831)

69: 338.79 6.091939 ( -2.026475 1.215993 -0.711827)

70: 340.97 3.685143 ( 0.903938 1.101099 -1.286710)

71: 348.59 61.822128 ( -5.532509 2.080952 -5.184893)

72: 365.27 0.504684 ( 0.411907 0.155464 -0.557538)

73: 385.05 9.352935 ( 1.414644 2.497488 -1.055590)

74: 387.44 1.407761 ( 0.726227 0.911231 0.223638)

75: 395.77 12.156400 ( 0.546552 -0.712770 -3.368923)

76: 408.07 61.642293 ( -3.040298 4.926437 -5.303687)

77: 408.82 101.577882 ( -1.963738 8.832886 -4.438664)

78: 413.55 45.878030 ( 2.881844 -6.051492 0.975939)

79: 419.63 8.490031 ( 1.686862 -1.433199 1.894853)

80: 424.77 7.147084 ( -0.613929 -2.324974 1.168191)

81: 427.71 17.789191 ( -0.343857 3.811523 1.772920)

82: 430.77 97.670677 ( 2.289914 -7.846696 -5.554848)

83: 441.77 144.574974 ( 3.157676 -8.147197 8.259978)

84: 472.99 0.496344 ( -0.288788 -0.408529 0.496034)

85: 479.88 2.962537 ( -0.817813 1.058956 1.082742)

86: 490.36 9.719207 ( -1.674664 -2.287169 -1.297523)

87: 496.62 2.950644 ( -0.478956 1.266076 -1.057495)

88: 498.56 19.939903 ( 1.998233 -3.921047 0.756541)

89: 514.48 9.810942 ( -0.727568 -1.131174 2.828786)

90: 528.50 4.719708 ( 1.043529 0.108553 1.902360)

91: 537.07 38.126078 ( 3.005121 -5.096287 1.767253)

92: 551.31 31.280841 ( 3.115011 1.797050 4.283475)

93: 554.07 18.405077 ( 3.185295 2.672138 -1.057663)

94: 557.60 149.084812 ( 4.775422 -9.684638 5.699820)

95: 564.66 102.370367 ( -0.332909 -9.627273 -3.094375)

96: 571.58 11.201437 ( -2.524018 2.064139 -0.755049)

97: 581.72 5.965429 ( -0.509762 1.188320 -2.072068)

98: 589.50 84.790154 ( 5.979586 -4.606345 5.274115)

99: 598.64 21.814510 ( -4.155017 0.033413 2.132892)

100: 600.54 30.260901 ( -3.608936 3.602841 2.063011)

101: 614.44 116.830020 ( 0.795157 3.223943 10.286104)

102: 622.49 115.229203 ( -9.311234 -5.073865 1.669136)

103: 625.53 37.412985 ( 4.519731 -1.243803 3.929118)

104: 626.42 1.593725 ( -0.892631 -0.628028 -0.634441)

105: 629.44 105.204384 ( -6.600364 7.358998 2.735821)

106: 634.16 284.184515 ( 8.290817 -7.088625 12.852948)

107: 640.43 16.047265 ( -0.116449 -3.646768 1.653721)

108: 667.19 59.014441 ( 1.216208 5.204801 5.517728)

109: 673.37 1.147601 ( 0.223480 0.391650 -0.971734)

110: 692.02 7.923955 ( -2.340889 1.384038 -0.727073)

111: 694.57 16.994564 ( -3.245181 -0.796762 -2.414236)

112: 698.78 35.796891 ( 1.811172 5.212987 2.311129)

113: 700.55 8.307554 ( 1.555595 -0.553279 2.362533)

114: 702.52 38.647175 ( -1.040955 -0.367484 6.117887)

115: 707.74 94.368726 ( 2.038568 -1.869299 -9.312287)

116: 712.59 65.252540 ( -1.083800 -5.926003 5.381487)

117: 717.40 57.235751 ( -1.682556 -6.421084 3.629661)

118: 722.32 4.176589 ( -0.960435 -1.615212 -0.803271)

119: 726.97 16.659394 ( 3.519611 -1.985745 -0.573191)

120: 728.17 11.306580 ( 2.889971 1.602907 0.620756)

121: 733.00 9.420464 ( -2.895169 -0.512189 -0.880978)

122: 739.69 38.886087 ( -5.914682 1.974483 -0.063578)

123: 741.38 5.208233 ( -1.895229 0.985451 -0.803260)

124: 750.96 4.644304 ( 0.153923 0.967532 -1.919503)

125: 755.72 7.152756 ( 1.473078 0.365738 2.202052)

126: 759.65 9.915604 ( 2.702365 -1.195005 1.088481)

127: 779.06 42.142195 ( 0.048274 6.393162 -1.125764)

128: 782.41 49.928232 ( -1.553124 0.941719 6.828558)

129: 791.61 27.510040 ( 1.042697 -4.233938 -2.914891)

130: 793.81 27.925442 ( 5.048452 1.555083 0.142440)

131: 807.10 21.487608 ( 1.109653 1.623730 4.197592)

132: 813.47 40.115880 ( -0.926143 4.118331 4.722022)

133: 814.93 4.981290 ( 0.300278 0.544717 2.143457)

134: 831.19 55.267363 ( 7.413116 -0.477641 0.291446)

135: 848.00 36.603652 ( 5.901996 -1.038444 0.831703)

136: 855.04 8.861249 ( -2.971773 0.102637 -0.138851)

137: 860.88 32.985535 ( 5.263291 -0.398877 2.263669)

138: 874.97 67.016001 ( -6.682281 -4.654659 -0.835025)

139: 875.25 61.544069 ( 6.766817 -3.245507 2.284939)

140: 886.54 39.512681 ( -4.553701 1.084151 -4.195367)

141: 907.60 40.286084 ( -2.332650 -5.479645 2.195066)

142: 910.88 202.313139 ( 2.682096 10.364369 9.364794)

143: 923.08 20.402935 ( 1.177721 0.760355 -4.293922)

144: 928.82 27.581806 ( -1.921104 -4.114634 -2.638362)

145: 929.59 0.814470 ( 0.208869 0.824095 -0.302839)

146: 938.33 29.124172 ( 0.200748 0.298349 5.384688)

147: 945.58 48.488967 ( 0.538004 3.150759 -6.186456)

148: 946.73 24.971362 ( 0.818723 -4.317105 -2.379845)

149: 956.80 46.975291 ( -6.332174 -2.446197 -0.946035)

150: 968.36 26.805620 ( -0.451467 -3.510203 3.778925)

151: 977.88 0.420363 ( 0.468497 0.417395 0.163265)

152: 982.53 7.950979 ( 1.119100 0.651720 2.504766)

153: 984.17 27.515775 ( -1.588321 -2.025994 -4.570378)

154: 985.12 18.567794 ( -3.113950 0.838722 -2.857911)

155: 985.67 20.835210 ( 0.635700 4.297835 1.399896)

156: 989.23 8.223098 ( 0.744240 -2.722700 0.506071)

157: 990.07 14.637569 ( 3.731962 -0.007668 0.842596)

158: 990.43 11.969342 ( -2.358126 -1.516322 2.027154)

159: 994.61 15.161187 ( -0.089839 1.465065 -3.606480)

160: 999.33 2.413810 ( -0.841366 0.825371 1.012264)

161: 1000.19 15.445054 ( -1.389108 1.694320 3.262623)

162: 1001.80 45.390752 ( -0.149649 6.359114 -2.220367)

163: 1002.29 2.884415 ( 0.916657 -0.961939 1.057747)

164: 1019.77 55.381700 ( 0.257684 6.992396 2.534107)

165: 1029.40 34.744617 ( 1.024548 -3.140840 -4.881602)

166: 1033.47 150.875272 ( -0.686162 -12.263949 -0.001455)

167: 1050.52 90.930032 ( -4.188083 -8.544299 -0.620442)

168: 1055.02 69.705030 ( -4.318273 1.086244 -7.062409)

169: 1069.73 5.755332 ( 1.441328 1.812390 0.627014)

170: 1079.83 135.641007 ( 2.476285 -2.929048 -10.996804)

171: 1086.26 23.140125 ( 0.345023 2.210964 4.258253)

172: 1100.50 65.466264 ( 4.687823 3.914182 5.307519)

173: 1105.91 55.009046 ( -3.827107 -0.694740 -6.315032)

174: 1110.22 210.915079 ( 3.701613 -11.487652 8.077561)

175: 1111.60 72.698430 ( -1.323057 -3.272201 7.761485)

176: 1116.29 76.398321 ( -1.608480 1.146668 -8.514474)

177: 1119.72 92.558278 ( -5.430060 -4.469838 6.564547)

178: 1124.33 44.942767 ( -4.042131 -5.328709 0.456951)

179: 1125.11 1.937824 ( -0.822072 0.388318 1.054149)

180: 1141.31 28.202417 ( 2.567177 -3.116632 -3.449439)

181: 1149.06 223.881133 ( 1.508636 13.785515 5.618249)

182: 1157.75 2.012236 ( 1.314321 0.284717 0.451366)

183: 1158.60 15.465904 ( 0.376740 3.291375 -2.119156)

184: 1169.78 28.497065 ( 3.894040 -1.703944 3.229566)

185: 1172.85 24.659416 ( 4.913099 0.658570 0.295233)

186: 1175.29 129.638722 ( 0.555161 -4.524620 10.433520)

187: 1183.77 41.725708 ( -0.541580 1.690849 -6.210751)

188: 1188.37 8.275636 ( -2.535870 0.330564 -1.317469)

189: 1207.31 32.420780 ( -2.888647 3.328024 -3.605656)

190: 1236.68 47.211282 ( 0.046075 -5.787544 -3.703174)

191: 1250.69 77.789945 ( 2.588693 4.280148 -7.264223)

192: 1253.43 269.362629 ( 0.102613 -14.203097 -8.223389)

193: 1255.55 28.604561 ( -1.110793 3.395579 -3.980043)

194: 1259.13 11.948979 ( 2.473620 1.945765 -1.429749)

195: 1267.31 6.840436 ( 0.913418 2.312043 0.812749)

196: 1272.11 52.159967 ( 1.003913 1.572996 6.976948)

197: 1273.56 472.326211 ( -0.778455 -18.782076 -10.906596)

198: 1278.08 4.056184 ( 1.410616 -0.040156 -1.436918)

199: 1279.67 196.106273 ( -2.165420 -5.569871 -12.664666)

200: 1284.53 110.809144 ( 6.628609 -3.332909 7.467422)

201: 1286.40 9.242703 ( -0.752201 1.777140 2.349185)

202: 1292.77 18.624895 ( -1.211724 0.068183 4.141494)

203: 1300.87 72.947740 ( 0.747513 7.989381 2.925536)

204: 1321.58 18.943778 ( 1.111620 4.118419 0.864121)

205: 1328.33 43.650845 ( 0.793813 5.716815 3.215389)

206: 1329.35 1.493556 ( -0.216626 0.893344 0.805336)

207: 1331.14 3.387199 ( 0.659034 1.332201 1.085410)

208: 1332.28 16.468821 ( 0.104740 -1.395883 3.809115)

209: 1341.20 20.918391 ( -1.349208 -3.745692 -2.251182)

210: 1349.20 100.996875 ( 6.161042 -4.287730 6.682351)

211: 1351.40 41.165526 ( -1.573104 -4.060343 4.712164)

212: 1353.85 55.255671 ( -0.859947 2.407631 -6.979934)

213: 1356.89 144.156942 ( 2.581684 10.750487 -4.681761)

214: 1358.67 8.184342 ( 0.268284 2.768188 0.670449)

215: 1359.74 27.057022 ( -0.817608 4.965571 1.315918)

216: 1361.37 12.884805 ( 0.837291 -3.386617 0.845325)

217: 1363.38 2.946102 ( -1.435114 -0.350466 -0.873913)

218: 1368.18 26.293556 ( 0.286718 4.904047 1.470262)

219: 1382.38 158.137826 ( -6.510149 -7.893054 -7.311326)

220: 1386.61 329.994277 ( 1.502425 15.754080 8.918854)

221: 1388.00 20.772367 ( -4.501274 -0.344898 -0.626054)

222: 1388.54 5.598429 ( -1.583992 0.700748 -1.611940)

223: 1389.74 14.690001 ( 3.764181 0.388742 -0.608130)

224: 1392.37 30.709011 ( -1.047136 -5.383911 0.791215)

225: 1393.88 14.799601 ( 3.561416 -0.715626 -1.266412)

226: 1395.35 41.521450 ( -2.122928 3.900865 -4.668820)

227: 1397.04 5.534893 ( 1.323490 -0.949954 1.697308)

228: 1398.49 18.903568 ( -0.581204 4.279954 -0.497757)

229: 1399.93 4.287518 ( -0.444460 -0.015403 2.022310)

230: 1401.72 18.131086 ( 3.638209 -1.946009 -1.052413)

231: 1407.32 10.533130 ( 2.516522 2.049431 -0.009152)

232: 1408.06 31.762895 ( 2.544441 4.928498 0.999314)

233: 1410.32 162.577347 ( -0.293289 -9.980932 -7.929207)

234: 1416.06 80.279797 ( -1.007897 4.003397 7.952154)

235: 1416.45 24.411419 ( 0.292291 4.188434 2.604420)

236: 1418.62 38.398511 ( -1.512394 1.804739 -5.731849)

237: 1421.00 18.420890 ( 3.057273 2.902083 -0.807396)

238: 1425.33 36.384687 ( -0.964268 3.491401 4.823380)

239: 1425.72 3.314937 ( -0.210256 0.804544 1.619703)

240: 1488.77 388.910100 ( 3.337664 18.202030 6.815880)

241: 1491.22 13.153804 ( 1.306248 2.286182 -2.494172)

242: 1506.99 2.683015 ( -0.226412 -0.368573 1.579844)

243: 1510.01 14.473270 ( -1.191704 -3.372768 1.295202)

244: 1534.39 240.983348 ( -3.250198 -9.976843 11.440375)

245: 1539.20 9.236967 ( -0.455244 -1.919591 -2.311902)

246: 1549.54 17.859068 ( -0.939776 0.827373 4.036253)

247: 1556.26 112.356849 ( -2.094433 -9.525114 -4.152397)

248: 1566.58 81.246998 ( -0.254026 5.772556 6.918097)

249: 1579.72 41.117304 ( 3.318317 2.843232 4.692772)

250: 1582.35 6.988782 ( -1.564586 -0.584614 2.049165)

251: 1604.22 77.749254 ( 3.284191 8.145975 -0.778737)

252: 1605.77 487.858541 ( 5.767595 20.214867 -6.778832)

253: 1614.13 156.216330 ( -1.302510 7.561810 9.866044)

254: 1617.06 24.119873 ( 0.058931 4.139610 -2.641975)

255: 1624.71 82.183206 ( 0.276078 6.671150 6.132108)

256: 1628.42 24.975561 ( -0.194814 4.518327 -2.126577)

257: 1639.12 33.457137 ( -1.959623 4.388984 3.217738)

258: 1645.64 4.438548 ( 0.044271 -1.173245 1.749310)

259: 1687.02 3.490441 ( 0.887249 1.076589 1.242653)

260: 1730.27 509.014339 ( 17.664813 -0.705342 -14.016819)

261: 1743.52 435.914978 ( 6.300065 14.554213 13.579361)

262: 2940.37 118.569516 ( -0.439539 -10.879617 0.101228)

263: 2952.28 53.103120 ( -1.448326 -6.853616 -2.008336)

264: 2956.27 45.441877 ( -4.723073 -3.876765 2.846955)

265: 2956.37 74.395751 ( 1.982045 -8.389877 -0.277870)

266: 2957.14 65.226994 ( -1.353033 -1.803085 7.755332)

267: 2957.68 50.588707 ( 2.461667 6.505455 -1.485920)

268: 2982.18 35.772303 ( -2.185002 4.640183 3.076811)

269: 2984.08 47.135648 ( -2.349537 2.405944 -5.985546)

270: 3002.40 41.077381 ( 0.972247 2.574177 5.788413)

271: 3003.32 18.568516 ( -2.796982 -1.728177 2.785465)

272: 3022.72 9.246366 ( 2.597319 -1.390585 0.752712)

273: 3022.74 41.245527 ( -6.287615 -1.035811 -0.799074)

274: 3027.57 12.082556 ( -3.301210 0.579975 0.920977)

275: 3028.41 12.700951 ( 2.752594 -2.150414 0.707033)

276: 3035.68 15.134956 ( -2.293560 1.348448 2.838349)

277: 3036.63 136.111045 ( -4.222541 -9.229822 5.752529)

278: 3037.21 21.343005 ( 1.621398 3.453478 -2.605295)

279: 3037.27 1.781536 ( -0.625148 -1.103842 -0.415041)

280: 3061.30 36.782941 ( 2.075711 3.805855 -4.241442)

281: 3065.13 14.128516 ( -1.194355 -0.672180 3.500029)

282: 3065.38 28.467076 ( -1.230079 -3.235861 4.059949)

283: 3068.51 20.573592 ( -0.341123 -4.126805 1.851136)

284: 3069.70 22.159660 ( 1.504718 0.814411 -4.385455)

285: 3072.13 12.454885 ( 1.050790 1.414196 3.057903)

286: 3073.51 2.750923 ( -1.459933 0.510017 0.599499)

287: 3074.24 25.581050 ( -1.514078 -2.967191 -3.805837)

288: 3081.26 4.839680 ( -0.280322 1.023038 1.927302)

289: 3085.55 26.817451 ( 1.404312 3.941098 3.051737)

290: 3086.44 76.641846 ( -2.212994 -8.145665 2.322208)

291: 3088.06 26.394210 ( 0.233694 2.488335 4.488629)

292: 3114.36 12.030701 ( 0.086555 -0.567066 -3.420767)

293: 3132.76 5.288901 ( 0.556843 -0.739949 -2.105066)

294: 3136.74 1.360735 ( -0.348625 -0.731736 0.838903)

295: 3138.69 0.402582 ( -0.223890 0.111388 0.583137)

296: 3146.06 5.953887 ( -0.725526 -2.273312 0.509460)

297: 3147.90 37.608320 ( -0.957362 -6.050862 -0.280793)

298: 3150.89 11.919169 ( -0.410504 0.647399 3.366234)

299: 3156.62 1.016288 ( 0.099220 -0.624329 -0.785275)

300: 3170.37 15.339555 ( 1.138771 3.036093 -2.196564)

301: 3179.36 4.025233 ( 0.978962 1.089071 -1.371420)

302: 3321.98 506.547495 ( -4.329594 0.723243 22.074398)

303: 3557.15 145.430618 ( -5.821019 -9.124977 -5.318002)

304: 3583.73 101.271321 ( 4.258754 -8.990453 1.518583)

305: 3593.40 122.173949 ( -4.270507 9.312450 -4.149096)

ESM Table S11Comparison of the electron energies of Fe(III)PPIX-L2complexes (N2- and S5-bound to the Fe(III) center ofFe(III)PPIX). All values are in kcal/mol

Complex / Uncorrected energy / Zero point energy (ZPE) / ZPE-corrected energy / Relative energy
Fe(III)PPIX-L2 (N2-bound) / -2587718.023 / 499.104 / -2587218.920 / 268.979
Fe(III)PPIX-L2 (S5-bound) / -2587443.272 / 493.331 / -2586949.941 / 0.000

ESMTable S12Electron localization function (ELF) and localized orbital locator (LOL) values for the noncovalent interactions in Fe(III)PPIX–MAPTSC complexes, computed at RIJCOSX-B3LYP-D3(BJ)/def2-TZVP level of theory

Fe(III)PPIX-L1 / Fe(III)PPIX-L2
Bonding interaction / ELF / LOL / Bonding interaction / ELF / LOL
Fe1―S76# / 0.36869 / 0.43218 / Fe1―N81# / 0.25455 / 0.36857
O39···H80# / 0.11167 / 0.26183 / O42···H80# / 0.12749 / 0.27662
O39···H82# / 0.02881 / 0.14708 / O42···H82# / 0.02922 / 0.14805
O39···H95# / 0.01761 / 0.11831 / C3···S76# / 0.02177 / 0.13006
C46···H95# / 0.05918 / 0.20079 / N30···H79# / 0.04684 / 0.18156
H75···H96# / 0.04260 / 0.17448 / O99···H67# / 0.00972 / 0.09046
C16···H87# / 0.01450 / 0.10851 / O99···C26# / 0.01139 / 0.09721
C12···H86# / 0.02454 / 0.13718 / C27···H101# / 0.02437 / 0.13680
C10···N83# / 0.02184 / 0.13024 / C23···C93# / 0.03809 / 0.16624
O42···H45† / 0.03220 / 0.15444 / C94···N21# / 0.02722 / 0.14354
O42···H72† / 0.03279 / 0.15569 / C19···C90# / 0.03114 / 0.15229
O40···H45† / 0.02101 / 0.12801 / H56···H97# / 0.00475 / 0.06500
H49···H47† / 0.04510 / 0.17872 / C12···H87† / 0.02801 / 0.14544
H52···H51† / 0.04138 / 0.17219 / H61···H75† / 0.04346 / 0.17589
H53···H66† / 0.03110 / 0.15212 / O43···H73† / 0.02079 / 0.12745
H65···H55† / 0.04522 / 0.17891 / C37···H45† / 0.01623 / 0.11407
C94···H82* / 0.05248 / 0.19065 / H55···H65† / 0.03718 / 0.16440
H53···H67† / 0.03062 / 0.15110
H51···H52† / 0.04716 / 0.18215
H47···H49† / 0.04726 / 0.18234
N81···H95* / 0.06836 / 0.21323

1