Nasir Shahzad, Riffat Un Nisa and Khurshid Ayub*

Substituents Effect on Thermal Electrocyclic Reaction of Dihydroazulene-Vinylheptafulvene Photoswitch; A DFT Study to Improve the Photoswitch

Nasir Shahzad, Riffat Un Nisa and Khurshid Ayub*

Department of Chemistry, COMSATS Institute of Information Technology, Abbottabad, Pakistan 22060

Phone: +92-992-383591(-7)

Fax: +92-992-383441

Email:

Table SI 1. Total energies of substituted DHAs, VHFs and their transition states in acetonitrile calculated at PBE0/6-31G(d,p) through polarization continuum model (PCM)

Substituent / DHA / VHF / TS
8a-formyl / -684.02747 / -684.03057 / -683.989471
8-formyl / -684.03978 / -684.63644 / -683.999374
7-formyl / -684.04142 / -684.03982 / -683.995045
6-formyl / -684.04607 / -684.0397 / -684.000731
5-formyl / -684.04273 / -684.03661 / -683.995586
4-formyl / -684.04112 / -684.03029 / -683.994828
8a-Br / -610.10463 / -610.0997 / -610.061708
8-Br / -610.10339 / -610.1078 / -610.069529
7-Br / -610.10855 / -610.10843 / -610.068897
6-Br / -610.10922 / -610.10845 / -610.068221
5-Br / -610.10892 / -610.10747 / -610.068811
4-Br / -610.10734 / -610.10474 / -610.065285
8a-Cl / -1030.2694 / -1030.2591 / -1030.21699
8-Cl / -1030.2645 / -1030.2673 / -1030.22749
7-Cl / -1030.2733 / -1030.2681 / -1030.22803
6-Cl / -1030.2733 / -1030.2681 / -1030.22711
5-Cl / -1030.2728 / -1030.2672 / -1030.228
4-Cl / -1030.2706 / -1030.2642 / -1030.2255
8a-F / -669.98127 / -669.97863 / -669.934459
8-F / -669.97749 / -669.98032 / -669.940711
7-F / -669.98007 / -669.98018 / -669.94184
6-F / -669.9826 / -669.98035 / -669.940251
5-F / -669.98211 / -669.97986 / -669.941277
4-F / -669.97917 / -669.98066 / -669.938806
8a-CH3 / -610.10463 / -610.0997 / -610.061708
8-CH3 / -610.10339 / -610.1078 / -610.069529
7-CH3 / -610.10855 / -610.10843 / -610.068897
6-CH3 / -610.10922 / -610.10845 / -610.068221
5-CH3 / -610.10892 / -610.10747 / -610.068811
4-CH3 / -610.10734 / -610.10474 / -610.065285
8a-NH2 / -626.13093 / -626.14804 / -626.108762
8-NH2 / -626.14114 / -626.14992 / -626.121301
7-NH2 / -626.1382 / -626.1509 / -626.112506
6-NH2 / -626.14384 / -626.15119 / -626.109458
5-NH2 / -626.14198 / -626.149 / -626.111727
4-NH2 / -626.13909 / -626.14862 / -626.105141
8a-NO2 / -775.12604 / -775.11793 / -775.078036
8-NO2 / -775.12872 / -775.12876 / -775.089976
7-NO2 / -775.13634 / -775.13035 / -775.08552
6-NO2 / -775.13983 / -775.13012 / -775.091171
5-NO2 / -775.13857 / -775.12871 / -775.086478
4-NO2 / -775.1327 / -775.11894 / -775.082832
8a-OH / -645.98201 / -645.98766 / -645.946094
8-OH / -645.98758 / -645.98992 / -645.956112
7-OH / -645.98546 / -645.99163 / -645.95298
6-OH / -645.99028 / -645.99164 / -645.956478
5-OH / -645.98936 / -645.98944 / -645.953293
4-OH / -645.98585 / -645.99076 / -645.948934
8a-SH / -968.86833 / -968.86513 / -968.824054
8-SH / -968.86981 / -968.87219 / -968.83444
7-SH / -968.87556 / -968.87364 / -968.833362
6-SH / -968.87606 / -968.87311 / -968.833362
5-SH / -968.87537 / -968.87182 / -968.83455
4-SH / -968.87488 / -968.86991 / -968.830536
8-N / -586.86541 / -586.84973 / -586.816619
7-N / -586.86731 / -586.85123 / -586.804455
6-N / -586.85838 / -586.85077 / -586.811633
5-N / -586.85815 / -586.85107 / -586.806162
4-N / -586.86774 / -586.85324 / -586.813116
H / -570.8350432 / -570.8366778 / -570.7953359

Table SI 2. Zero Point Corrected (ZPC) energies of DHAs, VHFs and their corresponding transiton states in acetonitrile calculated at PBE0/6-31G(d,p) through polarization continuum model (PCM)

Substituent / DHA / VHF / TS
8a-formyl / -683.85192 / -683.854708 / -683.81525
8-formyl / -683.86314 / -683.860617 / -683.824943
7-formyl / -683.86539 / -683.863726 / -683.820706
6-formyl / -683.86963 / -683.863681 / -683.82884
5-formyl / -683.86664 / -683.860759 / -683.821321
4-formyl / -683.86477 / -683.85462 / -683.820144
8a-Br / -609.90963 / -609.905422 / -609.868816
8-Br / -609.90861 / -609.913444 / -609.876373
7-Br / -609.91405 / -609.914004 / -609.875959
6-Br / -609.91484 / -609.914036 / -609.875163
5-Br / -609.91447 / -609.913102 / -609.87586
4-Br / -609.91279 / -609.909836 / -609.872116
8a-Cl / -1030.1124 / -1030.10258 / -1030.06179
8-Cl / -1030.1072 / -1030.11041 / -1030.07208
7-Cl / -1030.1162 / -1030.11116 / -1030.0726
6-Cl / -1030.1162 / -1030.1112 / -1030.07172
5-Cl / -1030.1157 / -1030.11028 / -1030.07261
4-Cl / -1030.1134 / -1030.10713 / -1030.06988
8a-F / -669.82249 / -669.820216 / -669.777777
8-F / -669.81872 / -669.821976 / -669.783392
7-F / -669.82148 / -669.821747 / -669.784595
6-F / -669.82408 / -669.821905 / -669.783034
5-F / -669.82365 / -669.821522 / -669.784369
4-F / -669.82051 / -669.822032 / -669.781691
8a-CH3 / -609.90963 / -609.905422 / -609.868816
8-CH3 / -609.90861 / -609.913444 / -609.876373
7-CH3 / -609.91405 / -609.914004 / -609.875959
6-CH3 / -609.91484 / -609.914036 / -609.875163
5-CH3 / -609.91447 / -609.913102 / -609.87586
4-CH3 / -609.91279 / -609.909836 / -609.872116
8a-NH2 / -625.94698 / -625.964259 / -625.926695
8-NH2 / -625.95718 / -625.966287 / -625.937992
7-NH2 / -625.95466 / -625.967222 / -626.930266
6-NH2 / -625.96051 / -625.967543 / -625.927479
5-NH2 / -625.95857 / -625.965499 / -625.929604
4-NH2 / -625.95556 / -625.964484 / -625.923064
8a-NO2 / -774.95697 / -774.949245 / -774.911181
8-NO2 / -774.95884 / -774.959714 / -774.922553
7-NO2 / -774.96679 / -774.961177 / -774.918142
6-NO2 / -774.97015 / -774.960952 / -774.923704
5-NO2 / -774.96905 / -774.959671 / -774.91903
4-NO2 / -774.96304 / -774.949896 / -774.915019
8a-OH / -645.81105 / -645.81647 / -645.776707
8-OH / -645.87606 / -645.818887 / -645.785771
7-OH / -645.81442 / -645.820317 / -645.770639
6-OH / -645.81915 / -645.820269 / -645.785878
5-OH / -645.81826 / -645.818247 / -645.783341
4-OH / -645.81473 / -645.819354 / -645.778807
8a-SH / -968.70267 / -968.699609 / -968.660186
8-SH / -968.70378 / -968.706558 / -968.669666
7-SH / -968.70964 / -968.707716 / -968.66863
6-SH / -968.71019 / -968.70739 / -968.66863
5-SH / -968.70949 / -968.70609 / -968.67005
4-SH / -968.709 / -968.703879 / -968.666067
8-N / -586.7103 / -586.695699 / -586.664078
7-N / -586.71231 / -586.696908 / -586.651949
6-N / -586.7035 / -586.696428 / -586.658924
5-N / -586.70327 / -586.697038 / -586.653487
4-N / -586.71276 / -586.699275 / -586.660612
H / -570.668281 / -570.669944 / -570.630022

Table SI 3. Gibbs Free energies of DHAs, VHFs and their corresponding transition states in acetonitrile calculated at PBE0/6-31G(d,p) through polarization continuum model (PCM)

Substituent / DHA / VHF / TS
8a-formyl / -683.8921 / -683.8959 / -683.85567
8-formyl / -683.9023 / -683.90244 / -683.86562
7-formyl / -683.9059 / -683.9057 / -683.86279
6-formyl / -683.9102 / -683.90573 / -683.86726
5-formyl / -683.9074 / -683.90282 / -683.86286
4-formyl / -683.905 / -683.8965 / -683.86093
8a-Br / -609.948 / -609.9458 / -609.9081
8-Br / -609.9471 / -609.9547 / -609.91658
7-Br / -609.9536 / -609.95521 / -609.89165
6-Br / -609.9545 / -609.95529 / -609.91591
5-Br / -609.954 / -609.95432 / -609.91635
4-Br / -609.9522 / -609.95057 / -609.91253
8a-Cl / -1030.151 / -1030.1432 / -1030.1016
8-Cl / -1030.146 / -1030.1516 / -1030.1125
7-Cl / -1030.156 / -1030.1525 / -1030.1131
6-Cl / -1030.156 / -1030.1526 / -1030.1124
5-Cl / -1030.755 / -1030.1516 / -1030.113
4-Cl / -1030.153 / -1030.4148 / -1030.1102
8a-F / -669.8609 / -669.85995 / -669.81702
8-F / -669.8572 / -669.86234 / -669.82259
7-F / -669.8611 / -669.86207 / -669.82442
6-F / -669.8631 / -669.86225 / -669.8224
5-F / -669.8267 / -669.8619 / -669.82387
4-F / -669.86 / -669.86227 / -669.82187
8a-CH3 / -609.948 / -609.9458 / -609.9081
8-CH3 / -609.9471 / -609.9547 / -609.91658
7-CH3 / -609.9536 / -609.95521 / -609.89165
6-CH3 / -609.9545 / -609.95529 / -609.91591
5-CH3 / -609.954 / -609.95432 / -609.91635
4-CH3 / -609.9522 / -609.95057 / -609.91253
8a-NH2 / -625.9855 / -626.00423 / -625.96617
8-NH2 / -625.9954 / -625.00751 / -625.97839
7-NH2 / -625.9943 / -626.00806 / -625.96992
6-NH2 / -626.0002 / -626.00854 / -625.96763
5-NH2 / -625.9977 / -626.00653 / -625.96933
4-NH2 / -625.9947 / -626.00505 / -625.96366
8a-NO2 / -774.9981 / -774.99172 / -774.95323
8-NO2 / -774.9992 / -775.00327 / -774.96457
7-NO2 / -775.0089 / -775.00478 / -774.96156
6-NO2 / -775.012 / -775.00457 / -774.9662
5-NO2 / -775.011 / -775.00341 / -774.96192
4-NO2 / -775.0046 / -774.99313 / -774.95705
8a-OH / -645.8495 / -645.85625 / -645.81653
8-OH / -645.8543 / -645.85949 / -645.82621
7-OH / -645.8539 / -645.86087 / -645.82272
6-OH / -645.8584 / -645.8607 / -645.82607
5-OH / -645.8572 / -645.85872 / -645.82283
4-OH / -645.854 / -645.85975 / -645.81853
8a-SH / -968.742 / -968.74056 / -968.70025
8-SH / -968.743 / -968.74856 / -968.71012
7-SH / -968.7498 / -968.74943 / -968.70941
6-SH / -968.7503 / -968.74935 / -968.70941
5-SH / -968.7496 / -968.7479 / -968.71081
4-SH / -968.7489 / -968.74535 / -968.70707
8-N / -586.7477 / -586.73487 / -586.70208
7-N / -586.7495 / -586.73612 / -586.69103
6-N / -586.7412 / -586.73566 / -586.69716
5-N / -586.7409 / -586.73616 / -586.69191
4-N / -586.7499 / -586.73843 / -586.69883
H / -570.707411 / -570.707666 / -570.668693

Table SI 4. Total energies of substituted DHAs, VHFs and their corresponding transition states in the gas phase calculated at PBE0/6-31G(d,p)

Total Energy
Substituent / DHA / VHF / TS
Parent / -570.659384 / -570.65258 / -570.609773
8a-formyl / -684.013608 / -684.013212 / -683.966425
8-formyl / -684.024031 / -684.018303 / -683.975707
7-formyl / -684.026579 / -684.021568 / -683.9717
6-formyl / -684.031225 / -684.022796 / -683.97933
5-formyl / -684.028658 / -684.019722 / -683.97278
4-formyl / -684.027137 / -684.014325 / -683.975348
8a-Br / -3141.60353 / -3141.58963 / -3141.54132
8-Br / -3141.59739 / -3141.59461 / -3141.55044
7-Br / -3141.6029 / -3141.59556 / -3141.55081
6-Br / -3141.60469 / -3141.59577 / -3141.54957
5-Br / -3141.6042 / -3141.59501 / -3141.5512
4-Br / -3141.60424 / -3141.59324 / -3141.54962
8a-Cl / -1030.2559 / -1030.24408 / -1030.19523
8-Cl / -1030.25271 / -1030.2515 / -1030.20644
7-Cl / -1030.26216 / -1030.25306 / -1030.20841
6-Cl / -1030.26216 / -1030.25325 / -1030.2069
5-Cl / -1030.26165 / -1030.25239 / -1030.20872
4-Cl / -1030.26036 / -1030.24985 / -1030.20591
8a-F / -669.96588 / -669.962685 / -669.912123
8-F / -669.965872 / -669.96421 / -669.918025
7-F / -669.968878 / -669.965009 / -669.922466
6-F / -669.971917 / -669.965018 / -669.917942
5-F / -669.971351 / -669.964487 / -669.922361
4-F / -669.969028 / -669.965937 / -669.918158
8a-CH3 / -610.093952 / -610.08421 / -610.041289
8-CH3 / -610.092859 / -610.092174 / -610.049146
7-CH3 / -610.0981 / -610.092648 / -610.049146
6-CH3 / -610.09874 / -610.092253 / -610.048537
5-CH3 / -610.098353 / -610.091214 / -610.048215
4-CH3 / -610.096826 / -610.088881 / -610.045129
8-N / -586.85072 / -586.834399 / -586.79651
7-N / -586.855405 / -586.8344 / -586.783469
6-N / -586.846044 / -586.836072 / -586.792712
5-N / -586.856685 / -586.837025 / -586.78528
4-N / -586.856685 / -586.838637 / -586.795105
8a-NH2 / -626.117229 / -626.130412 / -626.086804
8-NH2 / -626.129057 / -626.130404 / -626.090555
7-NH2 / -626.123946 / -626.127895 / -626.089092
6-NH2 / -626.129199 / -626.126425 / -626.079543
5-NH2 / -626.127083 / -626.123969 / -626.087066
4-NH2 / -626.124675 / -626.123409 / -626.079905
8a-NO2 / -775.111222 / -775.100084 / -775.051894
8-NO2 / -775.112282 / -775.111195 / -775.066348
7-NO2 / -775.120974 / -775.112273 / -775.062987
6-NO2 / -775.12411 / -775.113 / -775.069904
5-NO2 / -775.12374 / -775.112291 / -775.064169
4-NO2 / -775.119307 / -775.102554 / -775.062735
8a-OH / -645.968039 / -645.968461 / -645.925635
8-OH / -645.972487 / -645.967692 / -645.924847
7-OH / -645.970771 / -645.971363 / -645.923813
6-OH / -645.976403 / -645.971366 / -645.923818
5-OH / -645.97557 / -645.968008 / -645.930178
4-OH / -645.972284 / -645.970749 / -645.922116
8a-SH / -968.855374 / -968.847819 / -968.802125
8-SH / -968.856847 / -968.853804 / -968.809921
7-SH / -968.862895 / -968.855726 / -968.80894
6-SH / -968.863357 / -968.855005 / -968.80894
5-SH / -968.862718 / -968.853896 / -968.812698
4-SH / -968.863501 / -968.852163 / -968.808477

Table SI 5. Zero point corrected energies of substituted DHAs, VHFs and their corresponding transition states in the gas phase calculated at PBE0/6-31G(d,p)

ZPC Energy
Substituent / DHA / VHF / TS
Parent / -570.65938 / -570.65258 / -570.60977
8a-formyl / -683.83812 / -683.83767 / -683.79281
8-formyl / -683.8475 / -683.8427 / -683.80192
7-formyl / -683.85063 / -683.84568 / -683.79813
6-formyl / -683.85496 / -683.84686 / -683.80526
5-formyl / -683.85258 / -683.84396 / -683.79913
4-formyl / -683.85083 / -683.8387 / -683.80096
8a-Br / -3141.4472 / -3141.4338 / -3141.3875
8-Br / -3141.4408 / -3141.4384 / -3141.3962
7-Br / -3141.4463 / -3141.4392 / -3141.3964
6-Br / -3141.4481 / -3141.4394 / -3141.3952
5-Br / -3141.4477 / -3141.4387 / -3141.3968
4-Br / -3141.4475 / -3141.4369 / -3141.3951
8a-Cl / -1030.0988 / -1030.0877 / -1030.0408
8-Cl / -1030.0954 / -1030.0947 / -1030.0516
7-Cl / -1030.105 / -1030.0962 / -1030.0534
6-Cl / -1030.105 / -1030.0964 / -1030.052
5-Cl / -1030.1045 / -1030.0956 / -1030.0428
4-Cl / -1030.1031 / -1030.0929 / -1030.0508
8a-F / -669.80699 / -669.80438 / -669.75601
8-F / -669.807 / -669.80597 / -669.76164
7-F / -669.8102 / -669.80664 / -669.76591
6-F / -669.81328 / -669.80663 / -669.76158
5-F / -669.81278 / -669.8062 / -669.76579
4-F / -669.81025 / -669.8073 / -669.76165
8a-CH3 / -609.89892 / -609.89011 / -609.84868
8-CH3 / -609.89795 / -609.89788 / -609.85667
7-CH3 / -609.90382 / -609.8969 / -609.85572
6-CH3 / -609.90424 / -609.89786 / -609.85611
5-CH3 / -609.90382 / -609.8969 / -609.85572
4-CH3 / -609.90218 / -609.894 / -609.85237
8-N / -586.69568 / -586.68052 / -586.64447
7-N / -586.70042 / -586.68051 / -586.63159
6-N / -586.69124 / -586.68186 / -586.64046
5-N / -586.68305 / -586.6334
4-N / -586.70166 / -586.68473 / -586.64303
8a-NH2 / -625.93328 / -625.94608 / -625.90433
8-NH2 / -625.94489 / -625.94607 / -625.908
7-NH2 / -625.94042 / -625.94428 / -625.90703
6-NH2 / -625.94575 / -625.9429 / -625.89775
5-NH2 / -625.94364 / -625.90512
4-NH2 / -625.941 / -625.9395 / -625.89762
8a-NO2 / -774.94213 / -774.93164 / -774.88549
8-NO2 / -774.94234 / -774.94213 / -774.8993
7-NO2 / -774.95134 / -774.94309 / -774.89615
6-NO2 / -774.95439 / -774.9438 / -774.90262
5-NO2 / -774.95408 / -774.94314 / -774.89731
4-NO2 / -774.94949 / -774.93362 / -774.89514
8a-OH / -645.79708 / -645.79736 / -645.75675
8-OH / -645.80095 / -645.79694 / -645.75558
7-OH / -645.79966 / -645.80014 / -645.75455
6-OH / -645.80509 / -645.80014 / -645.75456
5-OH / -645.80431 / -645.79715 / -645.7606
4-OH / -645.80107 / -645.7993 / -645.75293
8a-SH / -968.68972 / -968.68253 / -968.63876
8-SH / -968.69073 / -968.68818 / -968.64609
7-SH / -968.69696 / -968.69 / -968.64526
6-SH / -968.69752 / -968.68944 / -968.64526
5-SH / -968.6969 / -968.68839 / -968.68627
4-SH / -968.69746 / -968.68636 / -968.64455

Table SI 6. Gibbs Free energies energies of substituted DHAs, VHFs and their corresponding transition states calculated at PBE0/6-31G(d,p)

Gibbs Free E
Substituent / DHA / VHF / TS
parent / -570.696976 / -570.691697 / -570.648028
8a-formyl / -683.878184 / -683.879035 / -683.832943
8-formyl / -683.886592 / -683.884426 / -683.842859
7-formyl / -683.891148 / -683.887674 / -683.839354
6-formyl / -683.895573 / -683.888803 / -683.846224
5-formyl / -683.893132 / -683.885909 / -683.840391
4-formyl / -683.891054 / -683.880484 / -683.841649
8a-Br / -3141.487248 / -3141.475138 / -3141.428065
8-Br / -3141.48054 / -3141.480637 / -3141.43723
7-Br / -3141.487123 / -3141.481552 / -3141.437777
6-Br / -3141.488864 / -3141.481777 / -3141.436669
5-Br / -3141.488424 / -3141.481084 / -3141.43818
4-Br / -3141.488066 / -3141.47919 / -3141.436393
8a-Cl / -1030.137799 / -1030.128201 / -1030.080496
8-Cl / -1030.134279 / -1030.135939 / -1030.091802
7-Cl / -1030.144697 / -1030.137473 / -1030.093782
6-Cl / -1030.144694 / -1030.137677 / -1030.092441
5-Cl / -1030.144195 / -1030.136833 / -1030.083094
4-Cl / -1030.142629 / -1030.134051 / -1030.091068
8a-F / -669.845351 / -669.84404 / -669.795161
8-F / -669.845366 / -669.846292 / -669.801076
7-F / -669.849322 / -669.846993 / -669.805306
6-F / -669.852169 / -669.846983 / -669.801107
5-F / -669.851634 / -669.846552 / -669.805155
4-F / -669.8493 / -669.847535 / -669.801062
8a-CH3 / -609.937359 / -609.930627 / -609.88784
8-CH3 / -609.936422 / -609.939072 / -609.896851
7-CH3 / -609.943358 / -609.938082 / -609.896097
6-CH3 / -609.943838 / -609.939041 / -609.896637
5-CH3 / -609.943358 / -609.938082 / -609.896097
4-CH3 / -609.941613 / -609.934703 / -609.892409
8-N / -586.733102 / -586.719622 / -586.682308
7-N / -586.737585 / -586.719622 / -586.670097
6-N / -586.728862 / -586.721043 / -586.678761
5-N / -586.722147 / -586.671829
4-N / -586.738763 / -586.723855 / -586.68104
8a-NH2 / -625.971748 / -625.986392 / -625.9432
8-NH2 / -625.983048 / -625.986387 / -625.947407
7-NH2 / -625.979742 / -625.984942 / -625.946734
6-NH2 / -625.985082 / -625.983707 / -625.937819
5-NH2 / -625.982754 / -625.981424 / -625.944775
4-NH2 / -625.980003 / -625.979973 / -625.937276
8a-NO2 / -774.983295 / -774.974303 / -774.926715
8-NO2 / -774.98263 / -774.985266 / -774.941388
7-NO2 / -774.993205 / -774.986537 / -774.939133
6-NO2 / -774.996158 / -774.98725 / -774.94495
5-NO2 / -774.995858 / -774.986598 / -774.940196
4-NO2 / -774.991088 / -774.976806 / -774.937493
8a-OH / -645.835578 / -645.837199 / -645.795559
8-OH / -645.83923 / -645.837447 / -645.795
7-OH / -645.83886 / -645.840615 / -645.79421
6-OH / -645.844164 / -645.8406 / -645.794219
5-OH / -645.84324 / -645.837728 / -645.800002
4-OH / -645.840144 / -645.839623 / -645.792584
8a-SH / -968.728934 / -968.723425 / -968.678917
8-SH / -968.729875 / -968.729779 / -968.686635
7-SH / -968.737035 / -968.731708 / -968.8089399
6-SH / -968.737746 / -968.731403 / -968.686269
5-SH / -968.737022 / -968.730229 / -968.689464
4-SH / -968.737241 / -968.728196 / -968.685227

Table SI 7. Energies of reaction, zero point corrected ER and Gibbs free energies of reaction (kcal mol-1) for substituted VHF to DHAs in acetonitrile calculated at PBE0/6-31G(d,p) through Polarization Continuum Model (PCM)

Substituent / E / ZPC / Gibbs Free E
8a-formyl / -1.95 / -1.75 / -2.41
8-formyl / -2.10 / -1.58 / 0.11
7-formyl / -1.01 / -1.04 / -0.10
6-formyl / -4.00 / -3.73 / -2.83
5-formyl / -3.84 / -3.69 / -2.90
4-formyl / -6.79 / -6.37 / -5.31
8a-Br / -3.09 / -2.64 / -1.38
8-Br / 2.77 / 3.04 / 4.76
7-Br / -0.07 / -0.03 / 1.02
6-Br / -0.48 / -0.50 / 0.50
5-Br / -0.91 / -0.86 / 0.19
4-Br / -1.63 / -1.85 / -1.02
8a-Cl / -6.43 / -6.17 / -5.18
8-Cl / 1.77 / 2.03 / 3.48
7-Cl / -3.27 / -3.17 / -2.25
6-Cl / -3.26 / -3.14 / -2.20
5-Cl / -3.52 / -3.39 / -2.36
4-Cl / -4.04 / -3.93 / -2.85
8a-F / -1.65 / -1.43 / -0.62
8-F / 1.77 / 2.04 / 3.21
7-F / 0.07 / 0.17 / 0.60
6-F / -1.41 / -1.36 / -0.57
5-F / -1.41 / -1.34 / -0.6
4-F / 0.93 / 0.96 / 1.44
8a-CH3 / -3.09 / -2.64 / -1.38
8-CH3 / 2.77 / 3.04 / 4.76
7-CH3 / -0.07 / -0.03 / 1.02
6-CH3 / -0.48 / -0.50 / 0.50
5-CH3 / -0.91 / -0.86 / 0.19
4-CH3 / -1.63 / -1.85 / -1.02
8a-NH2 / 10.73 / 10.84 / 11.74
8-NH2 / 5.52 / 5.72 / 7.60
7-NH2 / 7.97 / 7.88 / 8.62
6-NH2 / 4.61 / 4.41 / 5.21
5-NH2 / 4.40 / 4.35 / 5.53
4-NH2 / 5.98 / 5.60 / 6.51
8a-NO2 / -5.09 / -4.85 / -4.02
8-NO2 / 0.02 / 0.55 / 2.55
7-NO2 / -3.76 / -3.52 / -2.59
6-NO2 / -6.10 / -5.77 / -4.63
5-NO2 / -6.19 / -5.89 / -4.78
4-NO2 / -8.63 / -8.25 / -7.22
8a-OH / 3.55 / 3.40 / 4.24
8-OH / 1.47 / -35.88 / 3.28
7-OH / 3.87 / 3.70 / 4.35
6-OH / 0.85 / 0.70 / 1.47
5-OH / 0.05 / -0.01 / 0.95
4-OH / 3.08 / 2.90 / 3.62
8a-SH / -2.01 / -1.92 / -0.87
8-SH / 1.49 / 1.75 / 3.52
7-SH / -1.21 / -1.21 / -0.21
6-SH / -1.85 / -1.76 / -0.62
5-SH / -2.23 / -2.13 / -1.05
4-SH / -3.12 / -3.21 / -2.25
8-N / -9.84 / -9.16 / -8.07
7-N / -10.09 / -9.66 / -8.39
6-N / -4.78 / -4.43 / -3.49
5-N / -4.45 / -3.91 / -2.96
4-N / -9.10 / -8.46 / -7.18
H / 1.03 / 1.04 / 0.16

Table SI 8. Activation energies, zero point corrected activation energies and Gibbs free energies of activation (kcal mol-1) for substituted VHF to DHAs electrocyclization in acetonitrile calculated at PBE0/6-31G(d,p) through Polarization Continuum Model (PCM)

Substituent / E / ZPC / Gibbs Free E
8a-formyl / 25.79 / 24.76 / 25.25
8-formyl / 23.26 / 22.39 / 23.11
7-formyl / 28.10 / 27.00 / 26.93
6-formyl / 24.45 / 21.86 / 24.14
5-formyl / 25.74 / 24.75 / 25.08
4-formyl / 22.25 / 21.63 / 22.32
8a-Br / 23.84 / 22.97 / 23.66
8-Br / 24.01 / 23.26 / 23.92
7-Br / 24.81 / 23.87 / 39.88
6-Br / 25.25 / 24.39 / 24.71
5-Br / 24.26 / 23.37 / 23.83
4-Br / 24.76 / 23.67 / 23.87
8a-Cl / 26.45 / 25.59 / 26.12
8-Cl / 24.97 / 24.05 / 24.52
7-Cl / 25.15 / 24.20 / 24.71
6-Cl / 25.73 / 24.78 / 25.17
5-Cl / 24.57 / 23.64 / 24.17
4-Cl / 24.27 / 23.37 / 23.97
8a-F / 27.72 / 26.63 / 26.94
8-F / 24.85 / 24.21 / 24.94
7-F / 24.06 / 23.31 / 23.63
6-F / 25.17 / 24.39 / 25.00
5-F / 24.21 / 23.31 / 23.86
4-F / 26.26 / 25.31 / 25.35
8a-CH3 / 23.84 / 22.97 / 23.66
8-CH3 / 24.01 / 23.26 / 23.92
7-CH3 / 24.81 / 23.87 / 39.88
6-CH3 / 25.25 / 24.39 / 24.71
5-CH3 / 24.26 / 23.37 / 23.83
4-CH3 / 24.76 / 23.67 / 23.87
8a-NH2 / 24.65 / 23.57 / 23.88
8-NH2 / 17.96 / 17.76 / 18.27
7-NH2 / 24.09 / 22.52 / 23.93
6-NH2 / 26.19 / 25.14 / 25.67
5-NH2 / 23.39 / 22.52 / 23.34
4-NH2 / 27.29 / 25.99 / 25.97
8a-NO2 / 25.03 / 23.89 / 24.15
8-NO2 / 24.34 / 23.32 / 24.29
7-NO2 / 28.13 / 27.00 / 27.12
6-NO2 / 24.44 / 23.37 / 24.08
5-NO2 / 26.50 / 25.50 / 26.03
4-NO2 / 22.66 / 21.89 / 22.64
8a-OH / 26.08 / 24.95 / 24.93
8-OH / 21.21 / 20.78 / 20.88
7-OH / 24.25 / 31.17 / 23.94
6-OH / 22.06 / 21.58 / 21.73
5-OH / 22.68 / 21.90 / 22.52
4-OH / 26.25 / 25.44 / 25.86
8a-SH / 25.77 / 24.74 / 25.30
8-SH / 23.69 / 23.15 / 24.11
7-SH / 25.27 / 24.53 / 25.11
6-SH / 24.94 / 24.32 / 25.06
5-SH / 23.39 / 22.62 / 23.27
4-SH / 24.71 / 23.73 / 24.02
8-N / 20.77 / 19.84 / 20.58
7-N / 29.35 / 28.21 / 28.30
6-N / 24.56 / 23.53 / 24.16
5-N / 28.18 / 27.33 / 27.77
4-N / 25.18 / 24.26 / 24.85
H / 25.94 / 25.05 / 24.46

Table SI 9. Activation energies, zero point corrected activation energies and Gibbs free energies (kcal mol-1) of activation for substituted VHF to DHAs electrocyclization in the gas phase calculated at PBE0/6-31G(d,p)

Eact
Substituent / Total Energy / ZPC Energy / G F energy
Parent / 26.86 / 26.86 / 27.40
8a-formyl / 29.36 / 28.15 / 28.92
8-formyl / 26.73 / 25.59 / 26.08
7-formyl / 31.29 / 29.84 / 30.32
6-formyl / 27.28 / 26.11 / 26.72
5-formyl / 29.46 / 28.13 / 28.56
4-formyl / 24.46 / 23.69 / 24.37
8a-Br / 30.32 / 29.07 / 29.54
8-Br / 27.72 / 26.50 / 27.24
7-Br / 28.08 / 26.86 / 27.47
6-Br / 28.99 / 27.75 / 28.31
5-Br / 27.49 / 26.31 / 26.92
4-Br / 27.37 / 26.24 / 26.86
8a-Cl / 30.65 / 29.43 / 29.94
8-Cl / 28.27 / 27.10 / 27.70
7-Cl / 28.02 / 26.81 / 27.42
6-Cl / 29.09 / 27.84 / 28.39
5-Cl / 34.10 / 33.12 / 33.72
4-Cl / 27.57 / 26.39 / 26.97
8a-F / 31.73 / 30.35 / 30.67
8-F / 28.98 / 27.82 / 28.37
7-F / 26.70 / 25.56 / 26.16
6-F / 29.54 / 28.26 / 28.79
5-F / 26.43 / 25.36 / 25.98
4-F / 29.98 / 28.65 / 29.16
8a-CH3 / 26.93 / 26.00 / 26.85
8-CH3 / 27.00 / 25.86 / 26.49
7-CH3 / 27.30 / 25.84 / 26.35
6-CH3 / 27.43 / 26.20 / 26.61
5-CH3 / 26.98 / 25.84 / 26.35
4-CH3 / 27.45 / 26.13 / 26.54
8-N / 23.78 / 22.62 / 23.41
7-N / 31.96 / 30.70 / 31.08
6-N / 27.21 / 25.98 / 26.53
5-N / 32.47 / 31.15 / 31.58
4-N / 27.32 / 26.16 / 26.87
8a-NH2 / 27.36 / 26.20 / 27.10
8-NH2 / 25.00 / 23.89 / 24.46
7-NH2 / 24.35 / 23.37 / 23.98
6-NH2 / 29.42 / 28.34 / 28.80
5-NH2 / 23.16 / 22.52 / 23.00
4-NH2 / 27.30 / 26.28 / 26.79
8a-NO2 / 30.24 / 28.96 / 29.86
8-NO2 / 28.14 / 26.88 / 27.53
7-NO2 / 30.93 / 29.45 / 29.75
6-NO2 / 27.04 / 25.84 / 26.54
5-NO2 / 30.20 / 28.76 / 29.12
4-NO2 / 24.99 / 24.14 / 24.67
8a-OH / 26.87 / 25.48 / 26.13
8-OH / 26.89 / 25.95 / 26.64
7-OH / 29.84 / 28.60 / 29.12
6-OH / 29.84 / 28.60 / 29.10
5-OH / 23.74 / 22.93 / 23.67
4-OH / 30.52 / 29.10 / 29.52
8a-SH / 28.67 / 27.47 / 27.93
8-SH / 27.54 / 26.41 / 27.07
7-SH / 29.36 / 28.08 / -48.46
6-SH / 28.91 / 27.73 / 28.32
5-SH / 25.85 / 1.33 / 25.58
4-SH / 27.41 / 26.23 / 26.96

Table SI 10. Total reaction energies, zero point corrected reaction energies and Gibbs free energies of reaction (kcal mol-1) for substituted VHF to DHAs electrocyclization in the gas phase calculated at PBE0/6-31G(d,p)

ER
Substituent / Total Energy / ZPC Energy / G F energy
Parent / -4.27 / -4.27 / -3.31
8a-formyl / -0.25 / -0.28 / 0.53
8-formyl / -3.59 / -3.02 / -1.36
7-formyl / -3.14 / -3.11 / -2.18
6-formyl / -5.29 / -5.08 / -4.25
5-formyl / -5.61 / -5.41 / -4.53
4-formyl / -8.04 / -7.61 / -6.63
8a-Br / -8.72 / -8.40 / -7.60
8-Br / -1.74 / -1.49 / 0.06
7-Br / -4.60 / -4.45 / -3.50
6-Br / -5.59 / -5.45 / -4.45
5-Br / -5.77 / -5.59 / -4.61
4-Br / -6.90 / -6.64 / -5.57
8a-Cl / -7.41 / -7.00 / -6.02
8-Cl / -0.76 / -0.41 / 1.04
7-Cl / -5.71 / -5.52 / -4.53
6-Cl / -5.59 / -5.40 / -4.40
5-Cl / -5.81 / -5.61 / -4.62
4-Cl / -6.60 / -6.40 / -5.38
8a-F / -2.00 / -1.64 / -0.82
8-F / -1.04 / -0.65 / 0.58
7-F / -2.43 / -2.24 / -1.46
6-F / -4.33 / -4.17 / -3.25
5-F / -4.31 / -4.13 / -3.19
4-F / -1.94 / -1.85 / -1.11
8a-CH3 / -6.11 / -5.53 / -4.22
8-CH3 / -0.43 / -0.04 / 1.66
7-CH3 / -3.42 / -4.34 / -3.31
6-CH3 / -4.07 / -4.00 / -3.01
5-CH3 / -4.48 / -4.34 / -3.31
4-CH3 / -4.99 / -5.13 / -4.34
8-N / -10.24 / -9.51 / -8.46
7-N / -13.18 / -12.49 / -11.27
6-N / -6.26 / -5.89 / -4.91
5-N / -12.34 / -11.98 / -10.99
4-N / -11.32 / -10.63 / -9.35
8a-NH2 / 8.27 / 8.03 / 9.19
8-NH2 / 0.85 / 0.74 / 2.10
7-NH2 / 2.48 / 2.42 / 3.26
6-NH2 / -1.74 / -1.79 / -0.86
5-NH2 / -1.95 / -1.90 / -0.83
4-NH2 / -0.79 / -0.95 / -0.02
8a-NO2 / -6.99 / -6.58 / -5.64
8-NO2 / -0.68 / -0.13 / 1.65
7-NO2 / -5.46 / -5.18 / -4.18
6-NO2 / -6.97 / -6.64 / -5.59
5-NO2 / -7.18 / -6.86 / -5.81
4-NO2 / -10.51 / -9.96 / -8.96
8a-OH / 0.26 / 0.17 / 1.02
8-OH / -3.01 / -2.52 / -1.12
7-OH / 0.37 / 0.30 / 1.10
6-OH / -3.16 / -3.11 / -2.24
5-OH / -4.75 / -4.49 / -3.46
4-OH / -0.96 / -1.12 / -0.33
8a-SH / -4.74 / -4.51 / -3.46
8-SH / -1.91 / -1.60 / -0.06
7-SH / -4.50 / -4.37 / -3.34
6-SH / -5.24 / -5.07 / -3.98
5-SH / -5.54 / -5.34 / -4.26
4-SH / -7.11 / -6.97 / -5.68

Cartesian Coordinates

Parent DHA (unsubstituted) at PBE0

C 0.03278900 -0.04192600 -0.00253400

C 0.00846600 -0.09772500 1.35541700

C 1.15257400 -0.05891700 2.22101100

C 1.21111100 0.10258200 -0.81947600

C 2.38269200 -0.51388900 1.89821900

C 2.43757900 -0.36674200 -0.53593400

C 2.67170000 -1.28187400 0.63002800

H -0.92321000 0.03941100 -0.51328500

H -0.96408900 -0.05120600 1.83846800

H 1.01002400 0.36889900 3.21053400

H 1.08904600 0.66576600 -1.74168100

H 3.27463900 -0.10448600 -1.17608800

C 3.58574500 -0.45683800 2.69822900

H 3.65262400 0.07417600 3.64072400

C 4.58582100 -1.14757000 2.14538400

H 5.58839400 -1.28440100 2.52815200

C 4.15485200 -1.78803200 0.82812900

H 2.00365800 -2.14744700 0.55259000

C 4.18759500 -3.25095800 0.95090600

C 5.06798200 -1.39117700 -0.24885100

N 4.19273600 -4.39502900 1.08250300

N 5.79836500 -1.05521000 -1.07355800

Parent unsubstituted VHF at PBE0

C 0.01820300 0.02271700 0.00474300

C 0.02964000 0.05593300 1.36560200

C 1.17064800 0.03390400 2.22406300

C 1.14467500 -0.02870400 -0.87147300

C 2.49289900 0.15639000 1.92372700

C 2.47201500 0.09765100 -0.59480600

C 3.15363000 0.34169600 0.65390000

H -0.95459800 0.00335000 -0.48036700

H -0.93484100 0.05878000 1.86724100

H 0.90051500 -0.15919500 -1.92343900

H 3.13429700 0.04982200 -1.45772400

C 5.42956500 1.01185000 1.58270700

H 6.47344100 0.78064200 1.37495500

C 4.51772900 0.60466200 0.58089700

H 4.97770700 0.44506500 -0.39227900

C 5.24037200 1.72922800 2.74885400

C 4.01791300 2.36297500 3.10204000

C 6.34945900 1.96454800 3.61390200

N 7.25968800 2.14529600 4.31524000

N 3.01658600 2.89288700 3.37032900

H 3.16661400 0.08674200 2.77195700

H 0.94662400 -0.08278400 3.28160000

TS for VHF to DHA (unsubstituted)

C 0.00112700 -0.02123800 -0.01459700

C -0.00870200 -0.04082000 1.40093600

C 1.05098600 -0.01199000 2.27568900

C 2.43957800 -0.04020300 2.00626900

C 3.04787900 0.01181300 0.77475600

C 2.46722900 0.16105900 -0.50284700

C 1.13115800 0.15204500 -0.86709400

C 0.73090000 0.42968100 -2.25050700

C -0.29852500 1.28600800 -2.38886700

C -0.87433600 1.90794100 -1.17810400

C -0.09304700 2.80816000 -0.41771500

C -2.28034100 1.94699300 -1.03138300

N -3.44032100 1.90431700 -0.90889600

N 0.59108900 3.49235400 0.23558800

H -0.90084600 -0.37154300 -0.50248400

H -0.99730900 -0.11083000 1.84810000

H 0.78409700 -0.03719700 3.33019800

H 3.09232300 -0.10021400 2.87234200

H 4.13560300 -0.01381500 0.78187100

H 3.17053900 0.30860100 -1.31878000

H 1.30151800 0.04696500 -3.09142600

H -0.69961600 1.53965100 -3.36878200