Supporting Information
Towards Thermally Stable Cyclophanediene - Dihydropyrene photoswitches
Nasir Khan,a,b Nadeem S. Sheikh,c Ather F. Khan,d Ralf Ludwig,e,f Tariq Mahmood,a Wajid U. Rehman,b Yasair S. S. Al-Faiyz,c Khurshid Ayuba,c*
aDepartment of Chemistry, COMSATS Institute of Information Technology, Abbottabad, Pakistan 22060
bDepartment of Chemistry, Hazara University, Mansehra. Pakistan
cDepartment of Chemistry, Faculty of Science, King Faisal University, P.O. Box 380, Al-Ahsa 31982 Saudi Arabia
dInterdisciplinary Research Center in Biomedical Materials, COMSATS Institute of Information Technology, Lahore, Pakistan
eDepartment of Physical Chemistry, University of Rostock, Dr.-Lorenz-Weg 1, 18059 Rostock, Germany
f Leibniz-Institut für Katalyse an der Universität Rostock e. V. Alebert-Einstein-Strasse 29a, 18059 Rostock, Germany
Correspondence
+92-992-383591-6
+92-992-383441
Table 1. Total electronic, zero point corrected and Gibbs Free energies of cyclophanedienes calculated at B3LYP/6-31+G(d)
Substituent / ReactantElectronic Energy / Zero Point Energy / Gibbs Free Energy
BF2 / -1065.0243972 / -1064.7987630 / -1064.8440430
Br2 / -5759.1258386 / -5758.9194560 / -5758.9602130
CCMe / -847.8068714 / -847.5064280 / -847.5507100
CH2Cl / -1614.6810835 / -1614.4153410 / -1614.4597700
CH2F / -893.9652811 / -893.6967170 / -893.7414140
CH2I / -14534.0366897 / -14533.7739640 / -14533.8218170
CH2NH2 / -806.1775749 / -805.8592790 / -805.9021380
CH2OH / -845.9073951 / -845.6155760 / -845.6596670
Cl / -1536.0444243 / -1535.8371160 / -1535.8761930
COCl / -1762.7223432 / -1762.4961550 / -1762.5410470
CONH2 / -954.2637356 / -953.9848390 / -954.0289910
F / -815.3535819 / -815.1428330 / -815.1808070
GeBr3 / -20196.4021704 / -20196.1895910 / -20196.2508390
H / -616.8763842 / -616.6484340 / -616.6849160
NH3+ / -728.1887817 / -727.8986360 / -727.9373680
NMe2 / -884.7973587 / -884.4234170 / -884.4672650
O- / -766.0601926 / -765.8520850 / -765.8896160
OCH3 / -845.9140334 / -845.6221550 / -845.6637980
OH / -767.3169797 / -767.0812680 / -767.1193040
PH3+ / -1301.3331608 / -1301.0687940 / -1301.1108280
PHMe / -1379.3760316 / -1379.0755150 / -1379.1213510
S- / -1412.0352269 / -1411.8331450 / -1411.8730570
SiH2Me / -1276.8920677 / -1276.5774310 / -1276.6244880
SiH3 / -1198.2346631 / -1197.9783100 / -1198.0202850
SMe / -1491.8538737 / -1491.5701020 / -1491.6143150
I / -14455.3775207 / -14455.1733480 / -14455.2160790
NHMe / -806.2001439 / -805.8828100 / -805.9241410
PH2 / -1300.7315087 / -1300.4892170 / -1300.5298010
CH2Br / -5837.7567728 / -5837.4912400 / -5837.5363200
Isobutenyl / -928.9315018 / -928.5267090 / -928.5753760
Table 2. Total electronic, zero point corrected and Gibbs Free energies of transition states from cyclophanedienes to dihydropyrenes calculated at B3LYP/6-31+G(d)
Substituent / TSElectronic Energy / Zero Point Energy / Gibbs Free Energy
BF2 / -1064.9850807 / -1064.7634540 / -1064.8086950
Br2 / -5759.0968130 / -5758.8938710 / -5758.9347560
CCMe / -847.7631764 / -847.4669530 / -847.5154950
CH2Cl / -1614.6443090 / -1614.3828640 / -1614.4262920
CH2F / -893.9169649 / -893.6529810 / -893.6946570
CH2NH2 / -806.1419056 / -805.8277350 / -805.8699100
CH2OH / -845.8724087 / -845.5845280 / -845.6270090
Cl / -1536.0065739 / -1535.8031410 / -1535.8423930
COCl / -1762.6808259 / -1762.4586400 / -1762.5036550
CONH2 / -954.2285833 / -953.9534950 / -953.9980800
F / -815.3065309 / -815.1001400 / -815.1381260
GeBr3 / -20196.3843010 / -20196.1748590 / -20196.2368630
H / -616.8330983 / -616.6100580 / -616.6462410
NH3+ / -728.1510952 / -727.8654960 / -727.9055660
NMe2 / -884.7248306 / -884.3566960 / -884.4025560
O- / -765.9958103 / -765.7891920 / -765.8270700
OCH3 / -845.8643452 / -845.5700790 / -845.6132950
OH / -767.2608810 / -767.0195240 / -767.0571080
PH3+ / -1301.2955904 / -1301.0358350 / -1301.0773410
PHMe / -1379.3441745 / -1379.0476010 / -1379.0935490
S- / -1411.9876527 / -1411.7890710 / -1411.8292970
SiH2Me / -1276.8640749 / -1276.5532840 / -1276.6008290
SiH3 / -1198.2069309 / -1197.9543450 / -1197.9966270
SMe / -1491.7980902 / -1491.5181850 / -1491.5625330
NHMe / -806.1357863 / -805.8234260 / -805.8653680
PH2 / -1300.7030827 / -1300.4652350 / -1300.5064050
CH2Br / -5837.7162057 / -5837.4559100 / -5837.5011810
Isobutenyl / -928.8827071 / -928.4825380 / -928.5319630
Table 3. Total electronic, zero point corrected and Gibbs Free energies of dihydropyrenes calculated at B3LYP/6-31+G(d)
BF2 / ProductBr2 / Electronic Energy / Zero Point Energy / Gibbs Free Energy
CCMe / -1065.0431521 / -1064.8169860 / -1064.8604950
CH2Cl / -5759.1922937 / -5758.9857470 / -5759.0277860
CH2F / -847.8236599 / -847.5220340 / -847.5697770
CH2I / -1614.7038971 / -1614.4375580 / -1614.4796870
CH2NH2 / -893.9970279 / -893.7275600 / -893.7681010
CH2OH / -14534.0503549 / -14533.7869890 / -14533.8324820
Cl / -806.2162437 / -805.8968190 / -805.9377410
COCl / -845.9368672 / -845.6444230 / -845.6863220
CONH2 / -1536.0938268 / -1535.8859750 / -1535.9254100
F / -1762.7375167 / -1762.5110130 / -1762.5557510
GeBr3 / -954.2931408 / -954.0139450 / -954.0588160
H / -815.3831918 / -815.1721620 / -815.2097620
NH3+ / -20196.4689772 / -20196.2554550 / -20196.3186890
NMe2 / -616.9083280 / -616.6803490 / -616.7161010
O- / -728.2276214 / -727.9370630 / -727.9754200
OCH3 / -884.7855356 / -884.4116410 / -884.4549180
OH / -766.0378648 / -765.8334700 / -765.8710180
PH3+ / -845.9281842 / -845.6363560 / -845.6779650
PHMe / -767.3299328 / -767.0948210 / -767.1327520
S- / -1301.3776410 / -1301.1138240 / -1301.1549080
SiH2Me / -1379.4188030 / -1379.1170410 / -1379.1611610
SiH3 / -1412.0468820 / -1411.8436250 / -1411.8827090
SMe / -1276.9364166 / -1276.6210700 / -1276.6672510
I / -1198.2843922 / -1198.0273650 / -1198.0683070
NHMe / -1491.8928163 / -1491.6081660 / -1491.6520520
PH2 / -14455.4785522 / -14455.2718730 / -14455.3154540
CH2Br / -806.1923042 / -805.8743210 / -805.9153820
Isobutenyl / -1300.7849941 / -1300.5417200 / -1300.5815840
vinyl / -5837.7747840 / -5837.5098800 / -5837.5538800
cis propenyl / -928.9347350 / -928.5294360 / -928.5794630
t propenyl / -771.6803048 / -771.3872470 / -771.4277700
BF2 / -850.2992105 / -849.9496050 / -849.9956280
Br / -850.3199655 / -849.9706540 / -850.0152800
Table 4. Energies of activation for electrocyclization of cyclophanediene to dihydropyrenes calculated at B3LYP/6-31+G(d)
Substituent / Energies of activationElectronic Energy / ZP / Gibbs Free
BF2 / 24.67147726 / 22.15673294 / 22.18120581
Br2 / 18.21383974 / 16.05483056 / 15.97450934
CCMe / 27.4190276 / 24.77093751 / 22.09774704
CH2Cl / 23.07634811 / 20.37962603 / 21.00776304
CH2F / 30.3188745 / 27.44475549 / 29.34046169
CH2I / 9120246.096 / 9120081.233 / 9120111.261
CH2NH2 / 22.38282461 / 19.79415967 / 20.22337617
CH2OH / 21.95429837 / 19.48291496 / 20.49320525
Cl / 23.75148558 / 21.31963526 / 21.2098211
COCl / 26.05250016 / 23.54101889 / 23.46383522
CONH2 / 22.0584022 / 19.66865777 / 19.39694615
F / 29.52494948 / 26.79026308 / 26.78273297
GeBr3 / 11.21321826 / 9.244469954 / 8.770072773
H / 27.16231347 / 24.08130457 / 24.26892991
NH3+ / 23.64863677 / 20.79566483 / 19.95605712
NMe2 / 45.51207177 / 41.86806135 / 40.60551224
O- / 40.40050488 / 39.46595498 / 39.24820919
OCH3 / 31.17981754 / 32.67818472 / 31.69111228
OH / 35.20246719 / 38.74494657 / 39.02858086
PH3+ / 23.57578292 / 20.68208561 / 21.01341063
PHMe / 19.99063289 / 17.51630018 / 17.44601912
S- / 29.85326245 / 27.6568537 / 27.45981572
SiH2Me / 17.56574793 / 15.1524719 / 14.84624726
SiH3 / 17.40221896 / 15.03826517 / 14.84561975
SMe / 35.00467619 / 32.57841071 / 32.49369693
I / 9070886.72 / 9070758.6 / 9070785.414
NHMe / 40.3850054 / 37.26402415 / 36.88061584
PH2 / 17.83758505 / 15.04893283 / 14.68121226
CH2Br / 25.45624064 / 22.16991064 / 22.05005632
Isobutenyl / 30.6191378 / 27.71772212 / 27.24206992
vinyl / 25.48705135 / -484016.8135 / -484042.7855
Table 5. Energies of reaction for electrocyclization of cyclophanediene to dihydropyrenes calculated at B3LYP/6-31+G(d)
Substituent / Energies of reactionElectronic energy / ZP / Gibbs Free
BF2 / -11.7689 / -11.4351 / -10.32378629
Br2 / -41.7012 / -41.5982 / -42.40269944
CCMe / -10.5349 / -9.79291 / -11.96472364
CH2Cl / -14.3158 / -13.9414 / -12.49810671
CH2F / -19.9214 / -19.3543 / -16.74634603
CH2I / -8.57504 / -8.17331 / -6.692388817
CH2NH2 / -24.265 / -23.5567 / -22.34122073
CH2OH / -18.494 / -18.1018 / -16.72626572
Cl / -31.0005 / -30.6595 / -30.88413506
COCl / -9.52152 / -9.32354 / -9.226899688
CONH2 / -18.452 / -18.2643 / -18.71547084
F / -18.5805 / -18.4042 / -18.16953757
GeBr3 / -41.9219 / -41.3303 / -42.57651957
H / -20.045 / -20.027 / -19.56888376
NH3+ / -24.3723 / -24.1133 / -23.87799149
NMe2 / 7.419108 / 7.389552 / 7.747859796
O- / 14.01091 / 11.68109 / 11.67042168
OCH3 / -8.87976 / -8.91126 / -8.889927086
OH / -8.12819 / -8.50464 / -8.438747756
PH3+ / -27.9117 / -28.2568 / -27.66061876
PHMe / -26.8395 / -26.058 / -24.98115319
S- / -7.31369 / -6.5763 / -6.056721694
SiH2Me / -27.8294 / -27.3839 / -26.83418875
SiH3 / -31.2055 / -30.7825 / -30.13426121
SMe / -24.4369 / -23.8855 / -23.680326
I / -63.3982 / -61.8254 / -62.35875656
NHMe / 4.919486 / 5.326928 / 5.49635571
PH2 / -33.5626 / -32.9461 / -32.49432444
CH2Br / -11.3022 / -11.6968 / -11.01906682
Isobutenyl / -2.02886 / -1.71122 / -2.564631327
vinyl / -13.9709 / -484053 / -484078.2542
Table 6. Energies of transition states for sigmatropic rearrangement calculated at B3LYP/6-31+G(d)
Substituent / Transition statesElectronic / ZP energy / Gibbs Free energy
BF2 / -1065.0167886 / -1064.7917870 / -1064.8352870
Br2 / -5759.1916279 / -5758.9851310 / -5759.0261990
CH2Cl / -1614.6569720 / -1614.3940430 / -1614.4369310
CH2F / -893.9407288 / -893.6748420 / -893.7163720
CH2NH2 / -806.1883097 / -805.8723030 / -805.9141930
CH2OH / -845.9035788 / -845.6132350 / -845.6549590
Cl / -1536.0925464 / -1535.8849250 / -1535.9239790
F / -815.3512087 / -815.1414420 / -815.1792090
OCH3 / -845.8890068 / -845.6003630 / -845.6423930
OH / -767.2791099 / -767.0468430 / -767.0853360
SiH2Me / -1276.9129650 / -1276.5987450 / -1276.6451240
SiH3 / -1198.2595566 / -1198.0039070 / -1198.0453830
SMe / -1491.8849222 / -1491.6012900 / -1491.6458520
NHMe / -806.1365081 / -805.8213590 / -805.8625020
isobutenyl / -928.8763776 / -928.4738180 / -928.5230560
cis propenyl / -850.2406980 / -849.8943340 / -849.9396740
T propenyl / -850.2544177 / -849.9081600 / -849.9535500
Vinyl / -771.6154311 / -771.3254770 / -771.3662560
Table 7. Energies of products for sigmatropic rearrangement calculated at B3LYP/6-31+G(d)
Substituents / ProductsElectronic energy / ZP energy / Gibbs Free energy
BF2 / -1065.0561182 / -1064.8292750 / -1064.8748420
Br2 / -5759.1927979 / -5758.9858050 / -5759.0279850
CH2Cl / -1614.7132812 / -1614.4459650 / -1614.4883210
CH2F / -894.0047657 / -893.7344490 / -893.7751990
CH2NH2 / -806.2153109 / -805.8952640 / -805.9366340
CH2OH / -845.9514036 / -845.6573050 / -845.6986240
Cl / -1536.1003727 / -1535.8918080 / -1535.9313180
F / -815.3910433 / -815.1792400 / -815.2170560
OCH3 / -845.9347108 / -845.6421470 / -845.6836820
OH / -767.3364980 / -767.1005150 / -767.1385270
SiH2Me / -1276.9462990 / -1276.6300380 / -1276.6755170
SiH3 / -1198.2923217 / -1198.0344520 / -1198.0344520
SMe / -1491.8985059 / -1491.6134500 / -1491.6579300
isobutenyl / -928.9478792 / -928.5417870 / -928.5908360
cis propenyl / -850.3110644 / -849.9608410 / -850.0067810
T propenyl / -850.3271741 / -849.9772240 / -850.0222600
Vinyl / -771.6875979 / -771.3938160 / -771.4346000
Table 8. Energies of activation for sigmatropic rearrangement calculated at B3LYP/6-31+G(d)
Substituents / Energies of activationElectronic energy / ZP energy / Gibbs Free energy
BF2 / 16.5433467 / 15.81261189 / 15.81825948
Br2 / 0.417795825 / 0.386545852 / 0.995857576
CH2Cl / 29.44594604 / 27.30607589 / 26.82979618
CH2F / 35.32822009 / 33.08104582 / 32.46043893
CH2NH2 / 17.52885037 / 15.3840229 / 14.77659371
CH2OH / 20.88878724 / 19.57076629 / 19.68058045
Cl / 0.803463164 / 0.658884975 / 0.897966095
F / 20.06969909 / 19.27709184 / 19.17229775
OCH3 / 24.58419069 / 22.58594943 / 22.32176793
OH / 31.89185257 / 30.10665079 / 29.75399045
SiH2Me / 14.71610179 / 14.00914959 / 13.88490271
SiH3 / 15.58457494 / 14.72011785 / 14.38502778
SMe / 4.953622744 / 4.314755322 / 3.8905589
NHMe / 35.01258281 / 33.23415814 / 33.18270236
isobutenyl / 36.6198229 / 34.90082337 / 35.39592837
cis propenyl / 36.71714962 / 34.68307757 / 35.11166656
T propenyl / 41.1318672 / 39.21557869 / 38.73616144
Vinyl / 40.70886305 / 38.76126182 / 38.60061938
Table 9. Energies of reaction for sigmatropic rearrangement calculated at B3LYP/6-31+G(d)
Substituents / Energies of reactionElectronic energy / ZP energy / Gibbs Free energy
BF2 / -8.136350928 / -7.711464246 / -9.002878797
Br2 / -0.31639029 / -0.036395551 / -0.124874391
CH2Cl / -5.888611899 / -5.275472366 / -5.417917023
CH2F / -4.855543009 / -4.322912946 / -4.454062431
CH2NH2 / 0.585340862 / 0.975777273 / 0.694653016
CH2OH / -9.121729096 / -8.083577379 / -7.719621869
Cl / -4.107614436 / -3.660262914 / -3.707326126
F / -4.926890839 / -4.441512241 / -4.577054293
OCH3 / -4.095503503 / -3.633907515 / -3.587471812
OH / -4.119725369 / -3.573039093 / -3.623867362
SiH2Me / -6.201299883 / -5.627505196 / -5.186993527
SiH3 / -4.97583658 / -4.447159827 / 21.24433412
SMe / -3.570278051 / -3.315760198 / -3.688500841
NHMe / 505893.3297 / 505693.7922 / 505719.5584
isobutenyl / -8.24811037 / -7.750369834 / -7.136665543
cis propenyl / -7.438434862 / -7.050696742 / -6.998613454
T propenyl / -4.523464982 / -4.122737415 / -4.38001631
Vinyl / -4.576489534 / -4.122109906 / -4.285889885
13 – NMe2
C -3.48346100 0.27023700 0.00025100
C -2.76565400 0.34689100 -1.19655400
C -1.40208400 0.68604200 -1.22325100
C -0.60161100 0.31774700 -2.41003000
C 0.60154800 -0.31486300 -2.41041100
C 1.40202100 -0.68468200 -1.22410600
C 2.76564800 -0.34579800 -1.19711800
C 3.48353300 -0.27054800 -0.00027100
C 2.76573200 -0.34705300 1.19655800
C 1.40213100 -0.68601300 1.22327700
C 0.60169800 -0.31754500 2.41001400
C -0.60148300 0.31501900 2.41041700
C -1.40204800 0.68466800 1.22411500
C -2.76559500 0.34556600 1.19712500
C -0.82315900 1.18031200 0.00068000
C 0.82310500 -1.18024100 -0.00066500
H -4.54339000 0.03288400 0.00014600
H -3.24465600 0.07155600 -2.13505000
H -1.06543900 0.50105200 -3.38049800
H 1.06532700 -0.49707400 -3.38111500
H 3.24463300 -0.06946500 -2.13533000
H 4.54349700 -0.03335500 -0.00018900
H 3.24477700 -0.07170000 2.13502600
H 1.06557000 -0.50073700 3.38049000
H -1.06518800 0.49729300 3.38113900
H -3.24454700 0.06910900 2.13531800
N -0.21158600 -2.08068900 -0.00104700
N 0.21150400 2.08077100 0.00107700
C 0.68344400 2.69042100 1.23981700
H 1.07511800 3.68520000 1.01315000
H -0.14564300 2.79233200 1.94720000
H 1.47325200 2.10393400 1.72197800
C 0.68315000 2.69178000 -1.23709400
H -0.14623400 2.79518700 -1.94390700
H 1.07560800 3.68599000 -1.00931100
H 1.47230200 2.10536700 -1.72043600
C -0.68368300 -2.69013500 -1.23981800
H 0.14541800 -2.79240200 -1.94714600
H -1.07583000 -3.68473000 -1.01317000
H -1.47319300 -2.10329100 -1.72202600
C -0.68311800 -2.69190700 1.23706700
H -1.07523400 -3.68623600 1.00919400
H 0.14625000 -2.79509700 1.94391600
H -1.47249200 -2.10578500 1.72040600
14 – NHMe
C -3.52282400 0.11306300 0.01380500
C -2.82170700 -1.08465100 -0.14666900
C -1.47748500 -1.09972000 -0.56594600
C -0.62653200 -2.27366300 -0.27040100
C 0.62658000 -2.27367100 0.27027000
C 1.47740100 -1.09970800 0.56592000
C 2.82177900 -1.08467700 0.14706300
C 3.52294200 0.11299100 -0.01338000
C 2.81670300 1.32050100 0.08349500
C 1.48254600 1.35490900 0.51116100
C 0.63883100 2.53553300 0.24507300
C -0.63874400 2.53551800 -0.24516300
C -1.48248400 1.35492900 -0.51115700
C -2.81657800 1.32053200 -0.08329500
C -0.93041900 0.13558800 -1.03103700
C 0.93026600 0.13558600 1.03086000
H -4.56446300 0.10714100 0.32177200
H -3.29115700 -2.02817900 0.12768300
H -1.09364500 -3.24945800 -0.41221600
H 1.09368400 -3.24944500 0.41222000
H 3.29129300 -2.02824800 -0.12702700
H 4.56464900 0.10700700 -0.32111200
H 3.28510000 2.24964200 -0.23715100
H 1.11782000 3.50782400 0.36526200
H -1.11770200 3.50782200 -0.36539300
H -3.28489800 2.24969200 0.23741500
N 0.13391200 0.17954300 -1.87776900
H 0.53342600 1.09326100 -2.04049600
N -0.13446100 0.17952100 1.87719100
H -0.53209800 1.09369200 2.04188600
C 0.61566300 -0.90179000 -2.71350700
H -0.22107900 -1.54047100 -3.01847000
H 1.07130800 -0.46579800 -3.60810000
H 1.36026200 -1.52883900 -2.20867000
C -0.61564800 -0.90188300 2.71322800
H 0.22165900 -1.53877900 3.02064200
H -1.07403600 -0.46576700 3.60631300
H -1.35801900 -1.53085700 2.20756400