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[S1]
Supporting Information
for
Pyridyl vs bipyridyl anchoring groups of
porphyrin sensitizers for dye sensitized solar
cells
Panagiotis A. Angaridis,† Eleftherios Ferentinos,§ Georgios Charalambidis,§ Kalliopi
Ladomenou,§ Vasilis Nikolaou,§ S. Biswas, § Ganesh D. Sharma,‡* and Athanassios G.
Coutsolelos§*
† Department of Chemistry, Aristotle University of Thessaloniki, Thessaloniki 54124,
Greece
§ Department of Chemistry, University of Crete, Laboratory of Bioinorganic
Figure S1. ORTEP representation of X-ray crystal structure of 2b(THF) with all
atoms represented by thermal ellipsoids at the 35% probability level ...........S3
Table S1. Crystal data and structure refinement for 2b(THF)........................................S4
Table S2. Atomic coordinates (×104) and equivalent isotropic displacement
parameters (Å2×103) for 2b(THF) ..................................................................S5
Table S3. Bond lengths (Å) and angles (°) for 2b(THF) ................................................S7
Table S4. Anisotropic displacement parameters (Å2×103) for 2b(THF) ......................S16
Table S5. Hydrogen coordinates (×104) and isotropic displacement parameters
(Å2×103) for 2b(THF)...................................................................................S18
Table S6. Torsion angles (°) for 2b(THF) ....................................................................S20
Figure S2: 1H NMR spectrum of 1a...............................................................................S26
Figure S3: Aromatic region of the 1H NMR spectrum of 1a .........................................S26
Figure S4: 1H NMR spectrum of 3a...............................................................................S27
Figure S5: 13C NMR spectrum of 3a..............................................................................S27
Figure S6: Aromatic region of the 13C NMR spectrum of 3a ........................................S28
Figure S7: 1H NMR spectrum of 1b...............................................................................S28
Figure S8: Aromatic region of the 1H NMR spectrum of 1b .........................................S29
Figure S9: 13C NMR spectrum of 1b .............................................................................S29
Figure S10: Aromatic region of the 13C NMR spectrum of 1b ........................................S30
Figure S11: 1H NMR spectrum of 2b...............................................................................S30
Figure S12: 13C NMR spectrum of 2b .............................................................................S31
Figure S13: Aromatic region of the 13C NMR spectrum of 2b ........................................S31
Figure S14: 1H NMR spectrum of 3b...............................................................................S32
Figure S15: Aromatic region of the 1H NMR spectrum of 3b .........................................S32
Figure S16: 13C NMR spectrum of 3b .............................................................................S33
Figure S17: Aromatic region of the 13C NMR spectrum of 3b ........................................S33
Table S7: Cartesian coordinates of geometry optimized structure of 3a by DFT
calculation in THF........................................................................................S34
Table S8: Cartesian coordinates of geometry optimized structure of 3b by DFT
calculation in THF........................................................................................S36
[S3]
Figure S1. ORTEP representation of X-ray crystal structure of 2b(THF) with all
atoms represented by thermal ellipsoids at the 35% probability level.
[S4]
Table S1. Crystal data and structure refinement for 2b(THF).
_____________________________________________________________________Empirical formula C44 H38 N6 O ZnFormula weight 732.17Temperature 292(2) KWavelength 0.71073 ÅCrystal system MonoclinicSpace group C2/cUnit cell dimensions a = 21.201(7) Å α= 90°
b = 10.863(2) Å β= 98.94(4)°c = 32.160(6) Å γ = 90°
Volume 7317(3) Å3
Z 8Density (calculated) 1.329 g/cm3
Absorption coefficient 0.715 mm-1
F(000) 3056Crystal size 0.40 x 0.40 x 0.30 mm3
Theta range for data collection 1.94 to 29.37°Index ranges -27<=h<=28, -14<=k<=14, -43<=l<=43Reflections collected 47595Independent reflections 9536 [R(int) = 0.1188]Completeness to theta = 25.00° 99 % Absorption correction NumericalMax. and min. transmission 0.6868 and 0.6203Refinement method Full-matrix least-squares on F2
Data / restraints / parameters 9536 / 0 / 509Goodness-of-fit on F2 1.035Final R indices [I>2sigma(I)] R1 = 0.0680, wR2 = 0.0981R indices (all data) R1 = 0.1568, wR2 = 0.1178Largest diff. peak and hole 0.391 and -0.661 e.Å-3
Figure S3. Aromatic region of the 1H NMR spectrum of 1a (300 MHz, CDCl3 + 1% Et3N).
[S27]
Figure S4. 1H NMR spectrum of 3a (500 MHz, THF-d8).
Figure S5. 13C NMR spectrum of 3a (125 MHz, THF-d8).
[S28]
Figure S6. Aromatic region of the 13C NMR spectrum of 3a (125 MHz, THF-d8).
Figure S7. 1H NMR spectrum of 1b (500 MHz, CDCl3).
[S29]
Figure S8. Aromatic region of the 1H NMR spectrum of 1b (500 MHz, CDCl3).
Figure S9. 13C NMR spectrum of 1b (75 MHz, CDCl3).
[S30]
Figure S10. Aromatic region of the 13C NMR spectrum of 1b (75 MHz, CDCl3).
Figure S11. 1H NMR spectrum of 2b (500 MHz, CDCl3).
[S31]
Figure S12. 13C NMR spectrum of 2b (125 MHz, CDCl3).
Figure S13. Aromatic region of the 13C NMR spectrum of 2b (125 MHz, CDCl3).
[S32]
Figure S14. 1H NMR spectrum of 3b (500 MHz, THF-d8).
Figure S15. Aromatic region of the 1H NMR spectrum of 3b (500 MHz, THF-d8).
[S33]
Figure S16. 13C NMR spectrum of 3b (75 MHz, THF-d8).
Figure S17. Aromatic region of the 13C NMR spectrum of 3b (75 MHz, THF-d8).
[S34]
Table S7. Cartesian coordinates of geometry optimized structure of 3a in THF at the B3LYP/LANL2DG/6-31G* level with energy. E = -6830.9978981 Hartree/particle.
C 1.716452000 -3.600442000 2.453999000
C 0.805060000 -3.999410000 3.501758000
C 1.132975000 -3.279127000 4.609545000
C 2.254599000 -2.435049000 4.255862000
N 2.582563000 -2.645849000 2.937910000
C 1.743203000 -4.089659000 1.137492000
C 2.888776000 -1.525706000 5.128587000
C 3.951105000 -0.660392000 4.791620000
C 4.619956000 0.230763000 5.715833000
C 5.587234000 0.885372000 5.016338000
C 5.528299000 0.398184000 3.657471000
N 4.528871000 -0.542619000 3.550058000
C 6.346997000 0.799998000 2.589033000
C 6.348445000 0.336214000 1.261563000
C 7.183601000 0.815443000 0.184774000
C 6.850196000 0.099826000 -0.924727000
C 5.814292000 -0.833854000 -0.538679000
N 5.524721000 -0.662269000 0.795050000
C 5.196171000 -1.756452000 -1.410511000
C 4.150778000 -2.638959000 -1.061298000
C 3.567613000 -3.619727000 -1.951210000
C 2.600205000 -4.275249000 -1.252199000
C 2.585168000 -3.710375000 0.077115000
N 3.538736000 -2.722601000 0.167652000
C 5.688359000 -1.802582000 -2.824236000
Br 7.637642000 2.170695000 2.995434000
C 2.390059000 -1.474364000 6.539821000
C 6.979795000 -2.250301000 -3.129436000
[S35]
C 7.434976000 -2.294112000 -4.449522000
C 6.623882000 -1.891525000 -5.519670000
C 5.329458000 -1.442164000 -5.203510000
C 4.868595000 -1.398277000 -3.890327000
C 2.570166000 -2.551259000 7.419300000
C 2.088590000 -2.452330000 8.724904000
C 1.280383000 -0.349227000 8.363155000
C 1.723813000 -0.346921000 7.040373000
C 7.091469000 -1.925294000 -6.985749000
C 7.030298000 -0.496786000 -7.578180000
C 8.535377000 -2.442930000 -7.128616000
C 6.161767000 -2.856950000 -7.799891000
Zn 4.044348000 -1.643716000 1.862180000
N 1.451294000 -1.376272000 9.207322000
Br 0.456574000 -5.463959000 0.730672000
H 0.014219000 -4.727348000 3.400458000
H 0.651274000 -3.313411000 5.575864000
H 4.387804000 0.338803000 6.765312000
H 6.281657000 1.624299000 5.386614000
H 7.919323000 1.601393000 0.265492000
H 7.263720000 0.199538000 -1.917361000
H 3.865330000 -3.790201000 -2.975253000
H 1.962173000 -5.073555000 -1.599957000
H 7.635889000 -2.577715000 -2.327121000
H 8.441315000 -2.654739000 -4.631444000
H 4.661815000 -1.114547000 -5.995600000
H 3.863802000 -1.038406000 -3.685087000
H 3.085422000 -3.450078000 7.093692000
H 2.226162000 -3.280528000 9.418686000
H 0.758388000 0.519280000 8.762385000
[S36]
H 1.547128000 0.516971000 6.406446000
H 7.353179000 -0.506505000 -8.626286000
H 7.687905000 0.184986000 -7.026557000
H 6.016345000 -0.084131000 -7.546106000
H 8.821524000 -2.446029000 -8.186357000
H 8.641480000 -3.468152000 -6.755524000
H 9.251679000 -1.808039000 -6.594594000
H 5.120541000 -2.518515000 -7.774050000
H 6.192172000 -3.880424000 -7.408505000
H 6.477614000 -2.884973000 -8.849878000
Table S7. Cartesian coordinates of geometry optimized structure of 3b in THF at the B3LYP/LANL2DG/6-31G* level with energy. E=-7078.0874628 Hartree/particle.