Substituent Effect on the Meso-Substituted Porphyrins: Theoretical Screening of Sensitizer Candidates for Dye-Sensitized Solar Cells

Abstract

According to the concepts of attribute axis and attribute coordinate system, porphine and 11 kinds of bridge carbon substituted porphyrins as donors and 9 common acceptors A-I have been designed and calculated at the density functional B3LYP level. The substituent effects on the molecular orbital energy levels of the porphyrin derivatives have been discussed and promising donor-acceptor combinations are screened. Several novel zinc metalloporphyrins selected were then calculated by means of the DFT/TDDFT method in THF solvent. The electronic and spectroscopic properties of ZnTPP and the selected novel zinc porphyrin complexes have been investigated as solar cell sensitizers. The results show that the candidates selected are very promising to provide good performances as sensitizers, in which ZnTPPG is promising to challenge the current photo-electric conversion efficiency record 7.1% of porphyrin-sensitized solar cells. The concepts of attribute axis and attribute coordinate system are shown very helpful for tuning the molecular properties and the rational design of functional molecules with anticipated good properties.

Influence of phenyl-attached substituents on the vibrational and electronic spectra of meso-tetraphenylporphyrin: A DFT study

“…The direction of the charge transfer is from the phenyl rings converging to the porphine center. Such charge redistribution is desirable in dye sensitizer with β-linked π-spacer as it resembles to one of ZnTMPPI in Ma et al's work [29].…”

“…To investigate the effect systematically, the influence of common electron-affecting substituents, i.e. methyl, hydroxyl, dimethylamino, methyl carboxyl, cyano and nitro groups, on the four meso-phenyl rings were speculated relying on their vibrational and electronic spectra calculated by density functional theory (DFT) [26] and time-dependent DFT (TDDFT) [27], the methods which had made a number of successful predictions in earlier theoretical studies of dye sensitizers [8,[28][29][30].…”

The effect of anchoring group number on molecular structures and absorption spectra of triphenylamine sensitizers: a computational study

“…The computational cost of TD-DFT calculation is comparative to that of a Hartree-Fock based single excitation theory, such as, configuration interaction singles (CIS) or time-dependent Hartree-Fock (TD-HF) method and maintains a uniform accuracy for open-shell and closed-shell systems. DFT has been extensively used to study the structures and absorption spectra of sensitizers for DSSCs [4,[18][19][20][21][22][23][24][25][26][27][28][29][30][31][32][33][34].…”

Density Functional Theory Study on Triphenylamine-based Dye Sensitizers Containing Different Donor Moieties

“…In recent years, DFT has been extensively used to study the structures and absorption spectra of sensitizers for DSSCs. 4,[16][17][18][19][20][21][22][23][24][25][26][27][28][29][30][31][32] Triphenylamine has been widely used as an electron donor for metal-free organic sensitizers due to its excellent electrondonating capability and aggregation resistant nonplanar molecular configuration. 33 Aggregation can give rise to self-quench- 34 which experimentally proves that the donor moiety plays a crucial role in determining the conversion efficiency of DSSC.…”