The role of terminal groups in electronic structures and related properties: The case of push–pull porphyrin dye sensitizers for solar cells

Zhang, Cai‐Rong; Han, Li-Heng; Zhe, Jian-Wu; Jin, Neng-Zhi; Yu-jie, Shen; Gong, Ji‐Jun; Zhang, Haimin; Chen, Yuhong; Liu, Zi‐Jiang

doi:10.1016/j.comptc.2014.04.035

Cited by 13 publications

(10 citation statements)

References 86 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Furthermore, the absolute values of ∆ G inject for Q bands are smaller than that of B bands. The tendency agrees with that of other porphyrin dyes, such as YD2- o -C8 [ 39 , 44 ]. This suggests that the rate of electron injection from B bands might be faster than that from Q bands.…”

Section: Resultssupporting

confidence: 86%

“…Also, the torsion between porphyrin units is favorable for the reduction of dye aggregation and the inhibition of the approach of electrolyte to the semiconductor in the electrode. The introduction of rigid ethynyl in the conjugate bridges guarantees the existence of a molecular axis, which is helpful to generate a larger dipole moment and a suitable molecular orientation when dye sensitizers are adsorbed on the surfaces of the semiconductor in the electrode [ 39 , 40 ], and further affect the conduction band edge of the electrode materials [ 41 ].…”

Section: Resultsmentioning

confidence: 99%

“…It can be found from the MO analysis that the tert -butyl moieties of DTBC-MP, DTBC, DTBC-TP are independent of their frontier MOs. This suggests that the tert -butyl groups play the role of reducing dye aggregation [ 53 ], blocking the approach of electrolyte to the semiconductor electrode surfaces, and suppressing charge recombination [ 39 , 44 ]. For DTBC-MP, the Q and B band transitions that involved H → L, H − 2 → L, H − 1 → L (the H and L stand for HOMO and LUMO, respectively) configurations are intra-molecular CT excitations due to the relocation of MOs between the ground and final states.…”

Section: Resultsmentioning

confidence: 99%

“…The solvent effects were considered using a polarizable continuum model (PCM) method [ 63 , 64 ]. The calculations proved that the solvent effects generated negligible influence on the geometry of porphyrin dyes [ 39 ]. Therefore, considering the computational cost and accuracy, the TDDFT calculations in solution for the dyes in this work were conducted on the optimized geometries in the gas phase.…”

Section: Methodsmentioning

confidence: 99%

See 3 more Smart Citations

The Role of Porphyrin-Free-Base in the Electronic Structures and Related Properties of N-Fused Carbazole-Zinc Porphyrin Dye Sensitizers

Zhang

et al. 2015

IJMS

Self Cite

View full text Add to dashboard Cite

Dye sensitizers can significantly affect power conversion efficiency of dye-sensitized solar cells (DSSCs). Porphyrin-based dyes are promising sensitizers due to their performances in DSSCs. Here, based upon a N-fused carbazole-zinc porphyrin-free-base porphyrin triad containing an ethynyl-linkage (coded as DTBC), the novel porphyrin dyes named DTBC-MP and DTBC-TP were designed by varying the porphyrin-free-base units in the π conjugation of DTBC in order to study the effect of porphyrin-free-base in the modification of electronic structures and related properties. The calculated results indicate that, the extension of the conjugate bridge with the porphyrin-free-base unit results in elevation of the highest occupied molecular orbital (HOMO) energies, decrease of the lowest unoccupied molecular orbital (LUMO) energies, reduction of the HOMO-LUMO gap, red-shift of the absorption bands, and enhancement of the absorbance. The free energy changes demonstrate that introducing more porphyrin-free-base units in the conjugate bridge induces a faster rate of electron injection. The transition properties and molecular orbital characters suggest that the different transition properties might lead to a different electron injection mechanism. In terms of electronic structure, absorption spectra, light harvesting capability, and free energy changes, the designed DTBC-TP is a promising candidate dye sensitizer for DSSCs.

show abstract

Section: Resultssupporting

confidence: 86%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

See 2 more Smart Citations

The Role of Porphyrin-Free-Base in the Electronic Structures and Related Properties of N-Fused Carbazole-Zinc Porphyrin Dye Sensitizers

Zhang

et al. 2015

IJMS

Self Cite

View full text Add to dashboard Cite

show abstract

“…But one thing common in those studies was the asymmetrically substituted porphyrin. There were some studies on symmetrically substituted porphyrin, but none of them systematically investigated the effect of both substituents and central ions simultaneously on the electronic and photo-physical properties [15][16][17][18].…”

Section: Introductionmentioning

confidence: 99%

Design a better metalloporphyrin semiconductor: A theoretical studies on the effect of substituents and central ions

Mulya¹,

Santoso²,

Aziz³

et al. 2016

AIP Conference Proceedings

View full text Add to dashboard Cite

A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Puwere chosen as the central metal to see the effect of the elements on the nature of the group and the same period and reviewed the effect of substituent groups pull and push the electrons to the electronic properties of complex metalloporphyrin. The DFT/B3LYP/LANL2DZ and TD-DFT calculation were used to generate the optimized structure of, electronic and photophysical properties. The parameter is an Eg complex compound, DOS, and electronic absorption spectra. The calculations showed electron donating complexes tend to be better as a semiconductor because it lowers Eg complex compounds metalloporphyrin, NH2 group gave the smallest Eg compared to other groups.

show abstract

Push‐Pull N‐Annulated Perylene‐Based Sensitizers for Dye‐Sensitized Solar Cells: Theoretical Property Tuning by DFT/TDDFT

Hadsadee

Rattanawan

Tarsang³

et al. 2017

ChemistrySelect

View full text Add to dashboard Cite

We evaluate the effects of donor and π‐linker moieties on power‐conversion efficiency for a series of push‐pull type, N‐annulated perylene dyes for dye‐sensitized solar cells. Triphenylamine and diphenylamine are used as electron donors. We investigate the structural, optical, and electronic properties of dyes by performing density functional theory (DFT) calculations at the B3LYP level, using the 6‐311G(d,p) basis set. Electronic absorption wavelengths were investigated using time dependent DFT (TD‐DFT) calculations on M062x/6‐311G(d,p) in THF. Our calculated results reveal that the diphenylamine (DPA) donor provides a small dihedral angle between diphenylamine and the perylene core, resulting in a red‐shifted absorption spectrum. Introduction of an O‐methoxy substituent into diphenylamine improves its donor properties, red‐shifts the absorption wavelength, and increases the dipole moment, indicating increased intramolecular charge transfer in the O‐methoxy substituted dye. Incorporation of a C‐C triple bond in linker extends the π‐conjugation system and decreases the dihedral angle between N‐annulated perylene and cyanoacrylic acid; the dye adopts a planar structure, causing a red‐shift in the absorption spectrum. Our results demonstrate that use of computational design can to help the experimentalist for out looking future developments to identify push‐pull perylene sensitizers for highly efficient solar cells.

show abstract

The role of terminal groups in electronic structures and related properties: The case of push–pull porphyrin dye sensitizers for solar cells

Cited by 13 publications

References 86 publications

The Role of Porphyrin-Free-Base in the Electronic Structures and Related Properties of N-Fused Carbazole-Zinc Porphyrin Dye Sensitizers

The Role of Porphyrin-Free-Base in the Electronic Structures and Related Properties of N-Fused Carbazole-Zinc Porphyrin Dye Sensitizers

Design a better metalloporphyrin semiconductor: A theoretical studies on the effect of substituents and central ions

Push‐Pull N‐Annulated Perylene‐Based Sensitizers for Dye‐Sensitized Solar Cells: Theoretical Property Tuning by DFT/TDDFT

Contact Info

Product

Resources

About