Theoretical and experimental analysis of porphyrin derivatives with suitable anchoring groups for DSSC applications

2017 ◽  
Vol 21 (02) ◽  
pp. 88-102 ◽  
Author(s):  
Nora A. Sánchez-Bojorge ◽  
Simón Flores-Armendáriz ◽  
María E. Fuentes-Montero ◽  
Victor H. Ramos-Sánchez ◽  
Gerardo Zaragoza-Galán ◽  
...  
Keyword(s):  
Energy Levels ◽  
Dye Sensitized Solar Cells ◽  
Semiempirical Method ◽  
Basis Set ◽  
Orbital Energy ◽  
Geometrical Parameters ◽  
H Nmr ◽  
Porphyrin Derivatives ◽  
Lowest Unoccupied Molecular Orbital ◽  
Anchoring Groups

In this contribution, different porphyrin derivatives were experimentally synthesized and theoretically analyzed using several electronic structure methods to study the geometrical and electronic properties of A4, trans-A2B[Formula: see text]and A3B porphyrins bearing several functional groups (–OH, –COOH, -3,5-di-[Formula: see text]Bu, –OCH2CH2CH2COOEt and –OMe) suitable to be employed as dyes in Dye Sensitized Solar Cells (DSSC). A4 (R [Formula: see text] -H, -OMe, -OH, -3,5-di-tert-butyl, –OCH2CH2CH2COOEt) and A3B (R[Formula: see text][Formula: see text]R[Formula: see text][Formula: see text]R[Formula: see text][Formula: see text]–H; R[Formula: see text][Formula: see text]–OH and R[Formula: see text][Formula: see text]-3,5-di-[Formula: see text]Bu) porphyrins were synthesized and characterized by UV-vis and 1H NMR spectroscopies for comparison. The geometrical parameters were analyzed in the ground state and gas phase using the semiempirical method PM6 and the DFT functionals M06-2X and B3LYP, in combination with the 6-31G(d), DZVP and TZVP basis set. For calculations of the electronic and excited state properties, CAM-B3LYP, M06-2X and HSE06, using SMD as solvation model, were applied. This study revealed that HSE06/DZVP protocol is the best methodology to simulate electronic spectra in these porphyrin derivatives. Indeed, whereas substituent groups did not significantly affect the geometrical structure of the porphyrin derivatives studied, they do influence their electronic structures, mainly in the LUMO (lowest unoccupied molecular orbital) energy levels.

scholarly journals Effect of the second chromophore energy gap on photo-induced electron injection in di-chromophoric porphyrin-sensitized solar cells

2018 ◽  
Vol 5 (9) ◽  
pp. 181218 ◽  
Author(s):  
Long Zhao
Keyword(s):  
Solar Cells ◽  
Energy Gap ◽  
Dye Sensitized Solar Cells ◽  
Orbital Energy ◽  
Charge Generation ◽  
Organic Chromophores ◽  
Main Charge ◽  
Lowest Unoccupied Molecular Orbital ◽  
Organic Chromophore ◽  
Sensitized Solar Cells

This work investigates the effect of the second chromophore energy gap on charge generation in porphyrin-based di-chromophoric dye-sensitized solar cells (DSSCs). Three di-chromophoric porphyrin dyes (PorY, PorO and PorR) containing three organic chromophores with decreasing frontier orbital energy offsets, including a carbazole-triphenylamine chromophore (yellow, Y), a carbazole fused-thiophene chromophore (orange, O) or a carbazole-thiophene benzothiadiazole thiophene chromophore (red, R), were investigated using optical and electrochemical methods, steady-state photoluminescence and photovoltaic device characterization. Energy transfer from the organic chromophore to the porphyrin was suggested in PorY and PorO as the main charge generation mechanism in DSSCs using these di-chromophoric dyes. On the other hand, electron transfer from the photo-excited porphyrin to the organic chromophore as a competing pathway leading to the loss of photocurrent is suggested for PorR-sensitized solar cells. The latter pathway leading to a loss of photocurrent is due to the lower lying lowest unoccupied molecular orbital of the additional organic chromophore (R) and suggests the limitation of the current di-chromophoric approach to increase the overall efficiency of DSSCs.

Computational Study on Triphenylamine-Based Dyes Containing Benzimidazole Units for Dye-Sensitized Solar Cells

2013 ◽  
Vol 668 ◽  
pp. 110-114
Author(s):  
Zhong Quan Wan ◽  
Lin Lei Zhou ◽  
Chun Yang Jia ◽  
Xiao Jun Yao ◽  
Yu Shi
Keyword(s):  
Absorption Spectra ◽  
Molecular Orbital ◽  
High Efficiency ◽  
Computational Study ◽  
Electronic Absorption Spectra ◽  
Energy Levels ◽  
Dye Sensitized Solar Cells ◽  
Conduction Band Edge ◽  
Tio2 Electrode ◽  
Lowest Unoccupied Molecular Orbital

Three novel dyes (D1, D2 and D3) containing triphenylamine (TPA) unit as core and bearing different benzimidazole units as secondary electron-donors are designed. The geometries, electronic structures, and electronic absorption spectra of these dyes are studied by DFT and TD-DFT. The optimized results indicate that these dyes are all non-coplanar, which can help to inhibit the close intermolecular π-π stacking aggregation effectively. The lowest unoccupied molecular orbital (LUMO) energy levels of the dyes are higher than the conduction band edge of the TiO2, which ensures a high efficiency of electron transfer from these dyes to TiO2 electrode. As the highest occupied molecular orbital (HOMO) energy levels of these dyes are lower than those of I-/I-3, these molecules that lose electrons could be restored by getting electrons from electrolyte. The absorption spectra of these dyes are simulated, and the calculated results indicate that D3 can absorb more photons than those of D1, D2 and TPAR in the region from 250 to 580 nm, which should have the best performance of photo-to-electric conversion efficiency.

Synthesis of a new W-type of functional polymer for improving intermolecular charge transfer processes at donor/acceptor interfaces

2019 ◽  
Vol 31 (5) ◽  
pp. 521-527 ◽  
Author(s):  
Yun-Fan Zhang ◽  
Fawen Wu
Keyword(s):  
Charge Transfer ◽  
Energy Gap ◽  
Energy Levels ◽  
Coupling Reaction ◽  
Photocurrent Density ◽  
Orbital Energy ◽  
Functional Polymer ◽  
Suzuki Coupling Reaction ◽  
Donor Acceptor ◽  
Lowest Unoccupied Molecular Orbital

Optimizing charge transfer (CT) processes at donor/acceptor interfaces is an important subject to improving photocurrent density. Geometries of functional polymers play important roles in design of new types of polymers, which were used as electron donor to improve effective separation of electron-hole pairs at donor/acceptor interfaces. In this article, a novel W-type of polymer, poly(1-[4-(9-(2-ethylhexyl)carbazole-3-yl)]phenylazo-2-phenylazoacenaphthylene), was synthesized by a Suzuki coupling reaction for improving interaction between polymers and electron acceptors to enhance intermolecular CT. Geometry of combination of the polymer and C60 shows that main-chain of the polymer could sufficiently touch C60 derivatives. The polymer exhibited a broadband light absorption at the wavelength range from 250 to 650 nm. Ultraviolet–visible spectra and cyclic voltammetry curve suggest that the highest occupied, lowest unoccupied molecular orbital energy levels, and energy gap values are −5.09, −3.18 and 1.91 eV. Fluorescence quenching experiments shows that 99.9% of emission fluorescence of the polymer was quenched by added C60. Therefore, excited electrons at the polymer would be completely transferred to C60 molecules. This article suggests a new W-type functional polymer for improving intermolecular CT processes at donor/acceptor interfaces.

Molecular Orbital Calculations of Cu-Halides

1981 ◽  
Vol 36 (10) ◽  
pp. 1095-1099 ◽  
Author(s):  
H. Itoh
Keyword(s):  
Ab Initio ◽  
Molecular Orbital ◽  
Energy Levels ◽  
Basis Set ◽  
Orbital Energy ◽  
Ionic Character ◽  
Molecular Orbital Calculations ◽  
Ab Initio Hf ◽  
Mo Theory

An ab initio HF MO theory is applied to CuX, CuX2 (X = F and Cl) and (CuCl)3 . Although the detailed sequence of energy levels depends upon the basis set used, high-lying orbital energy levels have largely halogen p-like character, whereas low-lying orbital energy levels have largely Cu 3 d-like character. This is in agreement with the chemical intuition of a highly ionic character of these compounds.

Synthesis, crystal structure and photophysical properties of 1,4-bis(1,3-diazaazulen-2-yl)benzene: a new π building block

2018 ◽  
Vol 74 (2) ◽  
pp. 171-176
Author(s):  
Peili Sun ◽  
Zongyao Zhang ◽  
Hongxia Luo ◽  
Pu Zhang ◽  
Yujun Qin ◽  
...  
Keyword(s):  
Molecular Orbital ◽  
Building Block ◽  
Photophysical Properties ◽  
Condensation Reaction ◽  
Energy Levels ◽  
Three Dimensional ◽  
Experimental Result ◽  
Monoclinic System ◽  
H Nmr ◽  
Lowest Unoccupied Molecular Orbital

A dimerized 1,3-diazaazulene derivative, namely 1,4-bis(1,3-diazaazulen-2-yl)benzene [or 2,2′-(1,4-phenylene)bis(1,3-diazaazulene)], C22H14N4, (I), has been synthesized successfully through the condensation reaction between 2-methoxytropone and benzene-1,4-dicarboximidamide hydrochloride, and was characterized by 1H NMR and 13C NMR spectroscopies, and ESI–MS. X-ray diffraction analysis reveals that (I) has a nearly planar structure with good π-electron delocalization, indicating that it might serve as a π building block. The crystal belongs to the monoclinic system. One-dimensional chains were formed along the a axis through π–π interactions and adjacent chains are stabilized by C—H...N interactions, forming a three-dimensional architecture. The solid emission of (I) in the crystalline form exhibited a 170 nm red shift compared with that in the solution state. The observed optical bandgap for (I) is 3.22 eV and a cyclic voltammetry experiment confirmed the energy levels of the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO). The calculated bandgap for (I) is 3.37 eV, which is very close to the experimental result. In addition, the polarizability and hyperpolarizability of (I) were appraised for its further application in second-order nonlinear optical materials.

scholarly journals Structure, Electronic And Vibrational Study of 7-Methyl-2,3-Dihydro-(1,3)Thiazolo(3,2-A) Pyrimidin-5-One by Using Density Functional Theory

2018 ◽  
Vol 22 (2) ◽  
pp. 1-11
Author(s):  
Bhawani Datt Joshi ◽  
Janga Bahadur Khadka ◽  
Atamram Bhatt
Keyword(s):  
Density Functional Theory ◽  
Molecular Orbital ◽  
Density Functional ◽  
Basis Set ◽  
Orbital Energy ◽  
Potential Energy Distribution ◽  
Functional Theory ◽  
Hartree Fock ◽  
Solvent Phase ◽  
Lowest Unoccupied Molecular Orbital

 We have presented molecular structure and vibrational wavenumber assignments of 7-methyl-2,3-dihydro-(1,3)thiazolo(3,2-a)pyrimidin-5-one. Both ab initio Hartree-Fock and density functional theory employing 6-311++G(d,p) basis set have been used for the calculations. The scaled values of the calculated vibrational frequencies were used for assignments on the basis of potential energy distribution. The structure-activity relation has been interpreted by mapping molecular electrostatic potential surface. Electronic properties have been analyzed by using time dependent density functional theory (TD-DFT) for both gaseous and solvent phase. The calculated HOMO (highest occupied molecular orbital) and LUMO (lowest unoccupied molecular orbital) energy values show that the charge transfer occurs within the molecule. Journal of Institute of Science and TechnologyVolume 22, Issue 2, January 2018, Page: 1-11 

Novel π-extended porphyrin derivatives for use in dye-sensitized solar cells

2014 ◽  
Vol 18 (07) ◽  
pp. 569-578 ◽  
Author(s):  
Seung Hyun Chae ◽  
Kicheon Yoo ◽  
Yo Sub Lee ◽  
Min Ju Cho ◽  
Jong Hak Kim ◽  
...  
Keyword(s):  
Dye Sensitized Solar Cells ◽  
Acid Group ◽  
Molecular Structures ◽  
Electron Recombination ◽  
Dye Sensitized ◽  
Porphyrin Derivatives ◽  
Dye Aggregation ◽  
Anchoring Groups ◽  
Sensitized Solar Cells ◽  
And Diffusion

Two novel donor-π-acceptor (D-π-A type) porphyrin dyes were successfully synthesized and use in a dye-sensitized solar cell (DSSC). The molecular structures of both porphyrins are composed of the same dialkyl-substituted diphenylamino unit acting as the donor part, and two bisalkoxyphenyl substituents at the 5,15-meso positions. The acceptor part is composed of different ethyne-linked π-extended bridges, and a cyanoacrylic acid (Dye I) or carboxyphenyl (Dye II) moiety acting as anchoring groups. In order to investigate the effects of including the π-extended bridge between the porphyrin and acceptor unit, two different π-extended bridges such as 2,2′-bithiophene and 2-(phenylethynyl)-thiophene, were employed. In particular, Dye II contains two triple bonds between donor substituted porphyrin and carboxylic acid group. These modifications could potentially reduce dye aggregation on the TiO 2 surface. The charge recombination resistance and diffusion length for the cells with Dye II were relatively higher for all the measured ranges of bias potentials, implying that electron recombination loss from injected electrons was highly suppressed when Dye II molecules were adsorbed on the TiO 2 surface. Eventually, Dye II containing a 2,2′-bithiophene π-spacer and anchored trough a carboxyphenyl group exhibited a superior power conversion efficiency of 6.7% under AM 1.5 illumination (100 mW.cm-2) in a photoactive area of 0.46 cm2 than Dye I with a 2-(phenylethynyl)thiophene (PCE = 3.5%) anchored through a cyanoacrylic group.

scholarly journals A New Series of EDOT Based Co-Sensitizers for Enhanced Efficiency of Cocktail DSSC: A Comparative Study of Two Different Anchoring Groups

Molecules ◽  
2019 ◽  
Vol 24 (19) ◽  
pp. 3554 ◽  
Author(s):  
Ganesh Koyyada ◽  
Ramesh Kumar Chitumalla ◽  
Suresh Thogiti ◽  
Jae Hong Kim ◽  
Joonkyung Jang ◽  
...  
Keyword(s):  
Short Circuit ◽  
Energy Levels ◽  
Dye Sensitized Solar Cells ◽  
Short Circuit Current ◽  
Open Circuit ◽  
Design And Synthesis ◽  
New Class ◽  
Synthesis Strategy ◽  
Anchoring Groups ◽  
Sensitized Solar Cells

Herein, we report the design and synthesis strategy of a new class of five EDOT based co-sensitizers (CSGR1-5) by introducing different donors (2,3,4-trimethoxypheny, 2,4-dibutoxyphenyl, and 2,4-difluorophenyl) and anchoring groups (rhodamine-3-acetic acid and cyanoacetic acid) systematically. The synthesized metal-free organic co-sensitizers were employed for cocktail dye-sensitized solar cells along with N749 (black dye). The DSSC devices with a mixture of co-sensitizers (CSGR1-5) and N749 have shown a 7.95%, 8.40%, 7.81%, 6.56% and 6.99% power conversion efficiency (PCE) respectively, which was more than that of single N749 dye PCE (6.18%). Enhanced efficiency could be ascribed to the increased short circuit current (Jsc) and open circuit voltage (Voc). The increased Jsc was achieved due to enhanced light harvesting nature of N749 device upon co-sensitization with CSGR dyes and feasible energy levels of both the dyes. The Voc was improved due to better surface coverage which helps in decreasing the rate of recombination. The detailed optical and electrochemical properties were investigated and complimented with theoretical studies (DFT).

scholarly journals Microwave Assisted Synthesis, Antifungal Activity, and DFT Study of Some Novel Triazolinone Derivatives

2015 ◽  
Vol 2015 ◽  
pp. 1-7
Author(s):  
Na-Bo Sun ◽  
Jian-Zhong Jin ◽  
Fang-Yue He
Keyword(s):  
Antifungal Activity ◽  
Geometry Optimization ◽  
Pythium Ultimum ◽  
Basis Set ◽  
Orbital Energy ◽  
Microwave Assisted Synthesis ◽  
Good Activity ◽  
Full Geometry Optimization ◽  
H Nmr ◽  
Multistep Reaction

A series of some novel 1,2,4-triazol-5(4H)-one derivatives were designed and synthesized under microwave irradiation via multistep reaction. The structures of 1,2,4-triazoles were confirmed by1H NMR, MS, FTIR, and elemental analysis. The antifungal activities of 1,2,4-triazoles were determined. The antifungal activity results indicated that the compounds5c,5f, and5hexhibited good activity againstPythium ultimum, and the compounds5band5cdisplayed good activity againstCorynespora cassiicola. Theoretical calculation of the compound5cwas carried out with B3LYP/6-31G (d). The full geometry optimization was carried out using 6-31G(d) basis set, and the frontier orbital energy and electrostatic potential were discussed, and the structure-activity relationship was also studied.

scholarly journals Ground-State Redox Potentials Calculations of D-π-A and D-A-π-A Organic Dyes for DSSC and Visible-Light-Driven Hydrogen Production

Energies ◽  
2020 ◽  
Vol 13 (8) ◽  
pp. 2032
Author(s):  
Sanaz Mohammadpourasl ◽  
Fabrizia Fabrizi de Biani ◽  
Carmen Coppola ◽  
Maria Laura Parisi ◽  
Lorenzo Zani ◽  
...  
Keyword(s):  
Free Energy ◽  
Redox Potential ◽  
Ground State ◽  
Density Functional ◽  
Rational Design ◽  
Organic Dyes ◽  
Dye Sensitized Solar Cells ◽  
Basis Set ◽  
Orbital Energy ◽  
Redox Potentials

The prediction of ground-state redox potentials by quantum chemical methods has a prominent role in the rational design of novel organic photosensitizers both for dye-sensitized solar cells (DSSCs) and photocatalytic systems for the production of H2. Indeed, the ground-state redox potential of the photosensitizers is one of the key parameters to identify the most promising candidates for such applications. Here, the ground-state redox potentials of 16 organic donor-π-acceptor D-π-A and donor-acceptor-π-acceptor D-A-π-A dyes having a medium to large size of the conjugated scaffold are evaluated, using the methods of the Density Functional Theory (DFT), in terms of free energy differences between their neutral and oxidized ground-state forms. These results are compared to the available experimental data and to the computed highest occupied molecular orbital energy −ε(HOMO) values as an approximation of ground-state redox potentials according to Koopmans’ theorem. Using the MPW1K functional in combination with the 6-31+G* basis set, the strategy based on the free energy cycle, including solvent effects, reproduces with a good level of accuracy the observed values (mean absolute error (MAE) < 0.2 eV) and trend of redox potentials within related families of dyes. On the other hand, the −ε(HOMO) values are only able to capture the experimental trends in redox potential values.

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