DFT/TDDFT Investigation on donor-acceptor triazole-based copolymers for organic photovoltaics

Bedoura, Sultana; Xi, Hongwei; Goh, Ho Wee; Lim, Kok Hwa

doi:10.1016/j.molstruc.2021.131406

Cited by 6 publications

(3 citation statements)

References 55 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Cyanostilbene appended donor–π–acceptor (D−π–A) type systems, where the cyano moiety acts as the acceptor (A), are the more straightforward model for a comprehensive understanding of the effect of positional isomerism of α and β analogs of cyanostilbene because it allows flexibility in molecular design by changing either conjugating moiety (π) or donor unit (D) systematically. ,− Such systems are capable of fabricating excellent hole and electron transport facilities and executing push–pull effects, allowing electron transfer from the donor to the acceptor through the conjugated π-units. − Furthermore, D−π–A architecture having functionalized acrylonitrile compounds offers better nonlinear optical (NLO) performance. − For example, Singh and co-workers recently synthesized a series of cyanostilbene-based D−π–A systems containing the 9,9-dimethyl-9 H -fluoren-2-amine type of chromophores and observed a significant enhancement in the first hyperpolarizability and related intrinsic hyperpolarizability by modulating the π-conjugation pathways . In a continued work, the same group compared the first hyperpolarizabilities by extending the π-conjugation of D−π–A systems and found that lengthening of π-conjugation beyond a certain limit hardly improves the NLO response.…”

Section: Introductionmentioning

confidence: 99%

Theoretical Insights into the Structural and Optical Properties of D−π–A-based Cyanostilbene Systems of α and β Variants

Femina,

Sajith,

Remya

et al. 2024

ACS Omega

View full text Add to dashboard Cite

The π-conjugated organic molecules containing cyanostilbene motifs have been extensively investigated due to their great potential applications in several optoelectronic and biological fields. Developing efficient molecules in this respect requires strategic structural engineering and a deep understanding of the structure–property relationship at the molecular level. In this context, understanding the impact of positional isomerism in cyanostilbene systems is a fundamental aspect of designing desired materials with improved photophysical properties. Herein, we designed ten donor–π–acceptor (D−π–A) type cyanostilbene derivatives (P 1 – P 10 ) with different π linkers and compared their structural and optoelectronic properties arising from the positional variations of the –CN group (α and β- variations) through the utilization of density functional theory (DFT) and time-dependent DFT (TDDFT) methods. The topological analyses of the electron density are used to explain the relatively high stability of α isomer compared to that of β. Frontier molecular orbital analysis reveals that 17 molecules tend to show a reduced highest occupied molecular orbital–lowest unoccupied molecular orbital gap, and most of them showed a greater nonlinear optical (NLO) character compared to the parent molecule. TDDFT calculations indicate that β isomers show higher absorption maxima compared to their α counterparts. Among all the scrutinized molecules, the absorption maximum extended up to 602 nm for P 9 and it possesses the highest first-order hyperpolarizability. This study sheds light on positional isomers and their reactivity, absorption spectra, and NLO properties of D−π–A type architecture that can be suitably tuned by appropriating the π-bridge for practical applications.

show abstract

Section: Introductionmentioning

confidence: 99%

Theoretical Insights into the Structural and Optical Properties of D−π–A-based Cyanostilbene Systems of α and β Variants

Femina,

Sajith,

Remya

et al. 2024

ACS Omega

View full text Add to dashboard Cite

show abstract

“…Recently, many reports have been published on predicting chemical reactions using various methods [15][16][17][18][19][20][21][22][23][24][25][26]. Even in polymer science, efforts to predict polymer properties are still being explored, as published in various reports on computational approaches [27][28][29][30][31][32][33][34][35][36][37][38][39][40][41][42]. However, computational approaches do not easily predict and explain polymer synthesis because defining the representative chemical potential for polymers in DFT is difficult, with a high degree of freedom and computational complexity involving many atoms.…”

Section: Introductionmentioning

confidence: 99%

Experimental and Computational Approaches to Sulfonated Poly(arylene ether sulfone) Synthesis Using Different Halogen Atoms at the Reactive Site

et al. 2022

View full text Add to dashboard Cite

Engineering thermoplastics, such as poly(arylene ether sulfone), are more often synthesized using F-containing monomers rather than Cl-containing monomers because the F atom is considered more electronegative than Cl, leading to a better condensation polymerization reaction. In this study, the reaction’s spontaneity improved when Cl atoms were used compared to the case using F atoms. Specifically, sulfonated poly(arylene ether sulfone) was synthesized by reacting 4,4′-dihydroxybiphenyl with two types of biphenyl sulfone monomers containing Cl and F atoms. No significant difference was observed in the structural, elemental, and chemical properties of the two copolymers based on nuclear magnetic resonance spectroscopy, Fourier transform infrared spectroscopy, thermogravimetric analysis, X-ray diffraction, transmission electron microscopy, and electrochemical impedance spectroscopy. However, the solution viscosity and mechanical strength of the copolymer synthesized with the Cl-terminal monomers were slightly higher than those of the copolymer synthesized with the F-terminal monomers due to higher reaction spontaneity. The first-principle study was employed to elucidate the underlying mechanisms of these reactions.

show abstract

“…Dyes are other category of organic materials applied in photovoltaics, due to their high π-electron conjugations, leading to great electronic excitations and transitions [21][22][23]. These systems are characterized with low HOMO/LUMO energy gap, which gives insight into why these molecules act as semiconductors [24].…”

Section: Introductionmentioning

confidence: 99%

Understanding the Electronic Interactions, Vertical Excitation Analysis, and the Photovoltaic Properties of 5-(2-ethylhexyl)-1,3-di(furan-2-yl)-4H-thieno[3,4-c]pyrrole-4,6-dione

Enudi

Louis

Ogunwale

et al. 2021

Preprint

View full text Add to dashboard Cite

Organic photovoltaic (OPV) are a promising new class of photovoltaic as they offer several advantageous features including large surface area to volume ratio, low cost, lightweight properties, and durability. The limitation of OPV that prevented their adoption for use in the past was their low power conversion efficiency (PCE) but that drawback has been solved by the development of the donor-acceptor-donor (D-A-D) system with high conversion efficiencies. Herein, 5-(2-ethylhexyl)-1,3-di (furan-2-yl)-4H-thieno [3,4-c]pyrrole-4,6(5H)-dione (FTPF), a donor-acceptor-donor monomer was investigated for its optoelectronic, excited state, and photovoltaic properties using a density functional theory (DFT) and time-dependent density function theory (TD-DFT) at the B3LYP/6-31+G(d,p) theoretical method. The spectral analysis (FT-IR, UV-vis, and NMR), electronic molecular properties, natural bonding orbitals (MOs and NBOs) analyses, and excitation were studied at this level in gas, hexane, DMF, and THF. The UV-Vis spectrum showed that FTPF exhibited mono-absorption in non-polar gas and hexane, but dual absorptions in polar solvents (DMF and THF) having maximum wavelength (λmax) at 351, 359, 371 and 373 nm in gas, hexane, THF, and DMF respectively, showing a major red shift as solvent became polar. The hole-electron excitation studies of the first five singlet states: S0→S1/S2/S3/S4/S5 in gas and DMF phases showed that S0→S1 is a delocalized π→π* Rydberg excitations originating from the D-A-D C=C π bonds, S0→S2 is π→π* local excitation, while S0→S3 in water occurred as an n→π* from the carbonyl and azolide groups of the acceptor unit, but n→π* charge transfer (CT) in DMF. The S0→S5 in water and S0→S4 are n→π* LE type excitations, while S0→S5 in DMF conformed to a delocalized π→π* excitation extended over the D-A-D conjugated backbone. FTPF provided efficient electron injection in all studied solvent; showing that FTPF is a sure-bet for opto-electronic application.

show abstract

DFT/TDDFT Investigation on donor-acceptor triazole-based copolymers for organic photovoltaics

Cited by 6 publications

References 55 publications

Theoretical Insights into the Structural and Optical Properties of D−π–A-based Cyanostilbene Systems of α and β Variants

Theoretical Insights into the Structural and Optical Properties of D−π–A-based Cyanostilbene Systems of α and β Variants

Experimental and Computational Approaches to Sulfonated Poly(arylene ether sulfone) Synthesis Using Different Halogen Atoms at the Reactive Site

Understanding the Electronic Interactions, Vertical Excitation Analysis, and the Photovoltaic Properties of 5-(2-ethylhexyl)-1,3-di(furan-2-yl)-4H-thieno[3,4-c]pyrrole-4,6-dione

Contact Info

Product

Resources

About