Tuning optical properties of triphenylamine‐pyrrole by alkyl‐substituted thiobarbituric acid for dye‐sensitized solar cell

Abstract

Nonfullerene acceptors (NFAs) have been recently explored to tune the organic dye-sensitized solar cells. We designed three alkyl derivatives of NFAs from thiobarbituric acid (TBT1) decorated the triphenylamine featuring pyrrole unit (TPAP) to yield TPAP-TBT1, TPAP-TBT2, and TPAP-TBT3 for the potential activity in solar cell applications. Density functional theory (DFT) calculations using B3LYP level of theory and b3lyp/6-311g(d) basis set was used for the structures optimization. The TD-DFT calculations were performed for the structures orbitals (HOMO and LUMO) calculations. The electronic structures of TPAP-TBT2 derivative show the transethyl group on the structure, which facilitates the binding (−15.6 kcal/mol) to the semiconductor surface (TiO 2 ) rather than the steric-hindered N-benzyl derivative (−13.1 kcal/ mol). TBT alkyl substituents facilitate the intramolecular charge transfer within the dyes and improved the D-π-A electron mobility and the solar cell efficiency. The N-ethyl and N-benzyl derivatives showed better performance with respect to the calculated ΔG inject (−1.27) and (−1.22) and V OC values (1.45) and (1.40), respectively.

Pyrrole/thiophene π‐bridged two triphenylamine electron donor and substituted thiobarbituric electron acceptor for D‐π‐A‐D‐featured DSSC applications

“…In order to simulate the absorption spectra of the molecules, we performed the TD-DFT calculations on the optimized structures using CAM-B3LYP with 6-311g (d,p) basis set, which has been successfully used to simulate the UV-Vis absorption of organic molecules. [29,36,40] To validate the TD-DFT results, the simulated absorption spectra of TPAP (Scheme 1) using CAM-B3LYP with 6-311g(d,p) were 422 nm, which is in accordance with literature value (417 nm). [41] To investigate the molecular adsorption of the molecules on TiO 2 surface, the structures were optimized with the B3LYP/Lanl2DZ level of theory.…”

“…These results are in accordance with experimentally fabricated side‐chain polymer and small molecules attached to the triphenylamine unit to increase charge mobility, stability, and efficiency of DSSCs. [ 29–31 ] The ionization potential determines the ability to lose electrons after the light excitation, and the electron affinity determines the electron‐accepting properties, and calculated from Equations () and () [ 32 ] : …”

One-Pot Synthesis of Push–Pull Butadienes from 1,3-Diethyl-2-thiobarbituric Acid and Propargylic Alcohols

“…A wide variety of donor and acceptor units, as well as π-conjugated spacers, have been combined during the last decades for the construction of push-pull molecules. In this context, the pseudoaromatic 2-thioxodihydropyrimidine-4,6(1H,5H)-dione ring of thiobarbituric acid and its N-alkylated derivatives has been extensively employed as an electron-withdrawing moiety in push-pull chromophores [6][7][8][9]. Representative examples are dyes 3a,b, recently described by Dumur and co-workers, featuring p-methoxyphenyl and p-dimethylaminophenyl donor groups connected to the barbituric acid skeleton through a 1,3-butadiene chain spacer (Scheme 1), which showed a marked solvatochromic Citation: Francos, J.; Cadierno, V. A wide variety of donor and acceptor units, as well as π-conjugated spacers, have been combined during the last decades for the construction of push-pull molecules.…”

“…Representative examples are dyes 3a,b, recently described by Dumur and co-workers, featuring p-methoxyphenyl and p-dimethylaminophenyl donor groups connected to the barbituric acid skeleton through a 1,3-butadiene chain spacer (Scheme 1), which showed a marked solvatochromic Citation: Francos, J.; Cadierno, V. A wide variety of donor and acceptor units, as well as π-conjugated spacers, have been combined during the last decades for the construction of push-pull molecules. In this context, the pseudoaromatic 2-thioxodihydropyrimidine-4,6(1H,5H)-dione ring of thiobarbituric acid and its N-alkylated derivatives has been extensively employed as an electronwithdrawing moiety in push-pull chromophores [6][7][8][9]. Representative examples are dyes 3a,b, recently described by Dumur and co-workers, featuring p-methoxyphenyl and pdimethylaminophenyl donor groups connected to the barbituric acid skeleton through a 1,3-butadiene chain spacer (Scheme 1), which showed a marked solvatochromic behavior in solution [10,11].…”

Decoration of modified self‐assembly membrane by magnesium oxide and yttrium oxide nanoparticles for biosensors, supercapacitors, and water treatment

“…Recently, the applications of nanomaterials (NMs) are an important target to a lot of researchers in the various scientific fields due to their unique optical properties, surface area, and biological applications 1‐3 . Water treatment is one of the urgent challenges in the last times, so the countries usually search for a lot of solutions do not traditional finding the different sources of pure water, the NMs membrane considers one of the important solutions for removing the water pollutants and water desalination 4,5 . The various methods of water treatment by NMs depend on the two categories: the first is the adsorption method, and the other is the photocatalytic method, the two methods depend on the large surface area and the unique optical properties of NMs 6 .…”