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Structural and electronic properties of 4H-cyclopenta[2,1-b,3;4-b′]dithiophene S-oxide (BTO) derivatives with an S, S=O, O, SiH2, or BH2 bridge: semi-empirical and DFT study

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Abstract

In this paper, we theoretically studied the geometries, stabilities, and the electronic and thermodynamic properties of 4H-cyclopenta[2,1-b,3;4-b′]dithiopene S-oxide derivatives (BTO-X, with X = BH2, SiH2, S, S=O, or O) using semi-empirical methods, ab initio methods, and density functional theory. The geometries and thermodynamic parameters calculated by PM3 were in good agreement with those calculated with B3LYP/6-31 G*. The band gap calculated using B3LYP/6-31 G* ranged from 3.94 eV (BTO-O) to 3.16 eV (BTO-B). The absorption λ max calculated using B3LYP/6-31 G* was shifted to longer wavelengths when X = BH2, SiH2, or S=O (due to their electron-withdrawing effects) and to shorter wavelengths for BTO-S and BTO-O as compared to the λ max for the thiophene S-oxide (2TO) dimer. The changes in ΔH°, ΔS°, and ΔG° calculated using both semi-empirical and DFT methods were quite similar.

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Authors and Affiliations

  1. Department of Pure and Applied Chemistry, Ladoke Akintola University of Technology, Ogbomoso, Nigeria

    Semire Banjo & Odunola Olusegun Ayobami

  2. Department of Chemistry, University of Ibadan, Ibadan, Nigeria

    Adejoro Isaiah Ajibade

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  1. Semire Banjo
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  2. Odunola Olusegun Ayobami
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  3. Adejoro Isaiah Ajibade
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Correspondence to Semire Banjo.

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Banjo, S., Ayobami, O.O. & Ajibade, A.I. Structural and electronic properties of 4H-cyclopenta[2,1-b,3;4-b′]dithiophene S-oxide (BTO) derivatives with an S, S=O, O, SiH2, or BH2 bridge: semi-empirical and DFT study. J Mol Model 18, 2755–2760 (2012). https://doi.org/10.1007/s00894-011-1291-1

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