Diradical Character of Benzo- and Naphtho-Annelated Thiophene–Pyrrole Mixed Oligomer Dications

Takuya Kageyama; Shunsuke Uneme; Masayoshi Takase; Kotohiro Nomura; Tohru Nishinaga

doi:10.1071/CH13522

RESEARCH FRONT

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Diradical Character of Benzo- and Naphtho-Annelated Thiophene–Pyrrole Mixed Oligomer Dications

Takuya Kageyama ^A , Shunsuke Uneme ^A , Masayoshi Takase ^A , Kotohiro Nomura ^A and Tohru Nishinaga ^A ^B

+ Author Affiliations

- Author Affiliations

^A Department of Chemistry, Graduate School of Science and Engineering, Tokyo Metropolitan University, Hachioji, Tokyo 192-0397, Japan.

^B Corresponding author. Email: nishinaga-tohru@tmu.ac.jp

Australian Journal of Chemistry 67(5) 722-728 https://doi.org/10.1071/CH13522
Submitted: 28 September 2013 Accepted: 18 December 2013 Published: 8 January 2014

Abstract

Benzo- and naphtho-annelated thiophene–pyrrole mixed octamers Bz8TP-C_m and Np8TP-C_m, comprising benzo- or naphthodithiophene and two dithienylpyrrole units, were synthesised. Density functional theory (DFT) calculations based on B3LYP/6–31G(d) with the broken symmetry method predicted that dications Bz8TP-C₁²⁺ and Np8TP-C₁²⁺ have stronger diradical character than previously investigated non-annelated thiophene–pyrrole mixed octamer 8TP-C₁²⁺ (R¹ = R² = H). Compounds Bz8TP-C₈ and Np8TP-C₈ showed a one-step, two-electron oxidation process based on cyclic voltammetry analysis. Reaction with SbCl₅ involved a two-electron oxidation. Bz8TP-C₈²⁺ and Np8TP-C₈²⁺ displayed similar absorption spectra to that of nonamer 9TP-C₁₂²⁺ (R¹ = R² = H), rather than that of octamer 8TP-C₁₂²⁺, indicating the stronger diradical characters of octamers Bz8TP-C₈²⁺ and Np8TP-C₈²⁺, as enhanced by benzo- and naphtho-annelation, and were comparable with that of 9TP-C₁₂²⁺. Time-dependent-DFT calculations supported the conclusion obtained from the experimental results.

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Diradical Character of Benzo- and Naphtho-Annelated Thiophene–Pyrrole Mixed Oligomer Dications

Abstract

References

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