Issue 21, 2019

New π-extended catecholato complexes of Pt(ii) and Pd(ii) containing a benzothienobenzothiophene (BTBT) moiety: synthesis, electrochemical behavior and charge transfer properties

Abstract

Benzothienobenzothiophene (BTBT) and derivatives have received increasing attention as organic field-effect transistor materials and molecular conductors. This report presents the first synthesis of metal complexes involving a BTBT moiety, which was achieved by complexation of 2,2′-bipyridyl complexes of Pt(II) and Pd(II) with dihydroxy-substituted BTBT (1) as a new π-extended catecholato ligand (tBu2Bpy = 4,4′-di-tert-butyl-2,2′-dipyridyl). The resulting complexes M(tBu2Bpy)(O2BTBT) (M = Pt (3Pt) and Pd (3Pd)) were characterized by UV–vis spectroscopy, density functional theory (DFT) calculations, and cyclic voltammetry. The electron donating ability of BTBT was substantially enhanced upon including two oxygen substituents followed by metal coordination. This enabled chemical oxidation of 3Pt and 3Pd with a mild chemical oxidant (ferrocenium hexafluorophosphate) and formation of the one-electron-oxidized state. While 3Pt and 3Pd exhibited an absorption band originating from a catecholate → Bpy ligand-to-ligand charge transfer transition typical of this class of catecholato complexes, the radical cations exhibited a unique π–π* intramolecular charge transfer (ICT) transition absorption in which the π and π* orbitals were the newly incorporated benzothienothiophene-based donor and semiquinonato-based acceptor, respectively. The BTBT+ skeleton was electronically divided into two sites by the present chemical modification. The ICT properties of the complexes were found to be modulated by varying the metal ions. These findings offer a new approach to molecular design for (semi)conducting materials using optical properties.

Graphical abstract: New π-extended catecholato complexes of Pt(ii) and Pd(ii) containing a benzothienobenzothiophene (BTBT) moiety: synthesis, electrochemical behavior and charge transfer properties

Supplementary files

Article information

Article type
Paper
Submitted
22 12 2018
Accepted
27 3 2019
First published
27 3 2019

Dalton Trans., 2019,48, 7367-7377

New π-extended catecholato complexes of Pt(II) and Pd(II) containing a benzothienobenzothiophene (BTBT) moiety: synthesis, electrochemical behavior and charge transfer properties

K. Tahara, Y. Ashihara, T. Higashino, Y. Ozawa, T. Kadoya, K. Sugimoto, A. Ueda, H. Mori and M. Abe, Dalton Trans., 2019, 48, 7367 DOI: 10.1039/C8DT05057K

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