2018/08/31 by Keishiro Tahara, Tomoya Kadowaki, Jun‐ichi Kikuchi +4
Chemistry · Materials Science · #Conducting polymers and applications #Electrochemical Analysis and Applications #Photochemistry and Electron Transfer Studies
paper · pdf · doi:10.1246/bcsj.20180187
openalex publication_date 2018/08/31 · crossref created 2018/08/31 · crossref issued 2018/09/01 · crossref published 2018/09/01 · crossref published-online 2018/09/01 · crossref published-print 2018/11/15 · crossref deposited 2024/01/21 · openalex created_date 2025/10/10 · openalex updated_date 2026/07/29 · crossref indexed 2026/07/29
Abstract In this study, we report synthesis of a new series of mixed-valence (MV) complexes having intervalence charge transfer (IVCT) energies variable from the first to the third telecommunication window. This wide-range modulation was achieved by variation of covalently-dimerized catecholato ligands, in combination with Pd(II) ions, which lowered the oxidation potentials and enabled access to MV states. Importantly, we found that regulation of the conjugation lengths enabled energy gap control and annulation of an additional benzene ring switched the nature of the IVCT transitions. These changes were accompanied by a cross-over from moderately delocalized Class II to delocalized Class III character according to the Robin-Day classification. Through accurate comparisons with well-known ferrocene counterparts and their hetero-conjugate, our non-innocent ligand-based approach is found to be effective for controlling IVCT parameters. These findings offer a new approach to materials design for electro-optic switching.