5,20-Bis(α-oligothienyl)-substituted [26]hexaphyrins possessing electronic circuits strongly perturbed by meso-oligothienyl substituents

Hirotaka Mori, Masaaki Suzuki, Woojae Kim, Jong Min Lim, Dongho Kim, Atsuhiro Osuka

Research output: Contribution to journalArticle

11 Citations (Scopus)

Abstract

A series of [26]hexaphyrins(1.1.1.1.1.1) bearing two α-oligothienyl substituents at 5,20-positions have been synthesised and are shown to have a dumbbell hexaphyrin conformation, to which the α-oligothienyl groups are linked with small dihedral angles to form an acyclic helix-like conjugated network. While their distinct diatropic ring currents and four reversible reduction waves characteristic of aromatic [26]hexaphyrins indicate that the [26]hexaphyrin aromatic circuits are viable, the absorption spectra and excited state dynamics are significantly perturbed, which becomes increasingly evident with elongation of the oligothienyl substituents. DFT calculations of these hexaphyrins indicated that the LUMO and LUMO + 1 are localised on the hexaphyrin circuit and the HOMO and HOMO - 1 are spread over the acyclic helix-like conjugation network, which can explain the perturbed absorption spectra.

Original languageEnglish
Pages (from-to)1696-1700
Number of pages5
JournalChemical Science
Volume6
Issue number3
DOIs
Publication statusPublished - 2015 Mar 1

    Fingerprint

All Science Journal Classification (ASJC) codes

  • Chemistry(all)

Cite this