Experimental and computational studies of a multi-electron donor-acceptor ligand containing the thiazolo[5,4-d]thiazole core and its incorporation into a metal-organic framework

Abstract

A ligand containing the thiazolo[5,4-d]thiazole (TzTz) core (acceptor) with terminal triarylamine moieties (donors), N,N-(thiazolo[5,4-d]thiazole-2,5-diylbis(4,1-phenyl-ene))bis(N-(pyridine-4-yl)pyridin-4-amine (1), was designed as a donor-acceptor system for incorporation into electronically active metal-organic frameworks (MOFs). The capacity for the ligand to undergo multiple sequential oxidation and reduction processes was examined using UV/Vis-near-infrared spectroelectrochemistry (UV/Vis-NIR SEC) in combination with DFT calculations. The delocalized nature of the highest occupied molecular orbital (HOMO) was found to inhibit charge-transfer interactions between the terminal triarylamin..