Highly π-Extended TTF Analogues with a Conjugated Macrocyclic Enyne Core

The synthesis of a class of highly π-extended tetrathiafulvalene derivatives (1a and 1b) was explored using Sonogashira macrocyclization as a key step. The solid-state structure of 1b was characterized by X-ray single crystallography, showing a substantially bent, S-shaped molecular backbone and an ordered packing geometry in a π-alkyl−alkyl-π stacking fashion. Electronic and redox properties of 1b were investigated by UV−vis absorption, fluorescence spectroscopy, and cyclic voltammetry.