A New Series of Sandwich‐Type 5,5′‐Biterphenylenes: Synthetic Challenge, Structural Uniqueness and Photodynamics

Abstract

A new series of biaryls, bi‐linear‐terphenylenes (BLTPs), were prepared using the tert‐butyllithium‐mediated cyclization as the key synthetic step. The three‐dimensional structures of the studied compounds were verified using X‐ray crystallography and DFT calculations. Tetraaryl(ethynyl)‐substituted BLTPs are highly crowded molecules, and the internal rotation around the central C‐C bond is restricted due to a high barrier (>50 kcal/mol). These structures containseveral aryl/terphenylenyl/aryl sandwiches, where the through‐space π‐π (TSPP) interactions are strongly reflected in the shielding of 1H NMR chemical shifts, reduction of oxidation potentials, increasing aromaticity of the central six‐membered ring and decreasing antiaromaticity of the four‐membered rings in a terpheny‐lenyl moiety based on NICS(0) and iso‐chemical shielding surfaces. Despite the restricted C‐C bond associated intramolecular TSPP interactions for BLTPs in the ground state, to our surprise, the electronic coupling between two linear terphenylenes (LTPs) in BLTPs in the excited state is weak, so that the excited‐state behavior is dominated by the corresponding monomeric LTPs. In other words, all BLTPs undergo ultrafast relaxation dynamics via strong exciton‐vibration coupling, acting as a blue‐light absorber with essentially no emission.