Effect of t-BuS vs. n-BuS on the topology, Cu⋯Cu distances and luminescence properties of 2D Cu4I4/RS(CH2)4SR metal–organic frameworks

Abstract

CuI reacts with RS(CH₂)₄SR (R = n-Bu (L1); t-Bu (L2)) to afford the 2D coordination polymers [Cu₄I₄{μ-RS(CH₂)₄SR}₂]_n (R = n-Bu (1); t-Bu (2)). Their grid networks exhibit nodal Cu₄(μ₃-I)₄ clusters interconnected by dithioethers with mean Cu⋯Cu distances of 2.7265(10) and 2.911(2) Å for 1 and 2, respectively. This difference translates in a blue shift of the solid state emission bands and a decrease in emission lifetimes when trading R = n-Bu to the bulky t-Bu.