Solvatochromic behaviour of cyclic dithioether-functionalized triphenylamine ligands and their mechano-responsive Cu(i) coordination polymers

Abstract

Cu(I)-based coordination polymers (CPs) are known as efficient emissive materials providing an eco-friendly and cost-effective platform for the development of various functional materials and sensors. In addition to the nature of the metal center, organic ligands also play a crucial role in controlling the emissive properties of coordination polymers. Herein, we report on the synthesis of dithiane- and dithiolane-substituted triphenylamine ligands L₁ and L₂. These ligands were found to be emissive both in the solid state and in solution. In addition, these ligands exhibit solvatochromic behaviour due to the twisted intramolecular charge transfer (TICT) phenomenon. Next, coordination behaviour of these ligands was explored with Cu(I)X salts (X = Br and Cl) and four new 1D coordination polymers [{Cu(μ₂-X)₂Cu}(μ₂-L)]_n, CP1 (X = Br, L = L₁), CP2 (X = Cl, L = L₁), CP3 (X = Br, L = L₂), and CP4 (X = Cl, L = L₂) were synthesized and crystallographically characterized. The emission behaviour of all the CPs suggests ligand-centered transitions. On mechanical grinding, emission maxima (λ_em) for CP1 and CP2 were blue-shifted, whereas for CP3 and CP4 red-shifts were observed. All CPs were found to emit at 448 nm with increased intensity after grinding. It is supposed that grinding is responsible for a change in the spatial arrangement (dihedral angles) of the phenyl groups of triphenylamine, causing the observed emission shifts. Furthermore, the higher emission intensity after grinding suggests the occurrence of a similar phenomenon as an aggregation-induced quenching in these CPs.