Reversible Solvent‐Exchange‐Driven Transformations in Multifunctional Coordination Polymers Based on Copper‐Containing Organosulfur Ligands

Abstract

The preparation by simple direct synthesis of a series of coordination polymers based on copper with chloride or bromide and dipyrimidinedisulfide is reported. The structural characterisations of these compounds reveal a rich structural variety as a result of the number of coordination modes available to the organosulfur ligand, in combination with the bridging capabilities of the halides. Interestingly, some of the polymers displayed fully reversible solvent exchange/removal crystal‐to‐crystal 2D to 0D and 2D to 2D transformations. These materials show multifunctional electronic properties. Thus, some of them are semiconductors and present weak antiferromagnetic interactions, and the CuI/CuII coordination polymers present coexistence of paramagnetism with weak red emission. These compounds present some of the lowest NIR energy luminescence in d10 transition‐metal complexes.

Post-synthetic modification mechanism for 1D spin crossover coordination polymers

“…40,41 On the other hand, in 1D coordination polymers (1D-CP), the solvent affects the way the CP is arranged, changing its supramolecular architecture 42 or allowing its application as sensors of metal ions 43 by facilitating the exchange of cation, anion and ligands. 44,45 Moreover, this inspired computational scientists to try to simulate the effect of the solvent on supramolecular assemblies. For example, S. Bandyopadhyay et al computationally investigated the solvent's role in ligand recognition.…”

Strong luminescent copper(i) halide coordination polymers and dinuclear complexes with thioacetamide and N,N′-donor ligands

“…[38][39][40] However, design and structure prediction still remains a challenge. Despite the fact that there are some examples of CuIJI) halide coordination polymers based on ligands which contain at the same time hard N and soft S donor atoms, 5,[41][42][43][44][45] or organosulfur ligands and acetonitrile, 46,47 to the best of our knowledge, the combination of organosulfur and N-heteroaromatic ligands to obtain CuIJI) halide coordination polymers still remains unexplored. Introduction of N,N′ditopic ligands, such as 4,4′-bipyridine and pyrazine, to the CuX-thioacetamide system might lead to new compounds with intriguing structures and improved electrical and luminescence properties.…”

A crystalline and free-standing silver thiocarboxylate thin-film showing high green to yellow luminescence

“…Previous studies have shown that these small changes on metal•••metal distances can play a key role on the electrical and optical behavior of these semiconducting materials. 16,[22][23][24][25][26][27]…”