Sb- and Bi-based coordination polymers with N-donor ligands with and without lone-pair effects and their photoluminescence properties.

Fifteen new sublimable Sb- and Bi-based chlorido, bromido and iodido coordination polymers (CPs) with linear bispyridyl ligands are presented in this work and compared in terms of their crystal structures and photoluminescence properties. The Sb-CPs occur in two structural motifs: 1∞[Sb2X6(L)2] (X: Cl (a), Br (b), I (c); L: 1,2-bis(4-pyridyl)ethylene (bpe) (1), 1,2-bis(4-pyridyl)ethane (bpa) (2), 4,4'-bipyridine (bipy) (X: Br, I; 3)) with two polymorphs showing negligible stereochemical demand of the lone-pair and 1∞[SbCl3(bipy)] (3a) featuring a stereochemically active lone pair with significant 5p-contribution at SbIII. This is accompanied by differences in the coordination polyhedra being octahedral for high s-character, whereas a high p-character of the lone pair results in a square pyramid as the coordination sphere. The Bi-CPs are represented by the general formula 1∞[Bi2X6(L)2] (X: Cl (a), Br (b), I (c); L: 1,2-bis(4-pyridyl)ethylene (bpe) (4), 1,2-bis(4-pyridyl)ethane (bpa) (5)) and thus show no significant 6p-character of the lone pairs. For examining the parallels and differences between the SbIII- and BiIII-CPs, both are compared in terms of structures and luminescence properties, as well as with related literature known CPs. Altogether, this comparison of structures and properties allows for gaining new insights into the photoluminescence mechanisms of the Sb and Bi-containing CPs. For the first time, distinct hints on the participation of inter-valence charge transfer transitions in E3+-pairs (E: Sb, Bi) were observed for the Sb- and Bi-containing coordination polymers constructed from N-donor ligands.

Bismuth as a versatile cation for luminescence in coordination polymers from BiX3/4,4'-bipy: understanding of photophysics by quantum chemical calculations and structural parallels to lanthanides.

Coordination polymers (CPs) with bismuth(iii) as a connectivity centre have been prepared from BiX3 (X = Cl-I) and 4,4'-bipyridine (bipy) in order to implement Bi-based luminescence. The products were obtained via different synthetic routes such as solution chemistry, melt syntheses or mechanochemical reactions. Five neutral and anionic 1D-CPs are presented that show a chemical parallel to trivalent lanthanides forming isostructural or closely related 1D-CPs, of which five additional compounds are described. Bi3+ proves to be a versatile cation for luminescence resulting from energy transfer processes between a metal and a ligand in the presented CPs. Quantum chemical calculations were carried out to investigate Bi3+-participation in the luminescence processes. The calculated results allow an assignment of the bright transitions composed of mainly metal-to-ligand-charge transfer (MLCT) character. These results show that Bi3+ can form strongly luminescent coordination compounds with N-donor ligands.