Jens R Sorg1, Tilman Schneider1, Luise Wohlfarth1, Thomas C Schäfer2, Alexander Sedykh2, Klaus Müller-Buschbaum3. 1. Institute of Inorganic Chemistry, Julius-Maximilians-University Würzburg, Am Hubland, 97074 Würzburg, Germany. 2. Institute of Inorganic and Analytical Chemistry, Justus-Liebig-University Giessen, Heinrich-Buff-Ring 17, 35392 Giessen, Germany. Klaus.Müller-Buschbaum@anorg.chemie.uni-giessen.de. 3. Institute of Inorganic Chemistry, Julius-Maximilians-University Würzburg, Am Hubland, 97074 Würzburg, Germany and Institute of Inorganic and Analytical Chemistry, Justus-Liebig-University Giessen, Heinrich-Buff-Ring 17, 35392 Giessen, Germany. Klaus.Müller-Buschbaum@anorg.chemie.uni-giessen.de and Center for Materials Research (LAMA), Justus-Liebig-University Giessen, Heinrich-Buff-Ring 16, 35392 Giessen, Germany. kmbac@uni-giessen.de.
Abstract
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.
Fifteen new sublimable Sb- and n class="Chemical">Bi-based chlorido, bromido andiodido 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.
Authors: Thomas C Schäfer; Jonathan Becker; Marcel T Seuffert; Dominik Heuler; Alexander E Sedykh; Klaus Müller-Buschbaum Journal: Chemistry Date: 2022-03-18 Impact factor: 5.020