Carbonyl Chalcogenide Cluster-based Polymers

Abstract

Carbonyl chalcogenide metal coordination polymers have drawn much attention in recent decades owing to their fascinating structures, variable bonding modes, and potential applications in material science. While most polymers were constructed by transition metal carbonyls that were further linked by chalcogen atoms or chalcogen-containing ligands, some polymers were built from predesigned chalcogen-containing metal carbonyl clusters that were bridged by organic or inorganic ligands. The significant interactions between electronegative chalcogens and electropositive metal carbonyls along with variable non-classical weak interactions within the frameworks were found to enhance the stability of the resultant supramolecules and polymers under ambient conditions. In addition to some representative metal carbonyl chalcogenide polymers, this chapter will mainly cover carbonyl chalcogenide cluster-based supramolecules and polymers from groups 6 to 8 metals in terms of syntheses, structural features, and their potential applications in the fields of semiconductors, photodegradation, magnetism, catalysis, and adsorption/desorption.

Inorganic–organic hybrid Cu–dipyridyl semiconducting polymers based on the redox-active cluster [SFe3(CO)9]2−: filling the gap in iron carbonyl chalcogenide polymers

“…Metal cluster-based coordination frameworks have gained much attention due to their fascinating structures and intriguing physical and chemical properties. 1,2 Metal clusters can act as nodes or inorganic ligands which could couple with organic multidentate ligands to construct inorganic–organic hybrid polymeric structures. 1,2 Several reports have shown that metal carbonyl clusters could be used as secondary building units, 1,2 in which CO ligands effectively modulated the electronic structures and served as hydrogen bond acceptors within the frameworks.…”

“…1,2 Metal clusters can act as nodes or inorganic ligands which could couple with organic multidentate ligands to construct inorganic–organic hybrid polymeric structures. 1,2 Several reports have shown that metal carbonyl clusters could be used as secondary building units, 1,2 in which CO ligands effectively modulated the electronic structures and served as hydrogen bond acceptors within the frameworks. As a consequence, these metal carbonyl cluster-based polymers showed potential applications in catalysis, host–guest chemistry, and semiconductors.…”

“…As a consequence, these metal carbonyl cluster-based polymers showed potential applications in catalysis, host–guest chemistry, and semiconductors. 2…”

Supramolecular compounds assembled from the heteroleptic tetrahedral complex [{CpMo(CO)2}2(μ,η2-AsSb)] and metal salts

“…These compounds are, compared to the aforementioned literature tetrahedranes, more easily accessible, simple to handle, light-stable and their solids can be stored for years under an inert atmosphere at room temperature without showing any decomposition. Due to the fact that tetrahedranes and organometallic complexes, in general, are still rarely employed as building blocks in supramolecular chemistry, 17 we intensively studied the use of these tetrahedranes as ligands to stabilise transition metal ions. Accordingly, a wide variety of supramolecular coordination complexes (SCCs) and coordination polymers (CPs) were synthesised.…”