First cyano-bridged coordination polymers based on N,N’-chelated Ag(I) ions and octahedral rhenium(III) chalcocyanide clusters exhibiting unusually long-lived photoluminescence

First cyano-bridged coordination polymers based on N,N’-chelated Ag(I) ions and octahedral rhenium(III) chalcocyanide clusters exhibiting unusually long-lived photoluminescence

First examples of Ag(I)-containing coordination polymers based on octahedral rhenium(III) chalcocyanide clusters, namely [{Ag(bpy)}{Ag4(bpy)4(μ-CN)}{Re6Q8(CN)6}] (Q = S in 1 or Se in 2; bpy = 2,2′-bipyridine), have been hydrothermally synthesized and characterized by single-crystal X-ray diffraction...

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Bibliographic Details
Published in:Journal of molecular structure 2018-12, Vol.1173, p.627-634
Main Authors: Ermolaev, Andrey V., Smolentsev, Anton I., Brylev, Konstantin A., Kitamura, Noboru, Mironov, Yuri V.
Format: Article
Language:eng
Subjects:
Chalcocyanocomplex
Luminescence
Rhenium cluster
Silver(I) coordination polymers
X-ray crystal structure
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Summary:First examples of Ag(I)-containing coordination polymers based on octahedral rhenium(III) chalcocyanide clusters, namely [{Ag(bpy)}{Ag4(bpy)4(μ-CN)}{Re6Q8(CN)6}] (Q = S in 1 or Se in 2; bpy = 2,2′-bipyridine), have been hydrothermally synthesized and characterized by single-crystal X-ray diffraction, elemental and thermogravimetric analysis, EDS, IR and luminescence spectroscopy. The compounds are isostructural, crystallize in the orthorhombic system (space group Pccn, Z = 4) and possess a rigid 3D framework structure built up from {Re6Q8(CN)6}4– cluster anions and two distinct types of Ag(I)-containing cationic units, mononuclear {Ag(bpy)}+ and tetranuclear {Ag4(bpy)4(μ-CN)}3+, all of which are interconnected through cyanide bridging. The supramolecular structures of 1 and 2 are supported by argentophilic Ag⋯Ag interactions, but surprisingly show very limited π-π stacking of the pyridine rings. Both compounds are highly emissive in red region showing the longest lifetimes hitherto reported for the solid samples of hexarhenium cluster compounds. Cyano-bridged luminescent coordination polymers representing the first examples of rhenium cluster complexes with Ag(I) cations have been synthesized. [Display omitted] •System [Re6Q8(CN)6]4– – Ag+ – 2,2′-bipyridine.•First cyano-bridged coordination polymers based on octahedral rhenium(III) cluster anions and Ag+ cations.•The first examples of coordination polymers based on anionic chalcocyanide hexarhenium cluster complexes and transition metal cations exhibiting photoluminescence.
ISSN:0022-2860
1872-8014