Cyanide-bridged mixed-valence copper(II/I) coordination polymers: Unique 7-connected sev-type 3D network versus anionic 2D host network encapsulated with cationic complex.

Reactions of CuCl 2 , K 2 [Ni(CN) 4 ]/K 3 [Co(CN) 6 ], and 5-amino-1H-tetrazole led to cyanide-bridged mixed-valence Cu(II/I) complexes, [Cu(H 2 O) 3 Cu 3 (CN) 5 ] ( 1 ) and [Cu(H 2 O) 4 ][Cu 4 (CN) 6 ] ( 2 ).The uncommon semi-closed {Cu 2 (CN) 3 } dimmers in 1 are bridged by μ 3 -C,C,N cyanide ligands to afford rare 1D centipedal-like chain motifs, which are further bridged by μ 2 -C,N and metalloligand “CN–Cu(4)–CN” to finish sophisticated zeolite-like 3-D structure. Topologically, 1 is the first example of uninodal 7-connected sev -like cyanide-bridged network. Compound 2 consists of two-dimensional honeycomb-related anionic layers [Cu 4 (CN) 6 ] 2 − , within which the [Cu(H 2 O) 4 ] 2 + cations are intercalated into alternate interlamellar space. Compound 1 shows antiferromagnetic couple arising from pure ground-state configuration of Cu(II) mediated by diamagnetic bridges –CN–Cu I –CN −. The inclusion compound 2 shows blue photoluminescence originated from Cu(I) center to the unoccupied π* orbital of the cyanide ligand (MLCT) charge transfer. [ABSTRACT FROM AUTHOR]