Title

Copper(I) Cyanide Networks: Synthesis, Structure, and Luminescence Behavior. Part 2. Piperazine Ligands and Hexamethylenetetramine

Document Type

Article

Publication Date

8-17-2009

Abstract

A variety of photoluminescent, and in some cases thermochromic, metal-organic networks of CuCN were selfassembled in aqueous reactions with amine ligands: (CuCN)2(Pip) (1a), (CuCN)20(Pip)7 (1b), (CuCN)7(MePip)2 (2), (CuCN)2(Me2Pip) (3a), (CuCN)4(Me2Pip) (3b), (CuCN)7(EtPip)2 (4), (CuCN)4(Et2Pip) (5), (CuCN)3(BzPip)2 (6a), (CuCN)5(BzPip)2 (6b), (CuCN)7(BzPip)2 (6c), (CuCN)4(BzPip) (6d), (CuCN)2(Bz2Pip) (7), (CuCN)(Ph2CHPip) (8a), (CuCN)2(Ph2CHPip) (8b), (CuCN)3(HMTA)2 (9a), (CuCN)5(HMTA)2 (9b), and (CuCN)5(HMTA) (9c) (Pip ) piperazine, MePip ) N-methylpiperazine, Me2Pip ) N,N′-dimethylpiperazine, EtPip ) N-ethylpiperazine, Et2Pip ) N,N′- diethylpiperazine, BzPip ) N-benzylpiperazine, Bz2Pip ) N,N′-dibenzylpiperazine, Ph2CHPip ) N-(diphenylmethyl) piperazine, and HMTA ) hexamethylenetetramine). New X-ray structures are reported for 1b, 2, 3b, 4, 5, 6a, 6d, 7, 8b, 9b, and 9c. An important structural theme is the formation of (6,3) (CuCN)2(piperazine) sheets with or without threading of independent CuCN chains. Strong luminescence at ambient temperature is observed for all but complexes 6 and 7. All luminescent compounds show a broad emission band in the blue region at about 450 nm attributable to metal-to-ligand charge transfer behavior based on the large Stokes shift between excitation and emission maxima. 3, 8, and 9 are thermochromic due to an additional lower energy emission band, which is absent at 77 K.

Journal Title

INORGANIC CHEMISTRY

Volume

48

Issue

16

DOI

10.1021/ic901380b

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