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Cracking the framework of bulk CuCN with flexible bipyrazolyl-based ligands to assemble [CuCN]n-based coordination polymers

Solvothermal reactions of CuCN with a set of flexible bipyrazolyl-based ligands with different spacer lengths [(dmpz)(CH(2))(n)(dmpz)] (dmpz = 3,5-dimethyl-pyrazolyl; n = 1-6) gave rise to six [CuCN](n)-based coordination polymers [(CuCN)(3)L](n) (1: L = dmpzm; 2: L = dmpze), [(CuCN)(2)L](n) (3: L = dmpzpr; 4: L = dmpzb; 5: L = dmpzp; 6: L = dmpzh). Compounds 1-6were characterized by elemental analysis, IR, powder X-ray diffraction and single-crystal X-ray diffraction. 1 or 2 exhibits a 1D scolopendra-like chain assembled from a rare 1D zigzag [CuCN](n) chain with [CN-Cu-CN-Cu-L] (1: L = dmpzm; 2: L = dmpze) side arms. 3 or 4 shows a 2D (6,3) wave-like layer in which [Cu(6)(mu-CN)(6)L(2)](n) (L = dmpzpr or dmpzb) double chains are interconnected by pairs of L bridges. 5 consists of two [CuCN](n) single chains that are linked by dmpzp bridges to form a rare 1D chain with an oblong channel. has a 3D network in which the 2D [Cu(10)(mu-CN)(10)(dmpzh)(3)](n) layers are interconnected by pairs of dmpzh bridges. In addition, the photoluminescent properties of 1-6 in the solid state at ambient temperature were investigated.

Solvothermal assembly of a mixed-valence Cu(I,II) cyanide coordination polymer [Cu(II)Cu(I)2(µ-Br)2(µ-CN)2(bdmpp)]n by C–C bond cleavage of acetonitrile

Dissolving CuBr and 2,6-bis(3,5-dimethyl-1H-pyrazol-1-yl)pyridine (bdmpp) in MeCN followed by a solvothermal treatment afforded an unique mixed-valence Cu(I,II) cyanide coordination polymer [Cu(II)Cu(I)2(µ-Br)2(µ-CN)2(bdmpp)]n (1). Comparative reactions using CuCN and bdmpp under the same conditions gave rise to a different mixed-valence Cu(I,II) cyanide polymer [Cu(II)Cu(I)3(µ-CN)5(bdmpp)]n (2). Both reactions are involved in partial oxidation of Cu(I) into Cu(II) via O2 in open air while in the case of 1, the cyanide may be generated in situ from the C–C cleavage of acetonitrile under solvothermal conditions. 1 consists of a 2D (6,3) layer network in which the [Cu(I)8{Cu(II)(bdmpp)}4(µ-Br)8(µ-CN)7]n double chains are interconnected by a pair of µ-CN bridges. 2 shows a 2D (6,3) folded network in which the [Cu(I)6{Cu(II)(µ-CN)(bdmpp)}2(µ-CN)7]n double chains are inter-linked by a pair of µ-CN bridges. The luminescent properties of 1 and 2 in solid state at ambient temperature were also investigated.

CCDC 748986: Experimental Crystal Structure Determination

Related Article: Zhen-Hong Wei, Ling-Ling Li, Zhi-Gang Ren, Hong-Xi Li, Jian-Ping Lang, Yong Zhang, Zhen-Rong Sun|2009|Eur.J.Inorg.Chem.||4240|doi:10.1002/ejic.200900424