Alkoxo-bridged copper(II) complexes as nodes in designing solid-state architectures. The interplay of coordinative and d(10)d(10) metal-metal interactions in sustaining supramolecular solid-state architectures

作者：Paraschiv C; Andruh M^*; Ferlay S; Hosseini MW; Kyritsakas N; Planeix JM; Stanica N

来源：Dalton Transactions, 2005, (7): 1195-1202.

DOI：10.1039/b500231a

Four novel polymeric coordination networks have been obtained through self-assembly processes involving alkoxo-bridged copper(II) species as nodes, and anionic cyano-complexes as linkers: (infinity)(2)[{Cu-2(pa)(2)}{M(CN)(2)}(2)] (M = Ag, 1; Au, 2), (infinity)(3)[{Cu-4(mea)(4)}{Au(CN)(2)}(4)center dot H2O] 3, and (infinity)(3)[{Cu-2(pa)(2)}{Ni(CN)(4)}] 4 (pa = deprotonated propanolamine; mea = deprotonated monoethanolamine). The supramolecular architectures of compounds 1, 2 and 3 are sustained by argentophilic or strong aurophilic interactions. The solid-state architectures of 1 and 2, which are isomorphous, consist of infinite layers, constructed from binuclear alkoxo-bridged nodes and [M(CN)(2)](-) spacers. The layers are stacked in an offset parallel mode, and are further interconnected through Ag center dot center dot center dot Ag or Au center dot center dot center dot Au contacts (1 : Ag center dot center dot center dot Ag 3.015 angstrom; 2 : Au center dot center dot center dot Au 3.069 angstrom). Compound 3 consists of unique fourfold interpenetrating diamondoid nets. The diamondoid topology is built of heterocubane {Cu4O4} nodes, which are connected by [Au(CN)(2)](-)rods. The Cu-O distances within the {Cu4O4} node vary between 1.927(2) and 2.679(1) angstrom, showing unsymmetric bridging of the copper atoms. Aurophilic interactions are established between the bridging and terminal [Au(CN)(2)](-) metalloligands, and connect the interpenetrating nets, resulting in infinite chains of gold atoms (the Au center dot center dot center dot Au distances vary between 3.253 and 3.305 angstrom). Compound 4 exhibits a 3-D network constructed from {Cu-2(pa)(2)](2+) nodes connected by square-planar [Ni(CN)(4)](2-) ions. Compounds 1, 2 and 4 are weakly paramagnetic. The cryomagnetic investigation of 3 reveals a gradual increase, followed by a decrease of the v M T product, as the temperature is lowered. A superposition of ferro-(J(1) = +20.8 cm(-1)) and antiferromagnetic (J(2) = 6.4) interactions within the tetranuclear node was found. Antiferromagnetic interactions are established between the tetranuclear nodes (theta = 2.99 K)

• 出版日期2005