[Au(CN)4]-as a Supramolecular Building Block for Heterobimetallic Coordination Polymers

Abstract
A series of the first coordination polymers using the [Au(CN)4]- anion as a building block has been prepared. The planar tetracyanoaurate anion uses one, two, or four cyano groups to bridge to Ni(II) or Cu(II) centers and exhibits weak Au(III)−N(cyano) interactions between anions. Ni(en)2[Au(CN)4]2·H2O (1, en = ethylenediamine) is a molecular compound with the two [Au(CN)4]- anions coordinating in a trans orientation to Ni(II) without further cyanide coordination. Cu(dien)[Au(CN)4]2 (2, dien = diethylenetriamine) forms a similar molecular complex; however, the dimensionality is increased through weak intermolecular Au−N(cyano) interactions of 3.002(14) Å to form a 1-D zigzag chain. Cu(en)2[Au(CN)4]2 (3) also forms a molecular complex similar to 1, but with elongated axial bonds. The complex further aggregates through Au−N(cyano) interactions of 3.035(8) Å to form a 2-D array. In [Cu(dmeda)2Au(CN)4][Au(CN)4] (4, dmeda = N,N-dimethylethylenediamine) one [Au(CN)4]- anion coordinates via two cis-N(cyano) donors to the axial sites of two Cu(II) centers to form a 1-D zigzag chain of alternating [Cu(dmeda)2]2+ and [Au(CN)2]- units; the other [Au(CN)4]- anion forms a 1-D chain via Au−N(cyano) interactions. In [Cu(bipy)(H2O)2(Au(CN)4)0.5][Au(CN)4]1.5 (5, bipy = 2,2‘-bipyridine) one [Au(CN)4]- anion uses all four cyano moieties to bridge four different Cu(II) centers, creating a 1-D chain.

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