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Ávila, Manuel
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article
Atypical Metal‐Center Coordination in Two Cyanide‐Based Coordination Polymers
Abstract
<jats:title>Abstract</jats:title><jats:p>This contribution reports the crystal structure, solved and refined from single crystal XRD data, of two cyanide‐based coordination polymers, with K[Cu<jats:sub>2</jats:sub>(CN)<jats:sub>3</jats:sub>] ⋅ H<jats:sub>2</jats:sub>O (<jats:bold>1</jats:bold>) and [Cd(H<jats:sub>2</jats:sub>O)]<jats:sub>2</jats:sub>Cd(H<jats:sub>2</jats:sub>O)<jats:sub>2</jats:sub>[Cu(CN)<jats:sub>3</jats:sub>Cu(CN)<jats:sub>2</jats:sub>]<jats:sub>2</jats:sub> ⋅ 8H<jats:sub>2</jats:sub>O (<jats:bold>2</jats:bold>) as formula units. These coordination polymers are characterized by metal‐metal bonds between copper atoms. In <jats:bold>1</jats:bold>, the framework is formed by Cu−Cu(CN)<jats:sub>3</jats:sub> pseudo tetrahedral blocks linked by planar Cu<jats:sub>2</jats:sub>(CN)<jats:sub>3</jats:sub> units. In this material, a defined Cu−Cu bond was identified, which is congruent with the corresponding Raman spectrum. The K atom and water molecule occupy the framework cavities. In <jats:bold>2</jats:bold>, the Cu−Cu bond is observed in Cu<jats:sub>2</jats:sub>(CN)<jats:sub>6</jats:sub> blocks which remain linked to Cd(NC)<jats:sub>2</jats:sub>(H<jats:sub>2</jats:sub>O)<jats:sub>4</jats:sub> and Cd(NC)<jats:sub>4</jats:sub>(H<jats:sub>2</jats:sub>O)2 units occupying their axial and equatorial coordination positions, respectively. The solid framework is completed by the −N=C−Cu−C=N− chains linked to Cd(NC)<jats:sub>4</jats:sub>(H<jats:sub>2</jats:sub>O)<jats:sub>2</jats:sub> moieties. The crystal structure for <jats:bold>2</jats:bold> contains two different sites for the metal centers. The structural study was complemented by recording IR, Raman, and UV/Vis spectra. These two coordination polymers behave as semiconductor materials with a band gap of 2.79 and 3.43 eV, respectively, as derived from the Tauc plot of the corresponding UV/Vis spectrum. Band structure calculations properly supported these values. <jats:bold>1</jats:bold> is a material of an indirect band gap, while <jats:bold>2</jats:bold> has a direct band gap.</jats:p>