Dimensional Reduction of Re_6Se_8Cl_2: Sheets, Chains, and Discrete Clusters Composed of Chloride-Terminated [Re_6Q_8]~(2+)(Q=S, Se) Cores

摘要

Lack of access to certain transition metal halide and chalcohalide clusters through self-assembly methods has enkindled interest in cluster excision, a low-temperature procedure in which the desired sluster is removed intact in molecular form from itscovalently bound environment within an extended solid framework. As demonstrated for the n-dimensional phases Re_6Se_(4+n)Cl_(10-2n) (n=1-3), the effective use of current excision methodology is largely contingent upon the clusters being loosely bound in one or two dimensions. this however, is not always the case, and many clusters exist in a three-dimensional and/or more tightly bound framework. Our recent efforts have therefore focused on the development of a general high-temperature technique for producing frameworks of reduced connectivity, in hope of thereby gaining entry to a wealth of formerly inaccessible cluster chemistry. Herein, we describe such a technique, and demonstrate its efficacy by application to the Re_6Se_8Cl_2 parent structure.