The new coordination polymer [(Me3SnIV)3RhIII(SCN)6] = [Rh{μ‐(SCNSnMe3NCS)}3] (5) is readily accessible by straightforward self‐assembly of [Rh(SCN)6]3‐ and (dehydrated) {Me3Sn} ions. The architecture of 5 is strongly reminiscent of “super‐Prussian‐blue” systems reported earlier: there is a three‐dimensional (3‐D) framework involving {Rh8} pseudocubes as the basic building blocks, the Rh3+ ions being held apart by novel, nonlinear {SCN‐SnMe3‐NCS} spacers (d(Rh…︁Rh) = 1.27 nm). The complete lattice consists of two equivalent and independent, ideally interwoven 3‐D frameworks. Three homologues of 5 with slightly modified R3Sn units (R = Et, nPr and nBu) have been prepared as well, but display X‐ray powder diffraction patterns notably different from that of 5.
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Siebel et al. (1997) studied this question.
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