In the thyminate(2-)-bridged tetranuclear Cp*Rh(III) complexes incorporating a Na(+), Ca(2+) or Ln(3+) cation, homochiral aggregation of four Rh(III) centres was achieved to form metallacalix[4]arene-type clusters. The thyminate(2-) bridged two Rh(III) and the third metal ion with a μ3-1κN(1):2κ(2)N(3),O(2):3κO(2) mode in the Na(+) and Ca(2+) complexes, while in the Ln(3+) analogues it exhibited a different bridging mode, μ3-1κN(1):2κ(2)N(3),O(4):3κO(2).
Bis[2-(pyridin-2-yl)phenyl]rhodium(III) complexes bearing acetonitrile or monodeprotonated thyminate (Hthym−) were characterized by X-ray analysis, and in the latter complexes it was revealed that Hthym− coordinated to an RhIII centre through the N1 atom together with a hydrogen-bonded methanol or ethanol co-ligand in the cis position.
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