Structural Diversity in Paddlewheel Dirhodium(II) Compounds through Ionic Interactions: Electronic and Redox Properties
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- 作者：Pilar Amo-Ochoa ; Reyes Jim茅nez-Aparicio ; Josefina Perles ; M. Rosario Torres ; Marcello Gennari ; F茅lix Zamora
- 刊名：Crystal Growth & Design
- 出版年：2013
- 出版时间：November 6, 2013
- 年：2013
- 卷：13
- 期：11
- 页码：4977-4985
- 全文大小：490K
- 年卷期：v.13,no.11(November 6, 2013)
- ISSN：1528-7505
文摘
Reactions of dinuclear rhodium(II) tetracarboxylates, [Rh2(O2CR)4] (R = Me, Et), with halides (Br鈥?/sup> and I鈥?/sup>) or pseudohalides (OCN鈥?/sup>) yield dinuclear complexes with intriguing supramolecular architectures based on ionic interactions. The solid-state arrangement of the complexes presented here has been studied using single-crystal X-ray diffraction. Discrete anionic units with the axial positions occupied by isocyanate, Na2[Rh2(O2CMe)4(NCO)2]路4H2O (1), water and isocyanate, Na[Rh2(O2CMe)4(NCO)(H2O)] (2), iodide, {K2[Rh2(O2CEt)4I2]路H2O}n (3), and bromide ligands, {K2[Rh2(O2CEt)4Br2]路H2O}n (4) and K[Rh2(O2CEt)4(Br)0.5]2[Rh2(O2CEt)4(H2O)2] (5), have been found. Complex 1 shows monodimensional polymeric chains stabilized through ionic interactions, while complexes 2鈥?b>4 consist of two-dimensional layers. Finally, a three-dimensional network containing two kinds of dirhodium moieties has been found in complex 5. Speciation of the [Rh2(O2CR)4]/X鈥?/sup> (R = Me, Et; X = OCN, Br, I) systems was investigated in aqueous solution by UV鈥搗isible titrations, helping us to rationalize the obtention of different Rh鈥揦 stoichiometries in the crystal state. By cyclic voltammetry, we have evaluated the effect of X鈥?/sup> coordination on the oxidation properties of these dirhodium(II) units.