Variation of the Molecular Conformation, Shape, and Cavity Size in Dinuclear Metalla-Macrocycles Containing Hetero-Ditopic Dithiocarbamate–Carboxylate Ligands from a Homologous Series of N-Substituted Amino Acids

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• 作者：Aaron Torres-Huerta ; Jorge Cruz-Huerta ; Herbert Höpfl ; Luis G. Hernández-Vázquez ; Jaime Escalante-García ; Arturo Jiménez-Sánchez ; Rosa Santillan ; Irán F. Hernández-Ahuactzi ; Mario Sánchez
• 刊名：Inorganic Chemistry
• 出版年：2016
• 出版时间：December 5, 2016
• 年：2016
• 卷：55
• 期：23
• 页码：12451-12469
• 全文大小：873K
• ISSN：1520-510X

文摘

A homologous series of dithiocarbamate ligands derived from N-substituted amino acids was reacted with different diorganotin dichlorides to give 18 diorganotin complexes. Spectroscopic and mass spectrometric analysis evidenced the formation of assemblies with six-coordinate tin atoms embedded in skewed-trapezoidal bipyramidal coordination environments of composition C₂SnS₂O₂. Single-crystal X-ray diffraction analysis for three of the compounds revealed a one-dimensional polymeric structure for the complex with the ligand derived from 5-aminopentanoic acid, which through further intermolecular Sn···O interactions generated an overall two-dimensional coordination polymer containing 40-membered hexanuclear tin macrocycles. On the contrary, the ligands derived from 6-aminohexanoic and 8-aminooctanoic acid provided the expected 22- and 26-membered dinuclear macrocyclic structures. Density functional theory calculations for a representative series of macrocyclic complexes of composition [Me₂SnLx]₂ with Lx = ¯S₂CN(Me)-(CH₂)_x-COO¯ (x = 3–12) enabled a detailed analysis of the variations in the molecular conformation, shape, and cavity size of the macrocycles in dependence of the aliphatic spacer. Because of odd–even effects, the difunctional ligands can adopt either a curved or a twisted-pincer shape, while the SnS_xO_4-x (x = 0–4) moieties can act either as linear or angular tectons with varying connectivity angles.