title: 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.
abstract: 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]2with 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 SnSxO4-x(x = 0-4) moieties can act either as linear or angular tectons with varying connectivity angles.
authors.affiliation: Centro de Investigaciones Químicas, Instituto de Investigación en Ciencias Básicas y Aplicadas, Universidad Autónoma del Estado de Morelos , Av. Universidad 1001, Chamilpa, Cuernavaca 62209, Morelos, México.
authors.forename: Aaron
authors.initials: A
authors.lastname: Torres-Huerta
authors.affiliation: Centro de Investigaciones Químicas, Instituto de Investigación en Ciencias Básicas y Aplicadas, Universidad Autónoma del Estado de Morelos , Av. Universidad 1001, Chamilpa, Cuernavaca 62209, Morelos, México.
authors.forename: Jorge
authors.initials: J
authors.lastname: Cruz-Huerta
authors.affiliation: Centro de Investigaciones Químicas, Instituto de Investigación en Ciencias Básicas y Aplicadas, Universidad Autónoma del Estado de Morelos , Av. Universidad 1001, Chamilpa, Cuernavaca 62209, Morelos, México.
authors.forename: Herbert
authors.initials: H
authors.lastname: Höpfl
authors.affiliation: Centro de Investigaciones Químicas, Instituto de Investigación en Ciencias Básicas y Aplicadas, Universidad Autónoma del Estado de Morelos , Av. Universidad 1001, Chamilpa, Cuernavaca 62209, Morelos, México.
authors.forename: Luis G
authors.initials: LG
authors.lastname: Hernández-Vázquez
authors.affiliation: Centro de Investigaciones Químicas, Instituto de Investigación en Ciencias Básicas y Aplicadas, Universidad Autónoma del Estado de Morelos , Av. Universidad 1001, Chamilpa, Cuernavaca 62209, Morelos, México.
authors.forename: Jaime
authors.initials: J
authors.lastname: Escalante-García
authors.affiliation: Departamento de Química, Centro de Investigación y de Estudios Avanzados del Instituto Politécnico Nacional , Av. Instituto Politécnico Nacional 2508, San Pedro Zacatenco, México 07360, México.
authors.forename: Arturo
authors.initials: A
authors.lastname: Jiménez-Sánchez
authors.affiliation: Departamento de Química, Centro de Investigación y de Estudios Avanzados del Instituto Politécnico Nacional , Av. Instituto Politécnico Nacional 2508, San Pedro Zacatenco, México 07360, México.
authors.forename: Rosa
authors.initials: R
authors.lastname: Santillan
authors.affiliation: Centro Universitario de Tonalá, Universidad de Guadalajara , Av. Nuevo Periférico 555, Ejido San José Tatepozco, Tonalá 48525, Jalisco, México.
authors.forename: Irán F
authors.initials: IF
authors.lastname: Hernández-Ahuactzi
authors.affiliation: Centro de Investigación, Advanced Materials Research Center , Alianza Norte 202, PIIT, Carretera Monterrey-Aeropuerto Km. 10, Apodaca 66628, Nuevo Leon, México.
authors.forename: Mario
authors.initials: M
authors.lastname: Sánchez