title: Influence of Metal, Ligand and Solvent on Supramolecular Polymerizations with Transition-Metal Compounds: A Theoretical Study.
abstract: The nature of intermolecular interactions governing supramolecular polymerizations is very important for controlling their cooperativity. In order to address this problem, supramolecular columns made of PtIIand PdIIcomplexes of oligo(phenylene ethynylene)-based pyridine (OPE) and tetrazolylpyridine ligands (TEP) were investigated through the dispersion-corrected PM6 method. Aromatic, CH-π, M-Cl and metallophilic interactions helped stabilize the supramolecules studied, and their geometries and associated cooperativities were in excellent agreement with experimental data. The OPE ligand and/or the presence of PtIIled to stronger metallophilic interactions and also to cooperative supramolecular polymerizations, which clearly suggests that metallophilic interactions are a key factor for controlling cooperativity. The results indicate that sequential monomer addition is in general less spontaneous than the combination of two larger preformed stacks. The present theoretical investigations contribute to the further understanding of the relation between the thermodynamics of supramolecular polymerizations and the nature of different synthons.
authors.affiliation: Sao Carlos Institute of Chemistry, University of Sao Paulo (USP), Sao Carlos, Brazil.
authors.forename: Naidel A M S
authors.initials: NA
authors.lastname: Caturello
authors.affiliation: Sao Carlos Institute of Chemistry, University of Sao Paulo (USP), Sao Carlos, Brazil.
authors.forename: Zsolt
authors.initials: Z
authors.lastname: Csók
authors.affiliation: Organisch-Chemisches Institut, Westfälische Wilhelms-Universität Münster, 48149, Münster, Germany.
authors.forename: Gustavo
authors.initials: G
authors.lastname: Fernández
authors.affiliation: School of Pharmacy and Biomolecular Sciences, Liverpool John Moores University (LJMU), Byrom Str. Campus, Liverpool, L3 3AF, UK.|Sao Carlos Institute of Chemistry, University of Sao Paulo (USP), Sao Carlos, Brazil.
authors.forename: Rodrigo Q
authors.initials: RQ
authors.lastname: Albuquerque
keywords: cooperativity; self-assembly; semiempirical calculations; supramolecular polymerization; transition-metal complexes