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(Reference retrieved automatically from Web of Science through information on FAPESP grant and its corresponding number as mentioned in the publication by the authors.)

Influence of Metal, Ligand and Solvent on Supramolecular Polymerizations with Transition-Metal Compounds: A Theoretical Study

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Caturello, Naidel A. M. S. ; Csok, Zsolt ; Fernandez, Gustavo ; Albuquerque, Rodrigo Q.
Total Authors: 4
Document type: Journal article
Source: CHEMISTRY-A EUROPEAN JOURNAL; v. 22, n. 49, p. 17681-17689, DEC 5 2016.
Web of Science Citations: 3

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 Pt-II and Pd-II complexes of oligo(phenylene ethynylene)-based pyridine (OPE) and tetrazolylpyridine ligands (TEP) were investigated through the dispersion-corrected PM6 method. Aromatic, CH-pi, 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 Pt-II led 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. (AU)

FAPESP's process: 14/02071-5 - Theoretical investigation of the aggregation of cationic complexes of Ir(III) with potential application in LECs and OLEDs
Grantee:Rodrigo Queiroz de Albuquerque
Support type: Regular Research Grants