Equilibria between metallosupramolecular squares and triangles with the new rigid linker 1,4-bis(4-pyridyl)tetrafluorobenzene. Experimental and theoretical study of the structural dependence of NMR data

Montserrat Ferrer; Mounia Mounir; Oriol Rossell; Eliseo Ruiz; Miguel Angel Maestro

doi:10.1021/ic034489j

Equilibria between metallosupramolecular squares and triangles with the new rigid linker 1,4-bis(4-pyridyl)tetrafluorobenzene. Experimental and theoretical study of the structural dependence of NMR data

Inorg Chem. 2003 Sep 22;42(19):5890-9. doi: 10.1021/ic034489j.

Authors

Montserrat Ferrer¹, Mounia Mounir, Oriol Rossell, Eliseo Ruiz, Miguel Angel Maestro

Affiliation

¹ Departament de Química Inorgànica, Universitat de Barcelona, Martí i Franquès 1-11, 08028 Barcelona, Spain.

PMID: 12971757
DOI: 10.1021/ic034489j

Abstract

The new fluorinated rigid ligand L, 1,4-bis(4-pyridyl)tetrafluorobenzene, was used in combination with different diphosphine Pd(II) and Pt(II) triflates to build metallosupramolecular assemblies. Complex equilibria between triangular and square entities were detected for all the cases. Characterization of the equilibria was accomplished by 1H, 31P(1H), 19F, and 195Pt(1H) NMR in combination with mass spectrometry. The square/triangle ratio was seen to depend on several factors, such as the nature of the metal corners, the concentration, and the solvent. The relative stability of the square and triangular complexes was explored by using force field methods. A GIAO-DFT study was carried out to analyze the changes of the 31P and 1H NMR data with the geometry of the complexes.