Pyridine-based bispidine ligandsL1-L7, which differ in the substituent at theN7 position of the bispidine scaffold, have been studied by single crystal X-ray diffraction and density functional theory (DFT) calculations, also including solid-state algorithms. Qualitative description of the packing interactions and quantitative data on the stability of each ligand in the solid-state have been employed to draw reasonable predictions on the ligand potential for the formation of linear 1D coordination polymers (CPs) with Mn(ii)Cl2and on their resulting dynamic properties, in terms of adsorption and solvent exchange capabilities. The basic assumption lies in the fact that volume and polarizability of the ligands would similarly affect packing energies in both molecular solids and CP materials. The results here obtained confirm the data previously reported on CPs (those made fromL4are less dynamic than the ones withL1), but they also allow the prediction that CPs made withL2andL5should be more dynamic than expected, while CPs withL6andL7should not form altogether. This latter prediction was derived from the analysis of the steric and electronic factors of the ligand substituents on theN7 position and it is further substantiated by the obtainment of a 2?:?1 molecular complex, and not a CP, by crystallization ofL6with MnCl2

Combined structural and theoretical investigation on differently substituted bispidine ligands: predicting the properties of their corresponding coordination polymers

Martina Lippi;Antonino Famulari;Alessandro Sacchetti;Javier Martí-Rujas;Massimo Cametti
2020

Abstract

Pyridine-based bispidine ligandsL1-L7, which differ in the substituent at theN7 position of the bispidine scaffold, have been studied by single crystal X-ray diffraction and density functional theory (DFT) calculations, also including solid-state algorithms. Qualitative description of the packing interactions and quantitative data on the stability of each ligand in the solid-state have been employed to draw reasonable predictions on the ligand potential for the formation of linear 1D coordination polymers (CPs) with Mn(ii)Cl2and on their resulting dynamic properties, in terms of adsorption and solvent exchange capabilities. The basic assumption lies in the fact that volume and polarizability of the ligands would similarly affect packing energies in both molecular solids and CP materials. The results here obtained confirm the data previously reported on CPs (those made fromL4are less dynamic than the ones withL1), but they also allow the prediction that CPs made withL2andL5should be more dynamic than expected, while CPs withL6andL7should not form altogether. This latter prediction was derived from the analysis of the steric and electronic factors of the ligand substituents on theN7 position and it is further substantiated by the obtainment of a 2?:?1 molecular complex, and not a CP, by crystallization ofL6with MnCl2
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Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/11311/1143153
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