Peer-Reviewed Journal Details
Mandatory Fields
Gargari, MS,Stilinovic, V,Bauza, A,Frontera, A,McArdle, P,Van Derveer, D,Ng, SW,Mahmoudi, G
2015
December
Chemistry-A European Journal
Design of Lead(II) Metal-Organic Frameworks Based on Covalent and Tetrel Bonding
Published
()
Optional Fields
crystal engineering lead metal-organic frameworks noncovalent interactions supramolecular chemistry CHARGE-DENSITY ANALYSIS COORDINATION POLYMERS SUPRAMOLECULAR FORCE STRUCTURAL DIVERSITY HOLE INTERACTIONS LIGANDS CHEMISTRY COMPLEXES SIZE
21
17951
17958
Three solid materials, [Pb(HL)(SCN)(2)]center dot CH3OH (1), [Pb(HL)(SCN)(2)] (2), and [Pb(L)(SCN)](n) (3), were obtained from Pb(SCN)(2) and an unsymmetrical bis-pyridyl hydrazone ligand that can act both as a bridging and as a chelating ligand. In all three the lead center is hemidirectionally coordinated and is thus sterically optimal for participation in tetrel bonding. In the crystal structures of all three compounds, the lead atoms participate in short contacts with thiocyanate sulfur or nitrogen atoms. These contacts are shorter than the sums of the van der Waals radii (3.04-3.47 angstrom for Pb center dot center dot center dot S and 3.54 angstrom for Pb center dot center dot center dot N) and interconnect the covalently bonded units (monomers, dimers, and 2D polymers) into supramolecular assemblies (chains and 3D structures). DFT calculations showed these contacts to be tetrel bonds of considerable energy (6.5-10.5 kcalmol(-1) for Pb center dot center dot center dot S and 16.5 kcalmol(-1) for Pb center dot center dot center dot N). A survey of structures in the CSD showed that similar contacts often appear in crystals of Pb-II complexes with regular geometries, which leads to the conclusion that tetrel bonding plays a significant role in the supramolecular chemistry of Pb-II.
10.1002/chem.201501916
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