Design of Lead(II) Metal-Organic Frameworks Based on Covalent and Tetrel Bonding.
Chemistry
; 21(49): 17951-8, 2015 Dec 01.
Article
em En
| MEDLINE
| ID: mdl-26489982
ABSTRACT
Three solid materials, [Pb(HL)(SCN)2 ]â
CH3 OH (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 (3.04-3.47â
Å for Pbâ
â
â
S and 3.54â
Å for Pbâ
â
â
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 (6.5-10.5â
kcal mol(-1) for Pbâ
â
â
S and 16.5â
kcal mol(-1) for Pbâ
â
â
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) .
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MEDLINE
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En
Revista:
Chemistry
Ano de publicação:
2015
Tipo de documento:
Article