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On the pivotal role of tetrel bonding in the supramolecular architectures of PbII–NCS complexes with chelating thiosemicarbazide derivatives.
- Source :
- CrystEngComm; 3/21/2024, Vol. 26 Issue 11, p1637-1646, 10p
- Publication Year :
- 2024
-
Abstract
- Three new Pb<superscript>II</superscript> complexes [Pb(L<superscript>I</superscript>)(SCN)]<subscript>n</subscript>, {[Pb(L<superscript>II</superscript>)](SCN)}<subscript>n</subscript> and {[Pb(HL<superscript>III</superscript>)(SCN)](SCN)}<subscript>n</subscript> (HL<superscript>I</superscript> = N′-phenyl(pyridin-2-yl)methylene-N-phenylthiosemicarbazide, HL<superscript>II</superscript> = N′-amino(pyrazin-2-yl)methylenethiosemicarbazide, HL<superscript>III</superscript> = N′-amino(pyridin-2-yl)methylenethiosemicarbazide) have been synthesized and characterized by spectroscopic techniques and single crystal X-ray diffraction. In all complexes, the corresponding organic ligand behaves as a tridentate N,N′,S-chelating species. A 1D supramolecular polymeric aggregation in complex [Pb(L<superscript>I</superscript>)(SCN)]<subscript>n</subscript> is dictated by the Pb⋯NCS and Pb⋯S=C tetrel bonds formed between the [Pb(L<superscript>I</superscript>)(SCN)] species. 1D cationic coordination polymers ([Pb(L<superscript>II</superscript>)])<subscript>n</subscript><superscript>n+</superscript> in the structure of complex {[Pb(L<superscript>II</superscript>)](SCN)}<subscript>n</subscript> are linked into a 2D supramolecular polymeric layer through the Pb⋯NCS tetrel bonds and Pb⋯π(NCS) interactions formed with the nitrogen atom and the conjugated system of the free SCN<superscript>−</superscript> anions, respectively. The cationic species [Pb(HL<superscript>III</superscript>)(SCN)]<superscript>+</superscript> in the structure of complex {[Pb(HL<superscript>III</superscript>)(SCN)](SCN)}<subscript>n</subscript> produce a 1D supramolecular polymer due to the Pb⋯SCN and Pb⋯S=C tetrel bonds, further stabilized by the Pb⋯π(NCS) interactions formed with the conjugated system of the coordinated NCS<superscript>−</superscript> anion. The latter anions also link these 1D chains through the Pb⋯SCN tetrel bonds, yielding 1D supramolecular polymeric ribbons. The energetic relevance of the Pb⋯S and Pb⋯N tetrel bonds has been studied by DFT calculations. The tetrel bonds have been characterized using QTAIM and NCIplot analysis and rationalized using molecular electrostatic potential surface calculations. [ABSTRACT FROM AUTHOR]
Details
- Language :
- English
- ISSN :
- 14668033
- Volume :
- 26
- Issue :
- 11
- Database :
- Complementary Index
- Journal :
- CrystEngComm
- Publication Type :
- Academic Journal
- Accession number :
- 175940437
- Full Text :
- https://doi.org/10.1039/d3ce01207g