Journal
POLYHEDRON
Volume 205, Issue -, Pages -Publisher
PERGAMON-ELSEVIER SCIENCE LTD
DOI: 10.1016/j.poly.2021.115301
Keywords
Bis(salamo)-based ligand; Binuclear complex; Crystal structure; DFT; Fluorescence
Categories
Funding
- National Natural Science Foundationof China [21761018]
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X-ray analysis revealed the presence of two structurally independent but chemically identical binuclear complex molecules in complexes 1 and 2, while three structurally independent but chemically identical binuclear complex molecules were detected in complex 3.
A new symmetrical multi-halogen-substituted bis(salamo)-based tetraoxime ligand H3L and its corresponding penta-coordinated homo-binuclear Co(II) and Zn(II) complexes have been successfully synthesized. The three complexes, [{Co2(L)(OCH3)}2]CHCl3 (1), [{Zn2(L)(OCH3)}2]CH3OH (2) and [{Co2(L)(OCH2CH3)}3] 2CH3CH2OHCHCl3 (3), have been characterized by elemental analyses, FT-IR and UV-Vis absorption spectroscopy as well as X-ray single-crystal structure analyses. In complexes 1 and 2, two crystallographically independent but chemically identical binuclear complex molecules A and B were detected by X-ray analysis. However, in complex 3, three crystallographically independent but chemically identical binuclear complex molecules A, B and C were detected. All the penta-coordinated Co(II) and Zn(II) atoms in complexes 1 and 2 are located in the N2O2 cavities of the completely deprotonated (L)3- units and coordinated to one oxygen atom from one mu 2-bridged methoxyl group. The coordination environment of the Co(II) atoms in complexes 1 and 3 are similar, except that the mu 2-bridged methoxyl group is replaced with the mu 2-bridged ethoxyl group. Additionally, both of complexes 1 and 3 form 3D supramolecular structures through abundant intermolecular interactions, while complex 2 forms 1D supramolecular structure through intermolecular hydrogen bonds. The C-H pi interactions have been established in complexes 1 and 2, where the pi-system of H3L participates as pi-donor. Through the means of Hirshfeld surfaces and 2D fingerprint plot analyses, existing different non-covalent supramolecular interactions in the Co(II) and Zn(II) complexes have been explained. Furthermore, to obtain a better understanding of the fluorescence properties of H3L and its complexes 1-3, fluorescence titration experiments have been performed.
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