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- Title
Anion Effect on the Formation of Zinc‐Salicyaldimine Compounds in Neutral and Anionic Complex Forms: Synthesis, Characterization, <sup>1</sup>H NMR Studies, and Photophysical Properties.
- Authors
Tsai, Meng‐Jung; Su, Yo‐Ting; Wu, Jing‐Yun
- Abstract
Reactions of Zn(BF4)2 and ZnCl2 with a nitrile‐functionalized salicyaldimine ligand, 3‐(salicylideneimino)benzonitrile (Hsal‐3‐PhCN), in both 1 : 1 and 1 : 2 stoichiometry of metal‐to‐ligand, afforded zinc‐salicyaldimine compounds [Zn(sal‐3‐PhCN)2] (1) and [HNEt3][Zn(sal‐3‐PhCN)Cl2] (2), respectively. Compound 1 is a neutral zinc‐salicyaldimine complex, where the Zn(II) center is in a distorted {ZnN2O2} tetrahedral geometry, made up of two sal‐3‐PhCN ligands both in the N,O‐chelating mode. Comparably, 2 is an ionic zinc‐salicyaldimine compound, where the Zn(II) center is in a distorted {ZnNOCl2} tetrahedral geometry, made up of one sal‐3‐PhCN ligand in the N,O‐chelating mode and two chloro ligands. The results indicate that neutral and anionic forms of zinc‐salicyaldimine complexes would form under the domination of anion with different zinc‐binding abilities. 1H NMR studies indicate different degrees of decomplexation of 2 in different solvents, leading to a dynamic equilibrium between the zinc‐salicyaldimine complex form and the neutral form of salicyaldimine ligand. This is achieved by proton transfer and interpreted by the hydrogen‐bonding properties of the solvents. Photophysical studies reveal that Hsal‐3‐PhCN exhibited weak yellow fluorescence (λem=554 nm) while 1 and 2 emitted strong blue (λem=472 nm) and green (λem=504 nm) fluorescence, respectively, in solid‐state, and in comparison, much weaker emissions in solution phases.
- Subjects
ANIONS; FLUORESCENCE; STOICHIOMETRY; ZINC compounds; LIGANDS (Chemistry); BENZONITRILE
- Publication
European Journal of Inorganic Chemistry, 2021, Vol 2021, Issue 31, p3139
- ISSN
1434-1948
- Publication type
Article
- DOI
10.1002/ejic.202100377