Two-dimensional correlation infrared spectroscopy study on vanadoborate anionic skeleton regulated by countercations.

Autor: Meng MZ; College of Chemistry, Fuzhou University, Fuzhou 350002, Fujian, China., Shi GD; College of Chemistry, Fuzhou University, Fuzhou 350002, Fujian, China., Cheng LL; College of Chemistry, Fuzhou University, Fuzhou 350002, Fujian, China., Chen YP; College of Chemistry, Fuzhou University, Fuzhou 350002, Fujian, China; State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002, China. Electronic address: ypchen@fzu.edu.cn., Zhang YF; College of Chemistry, Fuzhou University, Fuzhou 350002, Fujian, China., Lin W; College of Chemistry, Fuzhou University, Fuzhou 350002, Fujian, China. Electronic address: wlin@fzu.edu.cn.
Jazyk: angličtina
Zdroj: Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy [Spectrochim Acta A Mol Biomol Spectrosc] 2024 Apr 15; Vol. 311, pp. 123992. Date of Electronic Publication: 2024 Feb 04.
DOI: 10.1016/j.saa.2024.123992
Abstrakt: Two novel vanadoborate compounds, [Cu(en) 2 ] 3 [Li(H 2 O)] 4 [Li(H 2 O) 3 ] 2 [V 12 B 18 O 50 (OH) 10 (H 2 O)] 2 ·33.5H 2 O (1) and (H 2 en) 4 [Li(H 2 O)] 4 [V 12 B 18 O 55 (OH) 5 (H 2 O)]·14H 2 O (2), were synthesized via hydrothermal synthesis under identical conditions except for temperature. Structural analysis revealed that although both contain [V 12 B 18 O 60 ] n- cluster anion, the different countercations potentially lead to variations in the [V 12 B 18 O 60 ] n- cluster anion skeletons. In compound 1, the V 4+ /V 5+ ratio was 10:2; while in compound 2 the ratio was 11:1. It is speculated that different countercations may influence the valence states of cluster anions. In this study, quantum chemical calculations revealed that the aromaticity and activity of the two compounds were different, and two-dimensional correlation infrared spectroscopy (2D-COS-IR) under magnetic perturbation confirmed that distinct response peaks of functional group vibrations to the magnetic field due to the different V 4+ /V 5+ ratios and aromaticity of the two compounds. An electrochemical analysis revealed that compound 2 exhibits higher electrocatalytic activity. The results of quantum chemical calculations are aligned not only with the changes in the 2D-COS-IR spectra but also with the conclusions obtained from experiments on electrochemical properties. Overall, this work proposes a novel strategy for interpreting the alteration of vanadoborate anionic skeleton due to the introduction of different countercations by combining 2D-COS-IR with quantum chemical calculations.
Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.
(Copyright © 2024 Elsevier B.V. All rights reserved.)
Databáze: MEDLINE
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