Wen-Jun Mi, Wen-Chao Bi, Ming-Ze Meng, Yi-Ping Chen, Yan-Qiong Sun
{"title":"A Spectroscopic Method for Distinguishing Two Novel Sandwich-Type Tungsten Oxide Cluster Compounds.","authors":"Wen-Jun Mi, Wen-Chao Bi, Ming-Ze Meng, Yi-Ping Chen, Yan-Qiong Sun","doi":"10.1177/00037028241254093","DOIUrl":null,"url":null,"abstract":"<p><p>This study introduces two novel sandwich-type tungsten-oxygen cluster compounds synthesized by hydrothermal methods, H<sub>4</sub>(C<sub>6</sub>H<sub>12</sub>N<sub>2</sub>H<sub>2</sub>)<sub>3</sub>{Na(H<sub>2</sub>O)<sub>2</sub>[Mn<sub>2</sub>(H<sub>2</sub>O)(GeW<sub>9</sub>O<sub>34</sub>)]}<sub>2</sub> (Compound 1) and H<sub>2</sub>(C<sub>6</sub>H<sub>12</sub>N<sub>2</sub>H<sub>2</sub>)<sub>3.5</sub>{Na<sub>3</sub>(H<sub>2</sub>O)<sub>4</sub>[Co<sub>2</sub>(H<sub>2</sub>O)(GeW<sub>9</sub>O<sub>34</sub>)]<sub>2</sub>}·17H<sub>2</sub>O (Compound 2). The two compounds comprise cluster anions [GeW<sub>9</sub>O<sub>34</sub>]<sup>10-</sup> coordinated with transition metal atoms, either Mn or Co, and are stabilized by organic ligands. These compounds are crystallized in the hexagonal crystal system and P6<sub>3</sub>/m space group. The two compounds were characterized through various techniques. Fourier transform infrared (IR) spectroscopy showed absorption peaks of anionic backbone vibrations of the Keggin cluster at 500-1000 cm<sup>-1</sup>, IR spectral peaks of δ(N-H) and ν<sub>as</sub>(C-N) of the ligand triethylenediamine at 1000-2000 cm<sup>-1</sup>, and IR spectral peaks of the ligand ν<sub>as</sub>(N-H) and ν<sub>as</sub>(O-H) of water at 3000-3500 cm<sup>-1</sup>. Despite similar one-dimensional (1D) IR spectra due to the same cluster anions and similar molecular structures, the two compounds exhibited distinct responses in two-dimensional correlation spectroscopy with IR under magnetic and thermal perturbations. Under magnetic perturbation, Compound 1 showed a strong response peak for ν<sub>as</sub>(W-O<sub>b</sub>-W), while Compound 2 exhibited a strong response peak for ν<sub>as</sub>(W=O<sub>d</sub>), possibly linked to differing magnetic particles. Similarly, Compound 1 displayed a strong response peak under thermal perturbation for ν<sub>as</sub>(W-O<sub>c</sub>-W). In contrast, Compound 2 showed a strong response peak for ν<sub>as</sub>(W=O<sub>d</sub>); these results may be attributed to the different hydrogen bonding connections between the two compounds, which affect the groups in distinct ways through vibration and transmit these vibrations to the W-O bonds. The research presented in this paper expands the theoretical and experimental data of 2D correlation IR spectroscopy.</p>","PeriodicalId":8253,"journal":{"name":"Applied Spectroscopy","volume":" ","pages":"37028241254093"},"PeriodicalIF":2.2000,"publicationDate":"2024-05-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Applied Spectroscopy","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1177/00037028241254093","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"INSTRUMENTS & INSTRUMENTATION","Score":null,"Total":0}
引用次数: 0
Abstract
This study introduces two novel sandwich-type tungsten-oxygen cluster compounds synthesized by hydrothermal methods, H4(C6H12N2H2)3{Na(H2O)2[Mn2(H2O)(GeW9O34)]}2 (Compound 1) and H2(C6H12N2H2)3.5{Na3(H2O)4[Co2(H2O)(GeW9O34)]2}·17H2O (Compound 2). The two compounds comprise cluster anions [GeW9O34]10- coordinated with transition metal atoms, either Mn or Co, and are stabilized by organic ligands. These compounds are crystallized in the hexagonal crystal system and P63/m space group. The two compounds were characterized through various techniques. Fourier transform infrared (IR) spectroscopy showed absorption peaks of anionic backbone vibrations of the Keggin cluster at 500-1000 cm-1, IR spectral peaks of δ(N-H) and νas(C-N) of the ligand triethylenediamine at 1000-2000 cm-1, and IR spectral peaks of the ligand νas(N-H) and νas(O-H) of water at 3000-3500 cm-1. Despite similar one-dimensional (1D) IR spectra due to the same cluster anions and similar molecular structures, the two compounds exhibited distinct responses in two-dimensional correlation spectroscopy with IR under magnetic and thermal perturbations. Under magnetic perturbation, Compound 1 showed a strong response peak for νas(W-Ob-W), while Compound 2 exhibited a strong response peak for νas(W=Od), possibly linked to differing magnetic particles. Similarly, Compound 1 displayed a strong response peak under thermal perturbation for νas(W-Oc-W). In contrast, Compound 2 showed a strong response peak for νas(W=Od); these results may be attributed to the different hydrogen bonding connections between the two compounds, which affect the groups in distinct ways through vibration and transmit these vibrations to the W-O bonds. The research presented in this paper expands the theoretical and experimental data of 2D correlation IR spectroscopy.
期刊介绍：
Applied Spectroscopy is one of the world''s leading spectroscopy journals, publishing high-quality peer-reviewed articles, both fundamental and applied, covering all aspects of spectroscopy. Established in 1951, the journal is owned by the Society for Applied Spectroscopy and is published monthly. The journal is dedicated to fulfilling the mission of the Society to “…advance and disseminate knowledge and information concerning the art and science of spectroscopy and other allied sciences.”
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