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":2,"journal":{"name":"ACS Applied Bio Materials","volume":null,"pages":null},"PeriodicalIF":4.6000,"publicationDate":"2024-05-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"ACS Applied Bio Materials","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1177/00037028241254093","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"MATERIALS SCIENCE, BIOMATERIALS","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.
求助内容：
应助结果提醒方式：
京公网安备 11010802042870号
