A Spectroscopic Method for Distinguishing Two Novel Sandwich-Type Tungsten Oxide Cluster Compounds

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 ν_as(C–N) of the ligand triethylenediamine at 1000–2000 cm^–1, and IR spectral peaks of the ligand ν_as(N–H) and ν_as(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 ν_as(W–O_b–W), while Compound 2 exhibited a strong response peak for ν_as(W=O_d), possibly linked to differing magnetic particles. Similarly, Compound 1 displayed a strong response peak under thermal perturbation for ν_as(W–O_c–W). In contrast, Compound 2 showed a strong response peak for ν_as(W=O_d); 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.

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Keywords

Tungsten oxide cluster compound crystal structure infrared spectroscopy IR‌two-dimensional correlation spectroscopy 2D-COS

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