Diagnosis of the Redox Levels of TCNQF4 Compounds Using Vibrational Spectroscopy
Diagnosis of the Redox Levels of TCNQF4 Compounds Using Vibrational Spectroscopy
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使用振动光谱诊断 TCNQF4 化合物的氧化还原水平
DOI：
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发表时间：
2014
期刊：
影响因子：
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通讯作者：
L. Martin
中科院分区：
文献类型：
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作者：
N. Haworth;Jinzhen Lu;Nguyen T. Vo;Thanh;C. Thompson;A. Bond;L. Martin
用密度泛函理论研究了TCNQF_4、TCNQF_41-和TCNQF_42-的振动光谱。在红外和拉曼光谱的频带分配已被澄清和一系列的诊断开发的TCNQF 4化合物的氧化还原水平表征。在C-C伸缩区（1460-1600 cm-1），TCNQF 40和TCNQF 41-显示出两个带，TCNQF 40在1600 cm-1处能量更高，TCNQF 41-在约1535 cm-1处能量更高;在TCNQF 42-中，两种模式在1500 cm-1以下吸收，通常合并为一个带。在C-F和内环C-C伸缩区（1290和1360 cm-1），TCNQF 40和TCNQF 41-显示出较强的吸收带，而TCNQF 42-吸收较弱或根本没有吸收。（额外的谱带，例如来自共结晶溶剂分子的谱带，可能使该区域复杂化。在腈伸缩区域（2000-2250 cm-1），模式对金属阳离子的腈配位高度敏感。所有三个氧化还原能级都能产生高于2200 cm-1的谱带，而低于2150 cm-1的谱带通常是由于TCNQF 42-。这种对配位的敏感性可能会影响许多有机分子离子的光谱。© 2014 WILEY-VCH Verlag GmbH & Co. KGaA，魏因海姆。
The vibrational spectroscopy of TCNQF4, TCNQF41- and TCNQF42- has been investigated by means of density functional theory. Band assignments in infrared and Raman spectra have been clarified and a series of diagnostics developed for redox level characterisation of TCNQF4 compounds. In the C£C stretching region (1460-1600 cm-1), TCNQF40 and TCNQF 41- show two bands, with the more energetic being at 1600 cm-1 in TCNQF40 and at approximately 1535 cm-1 in TCNQF41-; in TCNQF42- both modes absorb below 1500 cm-1, often merging to give a single band. In the C-F and endocyclic C-C stretching region (1290 and 1360 cm-1), TCNQF40 and TCNQF41- show strong bands, whereas TCNQF42- absorbs weakly or not at all. (Additional bands, e.g. from co-crystallised solvent molecules, may complicate this region.) In the nitrile stretching region (2000-2250 cm-1), modes are highly sensitive to nitrile coordination by metal cations. All three redox levels can produce bands above 2200 cm -1, however bands below 2150 cm-1 are usually due to TCNQF42-. This sensitivity to coordination is likely to affect the spectra of many organic molecular ions. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.