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单分子磁体-锰配合物的高压红外光谱研究

Pressure-Tuning Infrared Spectral Study on the Single-Molecule-Magnet Manganese Complexes

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【作者】 许振华陈志达Ian S Butler

【Author】 XU Zhen hua 1, CHEN Zhi da 1, Ian S Butler 2 1. The State Key Labosatory of Rare Earth Materials Chemistry and Applications, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China 2. Department of Chemistry, McGill University, 801 Sherbrooke Street West, Quebec, Montreal Canada, H3A 2K6

【机构】 北京大学化学与分子工程学院Department of Chemistry 稀土材料化学与应用国家重点实验室北京100871稀土材料化学与应用国家重点实验室McGill University801 Sherbrooke Street WestMontrealQuebecCanada H3A2K6

【摘要】 研究了单分子磁体锰配合物Ⅰ :[Mn1 2 O1 2 (O2 CC6 H4 3 Cl) 1 6 (H2 O) 3(3 Cl C6 H4 CO2 H) ]·(3 Cl C6 H4 CO2 H)和配合物Ⅱ :[Mn1 2 O1 2 (O2 CCH2 Br) 1 6 (H2 O) 4]·4 (CH2 Cl2 )的高压红外光谱 ,两者不同的压力诱导相转变的压力 (配合物Ⅰ :2 5~ 2 9kbar,配合物Ⅱ :2 9~ 35kbar)被观察到 ,两者均为二级压力诱导相转变。认为在压力诱导相转变时 ,也发生了配合物高自旋向低态自旋态的转变。配合物Ⅰ的平均压力灵敏度不同于通常情况 ,它在低压相区的平均压力灵敏度 (0 19cm- 1 ·kbar- 1 )比高压相区 (0 2 9cm- 1 ·kbar- 1 )低。而配合物Ⅱ与通常情况相似 ,在低压相区平均压力灵敏度 (0 34cm- 1 ·kbar- 1 )比高压相区 (0 2 3cm- 1 ·kbar- 1 )为高 ,即在高压相区的可压缩性比低压相区小。

【Abstract】 The infrared spectra (IR) of single molecule magnet manganese complexes [Mn 12 O 12 (O 2CC 6H 4 3 Cl) 16 (H 2O) 3(3Cl C 6H 4CO 2H)]·(3 Cl C 6H 4CO 2H)(Ⅰ) and [Mn 12 O 12 (O 2CCH 2Br) 16 (H 2O) 4]·4(CH 2Cl 2)(Ⅱ) were studied at high external pressure . The different pressure induced phase transition pressures were observed for both complexes (complex Ⅰ, 25 29 kbar) and (complex Ⅱ, 29 35 kbar). Both were second order pressure induced phase transition. The possible changes from higher spin to lower spin happened near the phase transition pressure following the changes of their structures when undergoing the high pressures. The average value of pressure sensitivities in the low pressure phase is unusually smaller (0 19 cm -1 ·kbar -1 ) than in the high pressure phase (0 29 cm -1 ·kbar -1 ) in the complex Ⅰ. On the contrary, the average value of the pressure sensitivities in the low pressure phase is higher (0 34 cm -1 ·kbar -1 ) than in the high pressure phase (0 23 cm -1 ·kbar -1 ) in the complex Ⅱ as usually, which means that the possibility of compression is lower in the high pressure phase than in the low pressure phase.

【基金】 国家自然科学基金 (50 2 0 30 0 1,2 0 0 2 30 0 5和G1 9980 61 30 7)资助项目
  • 【文献出处】 光谱学与光谱分析 ,Spectroscopy and Spectral Analysis , 编辑部邮箱 ,2004年06期
  • 【分类号】O657.3
  • 【下载频次】272
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