Exploring the thermochromism of sulfite-embedded polyoxometalate capsules.
Exploring the thermochromism of sulfite-embedded polyoxometalate capsules.
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DOI：
10.1039/c1cp20074g
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发表时间：
2011-04
期刊：
影响因子：
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通讯作者：
R. Tsunashima;D. Long;Toru Endo;S. Noro;T. Akutagawa;Takayoshi Nakamura;R. Cabrera;P. McMillan;P. Kögerler;L. Cronin
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文献类型：
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作者：
R. Tsunashima;D. Long;Toru Endo;S. Noro;T. Akutagawa;Takayoshi Nakamura;R. Cabrera;P. McMillan;P. Kögerler;L. Cronin
Dawson型多阴离子[α-Mo（18）O（54）（SO（3））（2）]（4-），以两个SO（3）（2-）为模板嵌入多钼酸盐（vi）笼中，在很宽的温度范围内（~ 500 K）表现出热色性。簇结构的温度依赖性，建立从X-射线晶体学，IR和拉曼光谱和DFT计算，是相关的降低HOMO-LUMO间隙在近紫外随着温度的升高。我们假设这是由于几何形状的变化，影响这一簇阴离子的占据和未占据的前沿分子轨道。
The Dawson-type polyanion [α-Mo(18)O(54)(SO(3))(2)](4-), with two SO(3)(2-) templates embedded inside a polyoxomolybdate(vi) cage, exhibits thermochromism over an exceptionally wide temperature range (∼500 K). The temperature dependence of the cluster structure, established from X-ray crystallography, IR and Raman spectroscopy and DFT calculations, is related to a decreasing HOMO-LUMO gap in the near UV with increasing temperature. We postulate this is due to geometrical changes that affect both the occupied and unoccupied frontier molecular orbitals of this cluster anion.