Chiral periodic mesoporous organosilicates based on axially chiral monomers: transmission of chirality in the solid state.
Chiral periodic mesoporous organosilicates based on axially chiral monomers: transmission of chirality in the solid state.
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DOI：
10.1021/ja804866e
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发表时间：
2008-10
影响因子：
15
通讯作者：
S. MacQuarrie;M. Thompson;A. Blanc;N. Mosey;R. Lemieux;C. Crudden
中科院分区：
文献类型：
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作者：
S. MacQuarrie;M. Thompson;A. Blanc;N. Mosey;R. Lemieux;C. Crudden
以纯有机单体为掺杂剂，以简单的4，4‘-双(三乙氧基硅基)联苯为主体材料，制备了手性介孔材料。对这些材料的圆二色谱分析表明，在固体状态下形成了新的手性聚集体，这与相邻芳基紧密接触时的电荷离域一致。只有当联苯和对映体纯联芳基都存在时，才能观察到这些聚集体。由这些相互作用产生的CD信号的红移结果是使用依赖于时间的DFT计算来计算建模的。
Chiral mesoporous materials have been prepared with purely organic monomers employing an enantiomerically pure biphenyl bis-siloxane as a dopant along with simple 4,4'-bis(triethoxysilyl)biphenyl as the bulk material. Analysis of these materials by CD spectroscopy indicates the formation of new chiral aggregates in the solid state consistent with charge delocalization from adjacent aryl rings in close contact. These aggregates are only observed when the biphenyl and enantiomerically pure biaryl are both present. The red-shift resulting of the CD signal resulting from these interactions is modeled computationally using time-dependent DFT calculations.