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镧系发光在固态中作为报告分子的应用:γ-磷酸锆/膦酸酯前手性层的去对称化和圆偏振发光。

The use of lanthanide luminescence as a reporter in the solid state: Desymmetrization of the prochiral layers of γ-zirconium phosphate/phosphonate and circularly polarized luminescence.

作者信息

Brunet Ernesto, Jiménez Laura, de Victoria-Rodriguez María, Luu Vinh, Muller Gilles, Juanes Olga, Rodríguez-Ubis Juan Carlos

机构信息

Departamento de Química Orgánica, Facultad de Ciencias C-1, Universidad Autónoma de Madrid, 28049 Madrid, Spain.

出版信息

Microporous Mesoporous Mater. 2013 Mar 15;169:222-234. doi: 10.1016/j.micromeso.2012.11.009.

Abstract

Solid-state CPL measurements were performed for the first time on hybrid, laminar materials based on γ-ZrP pillared with organic diphosphonates. Ad hoc optically pure diphosphonates were synthesized and the luminescence properties of their complexation with Tb(III) were verified in solution. CD and CPL measurements showed that the bistriazolylpyridine chromophores bonded to the metal provided an effective chiral environment that produced significant signals. In the case of the γ-ZrP-derived materials, experimental evidence and simple molecular modeling hinted to the occurrence of supramolecular chirality in the particles, induced by the intrinsic dissymmetry of the organic diphosphonates or by the intercalation of chiral species such as 1-phenethylamine. Chirality at the supramolecular level was revealed in the solid state by the CPL signals measured from reporter Tb(III) ions intercalated in the hybrid matrix.

摘要

首次对基于用有机二膦酸盐柱撑的γ-ZrP的混合层状材料进行了固态圆偏振发光(CPL)测量。合成了特定的光学纯二膦酸盐,并在溶液中验证了它们与Tb(III)络合的发光性质。圆二色性(CD)和CPL测量表明,与金属键合的双三唑基吡啶发色团提供了一个有效的手性环境,产生了显著的信号。对于源自γ-ZrP的材料,实验证据和简单的分子模型表明,颗粒中存在超分子手性,这是由有机二膦酸盐的固有不对称性或手性物种(如1-苯乙胺)的插层引起的。通过从插层在混合基质中的报告Tb(III)离子测量的CPL信号,在固态中揭示了超分子水平的手性。

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