Department of Chemistry, University of North Carolina, Chapel Hill, 27599, United States.
J Am Chem Soc. 2012 Jun 6;134(22):9050-3. doi: 10.1021/ja302110d. Epub 2012 May 24.
A highly porous and fluorescent metal-organic framework (MOF), 1, was built from a chiral tetracarboxylate bridging ligand derived from 1,1'-bi-2-naphthol (BINOL) and a cadmium carboxylate infinite-chain secondary building unit. The fluorescence of 1 can be effectively quenched by amino alcohols via H-bonding with the binaphthol moieties decorating the MOF, leading to a remarkable chiral sensor for amino alcohols with greatly enhanced sensitivity and enantioselectivity over BINOL-based homogeneous systems. The higher detection sensitivity of 1 is due to a preconcentration effect by which the analytes are absorbed and concentrated inside the MOF channels, whereas the higher enantioselectivity of 1 is believed to result from enhanced chiral discrimination owing to the cavity confinement effect and the conformational rigidity of the BINOL groups in the framework. 1 was quenched by four chiral amino alcohols with unprecedentedly high Stern-Volmer constants of 490-31200 M(-1) and enantioselectivity ratios of 1.17-3.12.
一种高多孔和荧光的金属-有机骨架(MOF),1,是由手性四羧酸桥联配体构建的,该配体来自 1,1'-联-2-萘酚(BINOL)和镉羧酸无限链次级构筑单元。1 的荧光可以通过与修饰 MOF 的联萘酚部分的氢键有效地被氨基醇猝灭,从而导致对氨基醇具有显著增强的灵敏度和对映选择性的手性传感器,超过基于 BINOL 的均相体系。1 的更高检测灵敏度是由于预浓缩效应,通过该效应,分析物被吸收并在 MOF 通道内浓缩,而 1 的更高对映选择性则归因于空腔限域效应和框架中 BINOL 基团的构象刚性增强的手性区分。1 被四个手性氨基醇猝灭,具有前所未有的高 Stern-Volmer 常数 490-31200 M(-1)和 1.17-3.12 的对映选择性比。