Hayduk Matthias, Schaller Torsten, Niemeyer Felix C, Rudolph Kevin, Clever Guido H, Rizzo Fabio, Voskuhl Jens
Faculty of Chemistry (Organic Chemistry), ZMB and CENIDE, University of Duisburg-Essen, Universitätsstraße 7, Essen, 45141, Germany.
Technische Universität Dortmund, Fakultät für Chemie und Chemische Biologie, Otto-Hahn-Straße 6, 44227, Dortmund, Germany.
Chemistry. 2022 Sep 12;28(51):e202201081. doi: 10.1002/chem.202201081. Epub 2022 Jul 25.
We present an in-depth investigation of cyclodextrin complexes with guest compounds featuring complexation-induced room temperature phosphorescence (RTP) in aqueous solution. Very interestingly, only the complexed regioisomers bearing lateral substituents on meta-position show RTP, whereas the stronger host-guest systems with para-substituted dyes show no RTP features. The reported systems were investigated regarding their complexation behavior in water using isothermal titration calorimetry and mass spectrometry. In the case of γ-CD very strong 1 : 1 inclusion complexes (K up to 5.13×10 M ) were unexpectedly observed. It was found that not only a strong binding to the cyclodextrin cavity is needed to restrict motion, inducing the emission, but also the conformation inside the cavity plays a pivotal role - as supported by an extensive NMR study and MD simulations.
我们对环糊精与客体化合物的复合物进行了深入研究，这些复合物在水溶液中具有络合诱导室温磷光（RTP）特性。非常有趣的是，只有在间位带有侧链取代基的络合区域异构体显示出RTP，而具有对位取代染料的更强的主客体体系则没有RTP特征。使用等温滴定量热法和质谱法研究了所报道的体系在水中的络合行为。对于γ-环糊精，意外地观察到非常强的1∶1包合物（K高达5.13×10 M）。研究发现，不仅需要与环糊精腔有强结合来限制运动以诱导发射，而且腔内的构象也起着关键作用——广泛的核磁共振研究和分子动力学模拟支持了这一点。
