Huang Yin-Hui, Ge Qing-Mei, Zhao Yong-Yi, Cong Hang, Zhao Jiang-Lin, Tao Zhu, Luo Qing-Ying
Key Laboratory of Macrocyclic and Supramolecular Chemistry of Guizhou Province, Guizhou University, Guiyang 550025, China.
Key Laboratory of Macrocyclic and Supramolecular Chemistry of Guizhou Province, Guizhou University, Guiyang 550025, China.
Spectrochim Acta A Mol Biomol Spectrosc. 2019 Jul 5;218:213-220. doi: 10.1016/j.saa.2019.04.011. Epub 2019 Apr 9.
Fluorescent chemosensors based on a new macrocyclic compound, multifarene[2,2], with modification by triazole-linked pyrene or anthracene were synthesized. These macrocyclic sensors exhibited high affinity and selectivity toward Ag over other metal ions, with ratiometric or enhanced response of their fluorescence emissions depending upon the substituent species for coordination to Ag, and an unexpected response to a concentration threshold of the metal cations was discovered. The experimental evidences of fluorescence spectra, H NMR titration, IR spectra, and high-resolution mass spectra suggested the coordination behaviors of the sensors with Ag, that is, the 1:1 complexes were formed with moderate association constants of about 10 L·mol, and the sulfur atoms on macrocyclic ligand should affinite to the metal cations. Energy-minimized structures and frontier orbitals were estimated by quantum chemical calculations with a view to rationalizing the fluorescence response of the multifarene[2,2] sensors upon binding to Ag.
合成了基于新型大环化合物多法烯[2,2]并经三唑连接的芘或蒽修饰的荧光化学传感器。这些大环传感器对Ag表现出比其他金属离子更高的亲和力和选择性，其荧光发射根据与Ag配位的取代基种类呈现比率或增强响应，并且发现了对金属阳离子浓度阈值的意外响应。荧光光谱、核磁共振氢谱滴定、红外光谱和高分辨率质谱的实验证据表明了传感器与Ag的配位行为，即形成了1:1配合物，其缔合常数适中，约为10 L·mol，大环配体上的硫原子应与金属阳离子亲和。通过量子化学计算估计了能量最小化结构和前沿轨道，以合理化多法烯[2,2]传感器与Ag结合时的荧光响应。
