Ligand Control of Supramolecular Chloride Photorelease
Ligand Control of Supramolecular Chloride Photorelease
复制标题
超分子氯化物光释放的配体控制
DOI：
10.1021/acs.inorgchem.8b00559
复制
发表时间：
2018
影响因子：
4.6
通讯作者：
Meyer, Gerald J.
中科院分区：
文献类型：
--
作者：
Turlington, Michael D.;Troian-Gautier, Ludovic;Sampaio, Renato N.;Beauvilliers, Evan E.;Meyer, Gerald J.
超分子组装被证明可以控制激发态氯化物的释放。设计了两个双阳离子发色团，其配体可识别 CH2Cl2 中的卤离子，并且发光激发态的偶极子指向相关氯离子的 12+ 或远离 22+。偶极子取向对基态平衡常数Keq∼4×106M–1影响不大，但引起激发态平衡的深刻变化。 [12+,Cl–]+ 的光激发导致光致发光光谱随时间变化，并出现与 Cl– 的光释放一致的双指数动力学。值得注意的是，激发态平衡常数降低了 20 倍，导致氯离子解离近 45%。相比之下，[22+,Cl–]+ 的光激发显示激发态平衡常数增加了 45 倍。数据表明，合理的设计和超分子组装能够实现氯离子的检测和光释放，并具有未来在生物学和化学领域应用的潜力。
Supramolecular assembly is shown to provide control over excited-state chloride release. Two dicationic chromophores were designed with a ligand that recognizes halide ions in CH2Cl2and a luminescent excited state whose dipole was directed toward,12+, or away,22+, from an associated chloride ion. The dipole orientation had little influence on the ground-state equilibrium constant,Keq∼ 4 × 106M–1, but induced a profound change in the excited-state equilibrium. Light excitation of[12+,Cl–]+resulted in time-dependent shifts in the photoluminescence spectra with the appearance of biexponential kinetics consistent with the photorelease of Cl–. Remarkably, the excited-state equilibrium constant was lowered by a factor of 20 and resulted in nearly 45% dissociation of chloride. In contrast, light excitation of[22+,Cl–]+revealed a 45-fold increase in the excited-state equilibrium constant. The data show that rational design and supramolecular assembly enables the detection and photorelease of chloride ions with the potential for future applications in biology and chemistry.