Interlocked dimerization of C3-Symmetrical boron difluoride complex: designing non-cooperative supramolecular materials for luminescent thin films
Interlocked dimerization of C3-Symmetrical boron difluoride complex: designing non-cooperative supramolecular materials for luminescent thin films
复制标题
DOI：
10.1039/c5ra11908a
复制
发表时间：
2015-07
期刊：
影响因子：
3.9
通讯作者：
S. Ogawa;M. Morikawa;G. Juhász;N. Kimizuka
中科院分区：
文献类型：
--
作者：
S. Ogawa;M. Morikawa;G. Juhász;N. Kimizuka
新开发了一种亲脂性复合物，其三个β-二酮二氟化硼（BF2dk）单元径向连接到中心苯环。 NMR 光谱和量子化学计算表明，随着 CHCl3 浓度的增加，C3 对称 BF2dk 复合物 (1) 形成自互补联锁二聚体 (1)2。响应互锁二聚体的形成，观察到从蓝色到黄色的显着发光颜色变化。静电相互作用、负凸面（BF2部分）和正凹面（每个臂上排列的三个质子）之间的氢键主要促成二聚化，而互锁二聚体的形成伴随着成分分子的构象变化，从而中断了进一步的缔合。因此，将联锁二聚体的氯仿溶液浇铸在固体支持物上得到均匀的薄膜，而没有不均匀的结晶。它为设计均质分子涂层的反协同系统提供了新的视角。
A lipophilic complex with radially-connected three β-diketonate boron difluoride (BF2dk) units to a central benzene ring was newly developed. The C3-symmetrical BF2dk complex (1) formed a self-complementary interlocked dimer (1)2 with increasing concentration in CHCl3 as revealed by NMR spectroscopy and quantum chemical calculations. A remarkable luminescence color change from blue to yellow was observed in response to the formation of interlocked dimers. Electrostatic interactions, hydrogen bonding between negative convexes (BF2 moiety) and positive concaves (three protons aligned on each arm) principally contribute to the dimerization, whereas the formation of interlocked dimers was accompanied by conformational changes of constituent molecules which interrupted further association. Consequently, casting of the chloroform solution of interlocked dimers on solid supports gave uniform thin films without uneven crystallization. It provides a new perspective for designing anti-cooperative systems for homogeneous molecular coatings.