Screening Libraries of Semifluorinated Arylene Bisimides to Discover and Predict Thermodynamically Controlled Helical Crystallization.
Screening Libraries of Semifluorinated Arylene Bisimides to Discover and Predict Thermodynamically Controlled Helical Crystallization.
复制标题
DOI：
10.1021/acscombsci.6b00143
复制
发表时间：
2016-11
影响因子：
--
通讯作者：
Ming-Shou Ho;Benjamin E. Partridge;Hao-Jan Sun;Dipankar Sahoo;Pawaret Leowanawat;M. Peterca;R. Graf;H. Spiess;X. Zeng;G. Ungar;P. Heiney;Chain‐Shu Hsu;V. Percec
中科院分区：
文献类型：
--
作者：
Ming-Shou Ho;Benjamin E. Partridge;Hao-Jan Sun;Dipankar Sahoo;Pawaret Leowanawat;M. Peterca;R. Graf;H. Spiess;X. Zeng;G. Ungar;P. Heiney;Chain‐Shu Hsu;V. Percec
合成，结构，和逆结构分析的库包含16个自组装的二萘嵌苯（PBI），1，6，7，12-四氯二萘嵌苯（Cl 4PBI），萘（NBI），和均苯四甲酸（PMBI）双酰亚胺功能化与环境友好的AB 3手性外消旋半氟化minidendron在其酰亚胺基团通过m = 0，1，2，和3亚甲基单元。这些半氟化的化合物在较低的温度下熔化比同源氢化化合物，允许通过结构分析筛选其所有的热致相，以发现螺旋桨状，齿轮状和倾斜的分子以及层状结构的螺旋控制的螺旋结晶。热力学控制的螺旋结晶被发现为螺旋桨状的PBI，Cl 4 PBI和NBI与m = 0。出乎意料的是，扭曲的C14 PBIs的组件表现出比平面的PBIs更高阶。具有m = 1、2和3的PBI形成具有柱内顺序的倾斜螺旋柱的受控制的柱状六边形2D晶格。PBI和Cl_4PBI（m = 1）通过最近发现的螺旋齿轮机制结晶，而NBI和PMBI（m = 1）形成倾斜的螺旋柱。m = 2的PBI、NBI和PMBI生成层状结构。具有m = 1、2和3的PBI、具有m = 1的NBI和具有m = 2的PMBI的3D和2D组件表现出3.4 π π-π堆叠。在这里和以前的工作中应用的库方法使得能够发现六个组件，这些组件通过热力学控制自组织成3D和2D周期性阵列，并提供分子原理来预测电子活性组分的超分子结构。
Synthesis, structural, and retrostructural analysis of a library containing 16 self-assembling perylene (PBI), 1,6,7,12-tetrachloroperylene (Cl4PBI), naphthalene (NBI), and pyromellitic (PMBI) bisimides functionalized with environmentally friendly AB3 chiral racemic semifluorinated minidendrons at their imide groups via m = 0, 1, 2, and 3 methylene units is reported. These semifluorinated compounds melt at lower temperatures than homologous hydrogenated compounds, permitting screening of all their thermotropic phases via structural analysis to discover thermodynamically controlled helical crystallization from propeller-like, cogwheel, and tilted molecules as well as lamellar-like structures. Thermodynamically controlled helical crystallization was discovered for propeller-like PBI, Cl4PBI and NBI with m = 0. Unexpectedly, assemblies of twisted Cl4PBIs exhibit higher order than those of planar PBIs. PBI with m = 1, 2, and 3 form a thermodynamically controlled columnar hexagonal 2D lattice of tilted helical columns with intracolumnar order. PBI and Cl4PBI with m = 1 crystallize via a recently discovered helical cogwheel mechanism, while NBI and PMBI with m = 1 form tilted helical columns. PBI, NBI and PMBI with m = 2 generate lamellar-like structures. 3D and 2D assemblies of PBI with m = 1, 2, and 3, NBI with m = 1 and PMBI with m = 2 exhibit 3.4 Å π-π stacking. The library approach applied here and in previous work enabled the discovery of six assemblies which self-organize via thermodynamic control into 3D and 2D periodic arrays, and provides molecular principles to predict the supramolecular structure of electronically active components.