Transformation from Kinetically into Thermodynamically Controlled Self-Organization of Complex Helical Columns with 3D Periodicity Assembled from Dendronized Perylene Bisimides
Transformation from Kinetically into Thermodynamically Controlled Self-Organization of Complex Helical Columns with 3D Periodicity Assembled from Dendronized Perylene Bisimides
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DOI：
10.1021/ja400639q
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发表时间：
2013-03-13
影响因子：
15
通讯作者：
Heiney, Paul A.
中科院分区：
文献类型：
--
作者：
Percec, Virgil;Sun, Hao-Jan;Heiney, Paul A.
我们的实验室报道了枝状苝3,4:9,10-四羧酸二亚胺（PBI）， （3,4,5）12G1-1-PBI，自组装成复杂的螺旋柱，包含枝状PBI的二聚体，每层有一个分子，具有不同的内二聚体和间二聚体旋转角度，但内二聚体和间二聚体的距离相同，为3.5 A，表现出四层2(1)螺旋重复。在高温下，具有短范围柱内有序的二维柱状六方相是热力学产物，而具有三维周期性的单斜柱状阵列是低温下的热力学产物。当加热和冷却速率高于10℃/min至1℃/min时，在低温下，二维柱状周期阵列是这种枝晶化PBI的动力学产物。本文报道了n = 12 ~ 6, m = 1的（3,4,5）nG1-m-PBI文库的合成和结构分析。结合差示扫描量热法，粉末和取向纤维的x射线衍射，包括图案模拟和电子密度图重建，以及固态核磁共振，所有这些都是温度和加热和冷却速度的函数，用于它们的结构分析。研究发现，在低温条件下，制备的n = 12 ~ 10呈现出三维层状阵列，在加热和冷却过程中不可逆地转变为周期性柱状结构。同样，n = 12的动力学控制的三维柱状相在n = 10、9、8、7和6时变为热力学控制的。这种前所未有的转变有望促进非分布式PBI和其他自组装构建块的功能设计。
The dendronized perylene 3,4:9,10-tetracarboxylic acid bisimide (PBI), (3,4,5)12G1-1-PBI, was reported by our laboratory to self-assemble into complex helical columns containing dimers of dendronized PBI with one molecule in each stratum, with different intra- and interdimer rotation angles but identical intra- and interdimer distance of 3.5 A, exhibiting a four-strata 2(1) helical repeat. A thermodynamically controlled 2D columnar hexagonal phase with short-range intracolumnar order represents the thermodynamic product at high temperature, while a kinetically controlled monoclinic columnar array with 3D periodicity is the thermodynamic product at low temperature. With heating and cooling rates higher than 10 degrees C/min to 1 degrees C/min, at low temperature the 2D columnar periodic array is the kinetic product for this dendronized PBI. Here the synthesis and structural analysis of a library of (3,4,5)nG1-m-PBI with n = 12 to 6 and m = 1 are reported. A combination of differential scanning calorimetry, X-ray diffraction on powder and orientated fibers, including pattern simulation and electron density map reconstruction, and solid-state NMR, all as a function of temperature and heating and cooling rate, was employed for their structural analysis. It was discovered that at low temperature the as-prepared n = 12 to 10 exhibit a 3D layered array that transforms irreversibly into columnar periodicities during heating and cooling. Also the kinetically controlled 3D columnar phase of n = 12 becomes thermodynamically controlled for n = 10, 9, 8, 7, and 6. This unprecedented transformation is expected to facilitate the design of functions from dendronized PBI and other self-assembling building blocks.