Formation of Rigid Organic Nanotubes with Controlled Internal Cavity Based on Frustrated Aggregate Internal Rearrangement Mechanism
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- 作者：Minwoo Han ; Jungin Hyun ; Eunji Sim
- 刊名：The Journal of Physical Chemistry B
- 出版年：2013
- 出版时间：June 27, 2013
- 年：2013
- 卷：117
- 期：25
- 页码：7763-7770
- 全文大小：380K
- 年卷期：v.117,no.25(June 27, 2013)
- ISSN：1520-5207
文摘
We introduce frustrated aggregate internal rearrangement (FAIR) mechanism for anisotropic higher-order structure formations, in which the anisotropy arose due to the structural frustration. We demonstrate the FAIR mechanism by investigating the recently observed rigid organic nanotube formations through the self-assembly of building blocks, which include rigid segments and make intermolecular H-bonds, whereas the principle of the FAIR mechanism is general and is not limited to H-bonding building blocks or nanotube formations. Initially, molecules aggregate into sheetlike structures driven by nonspecific and nondirectional intermolecular interactions such as 蟺鈥撓€ stacking or amphiphilicity. Weak intermolecular H-bonds provide additional stability to the structure. Within the aggregate, however, not all molecules have the right orientation for specific and directional H-bonds whereas collective internal rearrangement of rigid building blocks requires a large amount of energy to overcome kinetically trapped barriers. Consequently, instead of the fully H-bonded global equilibrium structure, self-assembled layers become trapped with partial and disordered H-bonding schemes at various fractions leading to an anisotropic layer that undergoes spontaneous transformation into curved structures. The FAIR mechanism can readily be extended to anisotropic higher-order structures other than nanotubes and to the assembly of diverse building blocks including hybrids such as polymer nanocomposites. Also the reversible transformation from metastable nanotubes into layered sheets is potentially useful for controlling internal cavity size of nanotubes.