| Transformation of Kinetically into Thermodynamically Controlled Self-Organization of Complex Helical Columns with 3D Periodicity Assembled from Dendronized Perylene Bisimides. | |
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MedLine Citation:
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PMID: 23406582 Owner: NLM Status: Publisher |
Abstract/OtherAbstract:
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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, different intra- and interdimer rotation angles but identical intra- and interdimer distance of 3.5Å, exhibiting a four-strata 21 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 ºC/min to 1 ºC/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, 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. |
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Authors:
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Virgil Percec; Hao-Jan Sun; Pawaret Leowanawat; Mihai Peterca; Robert Graf; Hans W Spiess; Xiangbing Zeng; Goran Ungar; Paul A Heiney |
Publication Detail:
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Type: JOURNAL ARTICLE Date: 2013-2-14 |
Journal Detail:
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Title: Journal of the American Chemical Society Volume: - ISSN: 1520-5126 ISO Abbreviation: J. Am. Chem. Soc. Publication Date: 2013 Feb |
Date Detail:
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Created Date: 2013-2-14 Completed Date: - Revised Date: - |
Medline Journal Info:
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Nlm Unique ID: 7503056 Medline TA: J Am Chem Soc Country: - |
Other Details:
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Languages: ENG Pagination: - Citation Subset: - |
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From MEDLINE®/PubMed®, a database of the U.S. National Library of Medicine
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