Gram-scale synthesis of two-dimensional polymer crystals and their structure analysis by X-ray diffraction
Gram-scale synthesis of two-dimensional polymer crystals and their structure analysis by X-ray diffraction
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DOI：
10.1038/nchem.2007
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发表时间：
2014-09-01
期刊：
影响因子：
21.8
通讯作者：
Schlueter, A. Dieter
中科院分区：
文献类型：
--
作者：
Kory, Max J.;Woerle, Michael;Schlueter, A. Dieter
石墨烯（一种具有拓扑平面重复单元的天然二维聚合物（2DP））的兴起对合成化学提出了挑战，并强调了直到最近还没有实现获得等效的共价键合的片状大分子。在这里，我们表明，非中心对称，对映体单晶的一个简单的单体可以光化学转化为手性2DP晶体和干净地逆转回单体。X射线衍射为这种合成的2DP建立了明确的结构证据，其具有全碳支架，并且可以在克级上合成。单体晶体是高度坚固的，可以容易地生长到大于1mm的尺寸，并且所得的2DP晶体剥落成纳米薄片。这种独特的特征组合表明，这些2DP可以在膜和非线性光学中找到用途。
The rise of graphene, a natural two-dimensional polymer (2DP) with topologically planar repeat units, has challenged synthetic chemistry, and has highlighted that accessing equivalent covalently bonded sheet-like macromolecules has, until recently, not been achieved. Here we show that non-centrosymmetric, enantiomorphic single crystals of a simple-to-make monomer can be photochemically converted into chiral 2DP crystals and cleanly reversed back to the monomer. X-ray diffraction established unequivocal structural proof for this synthetic 2DP, which has an all-carbon scaffold and can be synthesized on the gram scale. The monomer crystals are highly robust, can be easily grown to sizes greater than 1 mm and the resulting 2DP crystals exfoliated into nanometre-thin sheets. This unique combination of features suggests that these 2DPs could find use in membranes and nonlinear optics.