Sakamoto Ryota, Hoshiko Ken, Liu Qian, Yagi Toshiki, Nagayama Tatsuhiro, Kusaka Shinpei, Tsuchiya Mizuho, Kitagawa Yasutaka, Wong Wai-Yeung, Nishihara Hiroshi
Department of Chemistry, Graduate School of Science, The University of Tokyo, 7-3-1, Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.
Institute of Molecular Functional Materials, Department of Chemistry and Partner State Key Laboratory of Environmental and Biological Analysis, Hong Kong Baptist University, Waterloo Road, Hong Kong, China.
Nat Commun. 2015 Apr 2;6:6713. doi: 10.1038/ncomms7713.
Two-dimensional polymeric nanosheets have recently gained much attention, particularly top-down nanosheets such as graphene and metal chalcogenides originating from bulk-layered mother materials. Although molecule-based bottom-up nanosheets manufactured directly from molecular components can exhibit greater structural diversity than top-down nanosheets, the bottom-up nanosheets reported thus far lack useful functionalities. Here we show the design and synthesis of a bottom-up nanosheet featuring a photoactive bis(dipyrrinato)zinc(II) complex motif. A liquid/liquid interfacial synthesis between a three-way dipyrrin ligand and zinc(II) ions results in a multi-layer nanosheet, whereas an air/liquid interfacial reaction produces a single-layer or few-layer nanosheet with domain sizes of >10 μm on one side. The bis(dipyrrinato)zinc(II) metal complex nanosheet is easy to deposit on various substrates using the Langmuir-Schäfer process. The nanosheet deposited on a transparent SnO2 electrode functions as a photoanode in a photoelectric conversion system, and is thus the first photofunctional bottom-up nanosheet.
二维聚合物纳米片最近备受关注，尤其是自上而下制备的纳米片，如源自块状层状母体材料的石墨烯和金属硫族化物。尽管直接由分子组分制造的基于分子的自下而上的纳米片比自上而下的纳米片具有更大的结构多样性，但迄今为止报道的自下而上的纳米片缺乏有用的功能。在此，我们展示了一种具有光活性双（二吡咯）锌（II）配合物基序的自下而上的纳米片的设计与合成。三齿二吡咯配体与锌（II）离子之间的液/液界面合成产生多层纳米片，而气/液界面反应则在一侧产生畴尺寸大于10μm的单层或几层纳米片。双（二吡咯）锌（II）金属配合物纳米片易于使用朗缪尔-谢弗工艺沉积在各种基底上。沉积在透明SnO2电极上的纳米片在光电转换系统中用作光阳极，因此是首个具有光功能的自下而上的纳米片。
