Frauenrath synthesized a carbon-rich nanosheet using carbonization of an amphiphilic hexayne molecule 28. 2,2′:6′,2′′-Terpyridine/metal complex nanosheets based on a metal–ligand coordination linkage were reported by Schlüter 26, 27. For example, Schlüter and King created independently single-layer cycloaddition-induced anthracene 22, 23, 24, 25 nanosheets that featured carbon–carbon covalent bonds. The concept was proposed nearly a century ago, although it has only recently been realized 21. This series of nanosheets is fabricated directly from atomic, ionic and molecular components. These nanosheets originate from bulk-layered crystalline mother materials (that is, top-down nanosheets).Īnother type of nanosheets, namely molecule-based bottom-up nanosheets, is emerging. The broad attention and expected utility of graphene have stimulated research into other nanosheets, such as metal oxides 7, 8, 9, 10, 11, metal sulfides 12, 13, 14, 15 and metal hydroxides 16, 17, 18, 19, 20, which also exhibit desirable and useful properties (for example, semiconductivity 10, 15 and ferroelectricity 8, 14). Graphene, a prominent nanosheet with various attractive properties, has been investigated extensively for applications in electronics 1, 2, 3, photonics 4 and spintronics 5, 6. Nanosheets with two-dimensional polymeric structures have recently attracted significant attention. The nanosheet deposited on a transparent SnO 2 electrode functions as a photoanode in a photoelectric conversion system, and is thus the first photofunctional bottom-up nanosheet. The bis(dipyrrinato)zinc(II) metal complex nanosheet is easy to deposit on various substrates using the Langmuir–Schäfer process.
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. Here we show the design and synthesis of a bottom-up nanosheet featuring a photoactive bis(dipyrrinato)zinc(II) complex motif. 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. 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.
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