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      • Wafer-scale synthesis of monolayer two-dimensional porphyrin polymers for hybrid superlattices

        Zhong, Yu,Cheng, Baorui,Park, Chibeom,Ray, Ariana,Brown, Sarah,Mujid, Fauzia,Lee, Jae-Ung,Zhou, Hua,Suh, Joonki,Lee, Kan-Heng,Mannix, Andrew J.,Kang, Kibum,Sibener, S. J.,Muller, David A.,Park, Jiwoon American Association for the Advancement of Scienc 2019 Science Vol.366 No.6471

        <P><B>Single-layer porphyrin polymerization</B></P><P>Two-dimensional polymers can be made as monolayer sheets through controlled synthesis at an interface. However, it is often difficult to create intact sheets over large areas that can be transferred onto substrates. Zhong <I>et al.</I> polymerized derivatized porphyrin molecules during laminar flow at a sharp pentane-water interface to form sheets that are 5 centimeters in diameter (see the Perspective by MacLean and Rosei). The authors used electron microscopy and spectroscopy to confirm that they had produced intact monolayers. These films were then transferred onto monolayer sheets of molybdenum disulfide to form superlattices for use as capacitors.</P><P><I>Science</I>, this issue p. 1379; see also p. 1308</P><P>The large-scale synthesis of high-quality thin films with extensive tunability derived from molecular building blocks will advance the development of artificial solids with designed functionalities. We report the synthesis of two-dimensional (2D) porphyrin polymer films with wafer-scale homogeneity in the ultimate limit of monolayer thickness by growing films at a sharp pentane/water interface, which allows the fabrication of their hybrid superlattices. Laminar assembly polymerization of porphyrin monomers could form monolayers of metal-organic frameworks with Cu<SUP>2+</SUP> linkers or covalent organic frameworks with terephthalaldehyde linkers. Both the lattice structures and optical properties of these 2D films were directly controlled by the molecular monomers and polymerization chemistries. The 2D polymers were used to fabricate arrays of hybrid superlattices with molybdenum disulfide that could be used in electrical capacitors.</P>

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