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      Solid-state polymerisation via [2+2] cycloaddition reaction involving coordination polymers

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          Abstract

          Recent advancements in the construction of cyclobutane polymers viaphoto-dimerisation reaction in the monocrystalline solids of metal complexes, coordination polymers and metal–organic framework structures are reviewed.

          Abstract

          Highly crystalline metal ions containing organic polymers are potentially useful to manipulate the magnetic and optical properties to make advanced multifunctional materials. However, it is challenging to synthesise monocrystalline metal complexes of organic polymers and single-phase hybrid materials made up of both coordination and organic polymers by traditional solution crystallisation. This requires an entirely different approach in the solid-state by thermal or photo polymerisation of the ligands. Among the photochemical methods available, [2+2] cycloaddition reaction has been recently employed to generate cyclobutane based coordination polymers from the metal complexes. Cyclobutane polymers have also been integrated into coordination polymers in this way. Recent advancements in the construction of polymeric chains of cyclobutane rings through photo-dimerisation reaction in the monocrystalline solids containing metal complexes, coordination polymers and metal–organic framework structures are discussed here.

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          Most cited references149

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          Porous, crystalline, covalent organic frameworks.

          Covalent organic frameworks (COFs) have been designed and successfully synthesized by condensation reactions of phenyl diboronic acid {C6H4[B(OH)2]2} and hexahydroxytriphenylene [C18H6(OH)6]. Powder x-ray diffraction studies of the highly crystalline products (C3H2BO)6.(C9H12)1 (COF-1) and C9H4BO2 (COF-5) revealed expanded porous graphitic layers that are either staggered (COF-1, P6(3)/mmc) or eclipsed (COF-5, P6/mmm). Their crystal structures are entirely held by strong bonds between B, C, and O atoms to form rigid porous architectures with pore sizes ranging from 7 to 27 angstroms. COF-1 and COF-5 exhibit high thermal stability (to temperatures up to 500 degrees to 600 degrees C), permanent porosity, and high surface areas (711 and 1590 square meters per gram, respectively).
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            Luminescent metal-organic frameworks.

            Metal-organic frameworks (MOFs) display a wide range of luminescent behaviors resulting from the multifaceted nature of their structure. In this critical review we discuss the origins of MOF luminosity, which include the linker, the coordinated metal ions, antenna effects, excimer and exciplex formation, and guest molecules. The literature describing these effects is comprehensively surveyed, including a categorization of each report according to the type of luminescence observed. Finally, we discuss potential applications of luminescent MOFs. This review will be of interest to researchers and synthetic chemists attempting to design luminescent MOFs, and those engaged in the extension of MOFs to applications such as chemical, biological, and radiation detection, medical imaging, and electro-optical devices (141 references).
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              Covalent organic frameworks (COFs): from design to applications.

              Covalent organic frameworks (COFs) represent an exciting new type of porous organic materials, which are ingeniously constructed with organic building units via strong covalent bonds. The well-defined crystalline porous structures together with tailored functionalities have offered the COF materials superior potential in diverse applications, such as gas storage, adsorption, optoelectricity, and catalysis. Since the seminal work of Yaghi and co-workers in 2005, the rapid development in this research area has attracted intensive interest from researchers with diverse expertise. This critical review describes the state-of-the-art development in the design, synthesis, characterisation, and application of the crystalline porous COF materials. Our own opinions on further development of the COF materials are also presented for discussion (155 references).
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                Author and article information

                Journal
                CHCOFS
                Chemical Communications
                Chem. Commun.
                Royal Society of Chemistry (RSC)
                1359-7345
                1364-548X
                2016
                2016
                : 52
                : 21
                : 3989-4001
                Affiliations
                [1 ]Department of Chemistry
                [2 ]National University of Singapore
                [3 ]Singapore
                [4 ]Department of Chemistry and Research Institute of Natural Sciences
                [5 ]Gyeongsang National University
                [6 ]Jinju 660-701
                [7 ]South Korea
                Article
                10.1039/C5CC08374E
                42ab4004-cc88-4247-9db8-9257d5c483b8
                © 2016
                History

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