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      Molecular decoding using luminescence from an entangled porous framework

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          Chemosensors detect a single target molecule from among several molecules, but cannot differentiate targets from one another. In this study, we report a molecular decoding strategy in which a single host domain accommodates a class of molecules and distinguishes between them with a corresponding readout. We synthesized the decoding host by embedding naphthalenediimide into the scaffold of an entangled porous framework that exhibited structural dynamics due to the dislocation of two chemically non-interconnected frameworks. An intense turn-on emission was observed on incorporation of a class of aromatic compounds, and the resulting luminescent colour was dependent on the chemical substituent of the aromatic guest. This unprecedented chemoresponsive, multicolour luminescence originates from an enhanced naphthalenediimide–aromatic guest interaction because of the induced-fit structural transformation of the entangled framework. We demonstrate that the cooperative structural transition in mesoscopic crystal domains results in a nonlinear sensor response to the guest concentration.


          Distinguishing closely related molecules using chemosensor materials is a continuing challenge. Here, an entangled porous coordination polymer is developed, which confines volatile organic compounds, and allows photoluminescence-based distinction of structurally similar aromatic molecules.

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          Most cited references 25

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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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            A homochiral metal-organic porous material for enantioselective separation and catalysis

            Inorganic zeolites are used for many practical applications that exploit the microporosity intrinsic to their crystal structures. Organic analogues, which are assembled from modular organic building blocks linked through non-covalent interactions, are of interest for similar applications. These range from catalysis, separation and sensor technology to optoelectronics, with enantioselective separation and catalysis being especially important for the chemical and pharmaceutical industries. The modular construction of these analogues allows flexible and rational design, as both the architecture and chemical functionality of the micropores can, in principle, be precisely controlled. Porous organic solids with large voids and high framework stability have been produced, and investigations into the range of accessible pore functionalities have been initiated. For example, catalytically active organic zeolite analogues are known, as are chiral metal-organic open-framework materials. However, the latter are only available as racemic mixtures, or lack the degree of framework stability or void space that is required for practical applications. Here we report the synthesis of a homochiral metal-organic porous material that allows the enantioselective inclusion of metal complexes in its pores and catalyses a transesterification reaction in an enantioselective manner. Our synthesis strategy, which uses enantiopure metal-organic clusters as secondary building blocks, should be readily applicable to chemically modified cluster components and thus provide access to a wide range of porous organic materials suitable for enantioselective separation and catalysis.
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              Postsynthetic modification of metal-organic frameworks.

              The modification of metal-organic frameworks (MOFs) in a postsynthetic scheme is discussed in this critical review. In this approach, the MOF is assembled and then modified with chemical reagents with preservation of the lattice structure. Recent findings show amide couplings, isocyanate condensations, 'click' chemistry, and other reactions are suitable for postsynthetic modification (PSM). In addition, a number of MOFs, from IRMOF-3 to ZIF-90, are amenable to PSM. The generality of PSM, in both scope of chemical reactions and range of suitable MOFs, clearly indicates that the approach is broadly applicable. Indeed, the rapid increase in reports on PSM demonstrates this methodology will play an increasingly important role in the development of MOFs for the foreseeable future (117 references).

                Author and article information

                Nat Commun
                Nature Communications
                Nature Publishing Group
                January 2011
                25 January 2011
                : 2
                : 168
                [1 ]simpleERATO Kitagawa Integrated Pores Project, Japan Science and Technology Agency (JST), Kyoto Research Park Building no. 3 , Shimogyo-ku, Kyoto 600-8815, Japan.
                [2 ]simpleDepartment of Synthetic Chemistry and Biological Chemistry, Graduate School of Engineering, Kyoto University, Katsura , Nishikyo-ku, Kyoto 615-8510, Japan.
                [3 ]simpleDepartamento de Química Física, Universidad del País Vasco UPV/EHU, Apartado 644 , Bilbao 48080, Spain.
                [4 ]simpleInstitute for Integrated Cell-Material Sciences, Kyoto University , Yoshida, Sakyo-ku, Kyoto 606-8501, Japan.
                [5 ]simpleX-ray Research Laboratory, Rigaku Co. Ltd , 3-9-12 Matsubara-cho, Akishima, Tokyo 196-8666, Japan.
                [6 ]Present address: simpleJapan Synchrotron Radiation Research Institute/SPring-8, Kouto , Sayo, Hyogo 679-5198, Japan.
                Author notes
                Copyright © 2011, Nature Publishing Group, a division of Macmillan Publishers Limited. All Rights Reserved.

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