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      Three New Supramolecular Coordination Polymers Based on 1H-pyrazolo[3,4-b]pyridin-3-amine and 1,3-benzenedicarboxylate Derivatives

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          Abstract

          Three new supramolecular coordination polymers, namely [Zn(1,3-BDC)(HL)] n (Polymer 1), [Zn 3(1,3,5-BTC) 2(HL) 2(H 2O) 2] n (Polymer 2), and [Zn 9(5-SO 3-1,3-BDC) 2(L) 8(OH) 4] n (Polymer 3), were synthesized under solvothermal conditions, based on 1H-pyrazolo[3,4-b]pyridin-3-amine (HL) along with 1,3-benzenedicarboxylate (1,3-BDC) and its derivatives, such as 1,3,5-benzenetricarboxylate (1,3,5-BTC) and 5-sulfo-1,3-benzenedicarboxylate (5-SO 3-1,3-BDC). Polymers 1–3 were characterized by elemental analysis, IR spectroscopy, powder X-ray diffraction (PXRD), and single crystal X-ray diffraction analysis. Polymer 1 exhibited a two-dimensional (2D) 4-connected sql net. The neighboring 2D nets were further linked into a 3D supramolecular network by hydrogen-bonding interactions. Polymer 2 displayed a 3D (4, 4, 4)-connected network, which was further stabilized by R 2 2 (14) and S(9) hydrogen-bonding rings along with π–π interactions. The 2D sheet structure of Polymer 3 was constructed by novel quasi-linear nonanuclear Zn(II) units, which further extended into a 3D supramolecular structure by hydrogen-bonding interactions. The solid-state photoluminescence properties of Polymers 1–3 were also investigated.

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          Functional Porous Coordination Polymers

          The chemistry of the coordination polymers has in recent years advanced extensively, affording various architectures, which are constructed from a variety of molecular building blocks with different interactions between them. The next challenge is the chemical and physical functionalization of these architectures, through the porous properties of the frameworks. This review concentrates on three aspects of coordination polymers: 1). the use of crystal engineering to construct porous frameworks from connectors and linkers ("nanospace engineering"), 2). characterizing and cataloging the porous properties by functions for storage, exchange, separation, etc., and 3). the next generation of porous functions based on dynamic crystal transformations caused by guest molecules or physical stimuli. Our aim is to present the state of the art chemistry and physics of and in the micropores of porous coordination polymers.
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            Dynamic porous properties of coordination polymers inspired by hydrogen bonds.

            In a decade, many porous coordination polymers have been synthesized, providing a variety of properties ranging from storage, separation, exchange of guests in their cavities, magnetism, conductivity and catalysis by their frameworks. In this tutorial review, we focus on the hydrogen bonding type arrangements for dynamic porous coordination polymers exhibiting elastic guest accommodations, in contrast to rigid three-dimensional (3-D) frameworks. Such dynamic porous properties induce highly-selective guest accommodation and magnetic modulation, and could now be considered a new class of practical materials.
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              Crystal engineering: from molecule to crystal.

              How do molecules aggregate in solution, and how do these aggregates consolidate themselves in crystals? What is the relationship between the structure of a molecule and the structure of the crystal it forms? Why do some molecules adopt more than one crystal structure? Why do some crystal structures contain solvent? How does one design a crystal structure with a specified topology of molecules, or a specified coordination of molecules and/or ions, or with a specified property? What are the relationships between crystal structures and properties for molecular crystals? These are some of the questions that are being addressed today by the crystal engineering community, a group that draws from the larger communities of organic, inorganic, and physical chemists, crystallographers, and solid state scientists. This Perspective provides a brief historical introduction to crystal engineering itself and an assessment of the importance and utility of the supramolecular synthon, which is one of the most important concepts in the practical use and implementation of crystal design. It also provides a look to the future from the viewpoint of the author, and indicates some directions in which this field might be moving.
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                Author and article information

                Journal
                Polymers (Basel)
                Polymers (Basel)
                polymers
                Polymers
                MDPI
                2073-4360
                07 May 2019
                May 2019
                : 11
                : 5
                : 819
                Affiliations
                College of Chemistry and Materials Science, Huaibei Normal University, Huaibei 235000, China; 13365613602@ 123456163.com (Q.-H.D.); pangao_1992@ 123456163.com (F.D.); raner28@ 123456163.com (R.A.); dongliu@ 123456chnu.edu.cn (D.L.); miaotifang@ 123456163.com (T.-F.M.)
                Author notes
                [* ]Correspondence: xuyun88@ 123456163.com ; Tel.: +86-0561-380-2235
                Article
                polymers-11-00819
                10.3390/polym11050819
                6571696
                31067709
                7e174937-fc06-4493-9242-b1ee6fcdfa9d
                © 2019 by the authors.

                Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license ( http://creativecommons.org/licenses/by/4.0/).

                History
                : 10 April 2019
                : 03 May 2019
                Categories
                Article

                supramolecular coordination polymers,nonanuclear zinc unit,hydrogen-bonding interactions,photoluminescence

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