Crystallization of copper(II) sulfate based minerals and MOF from solution: Chemical insights into the supramolecular interactions PDF20160505-7359-A4GU7J

Title	Crystallization of copper(II) sulfate based minerals and MOF from solution: Chemical insights into the supramolecular interactions
Author	Dinesh Kumar
Pages	13
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File Type	PDF20160505-7359-A4GU7J
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J. Chem. Sci., Vol. 122, No. 5, September 2010, pp. 757–769. © Indian Academy of Sciences. Crystallization of copper(II) sulfate based minerals and MOF from solution: Chemical insights into the supramolecular interactions M SINGH, D KUMAR, J THOMAS and A RAMANAN* Department of Chemistry, Indian Inst...

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J. Chem. Sci., Vol. 122, No. 5, September 2010, pp. 757–769. © Indian Academy of Sciences. 757 *For correspondence Crystallization of copper(II) sulfate based minerals and MOF from solution: Chemical insights into the supramolecular interactions M SINGH, D KUMAR, J THOMAS and A RAMANAN* Department of Chemistry, Indian Institute of Technology, New Delhi 110 016 e-mail: [email protected] Abstract. Crystallization of solids, molecular or non-molecular from solution is a supramolecular r tion. Nucleation of a lattice structure at supersaturation can be conceived to result from a critica a high energy intermediate (supramolecular transition state). Conceptualization of a struct critical nucleus in terms of aggregation of tectons through non-covalent interactions provides che insights into the architecture of a solid. The retrosynthetic analysis of copper-based minerals and als ofers an elegant description for the crystal packing. It addresses the infuence of the geomet tionality and reactivity of copper tecton(s) in directing a specifc supramolecular aggregat mechanistic approach provides guiding principles to chemists to account for the experimentally c lized solids and a platform to practice structure-synthesis correlation. Rationalization of the same sition with diferent atomic arrangements (polymorphs), compositional variation leading to pseudopolymorphs, degree of hydration (anhydrous to hydrated), water clusters, role of solvent, all be justifed on molecular basis. Also, the method gives predictive components including direct synthesize new solids. In a nutshell, the paper is an attempt to generalize the crystallization of in solids from solution by recognizing supramolecular interactions between metal tectons and gain for designing new MOF. Keywords. Crystallization; nucleation; supramolecular interaction; copper-based minerals; co tion polymer; MOF. 1. Introduction Materials research for the past few decades have been dominated by 3d transition metal based non- molecular oxides, halides, chalcogenides owing to their rich structural chemistry and a range of elec- tronic, magnetic, optical and catalytic properties. 1,2 Most of these materials are obtained through con- ventional solid state route wherein the reaction is essentially difusion-controlled leading to thermo- dynamically stable phases. However, in the recent past the focus has diverted towards another class of materials, organic inorganic hybrids 3 that include coordination polymers(CP) and metal organic frameworks (MOF) wherein the hard properties of inorganic ceramics and the fexibility of soft organic matrix are being integrated to obtain functional ma- terials. 4–6 Unlike molecular synthesis, preparation of solids relies heavily on exploratory methods, and it is well-recognized that the complexity of the possi- bilities often defes predictability. 7,8 In fgure 1 we highlight the three major activities of the chemistry of materials namely synthesis, structure and pro- perty at the corners of a triangle. Structure–property relationship is widely investigated for the past fe decades; Yaghi's reticular synthesis of MOF is a no- table example. 9,10 While structure–synthesis correla- tion is rarelyattempted due to lack of suitable mechanisms, designing or engineering a crystal t exhibit a particular set of properties for example porosity towards gas storage and separation still remains an elusive dream. Figure 1. Three major activities of the chemistry of materials....