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Role of Temperature and Time in the Formation of Infinite -M-O-MLinkages and Isolated Clusters in MOFs: A Few Illustrative Examples

Mahata, Partha and Prabu, Manikanda and Natarajan, Srinivasan (2008) Role of Temperature and Time in the Formation of Infinite -M-O-MLinkages and Isolated Clusters in MOFs: A Few Illustrative Examples. In: Inorganic Chemistry, 47 (19). pp. 8451-8463.

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The role of temperature and time of reaction in the formation of metal-organic frameworks (MOFs) has been studied in two systems of compounds, manganese oxybis(benzoate) and manganese trimellitates, and the results compared and contrasted with other similar studies in the literature. The investigation reveals the formation of six different phases in oxybis(benzoate) and three phases in trimellitate systems. The low-temperature phases in both systems of compounds possess $Mn_{4}$ cluster units linked by the carboxylate ligands, while the high-temperature phase, irrespective of the duration of the reaction, has a three-dimensional structure with -Mn-O-Mn- linkages with brucite-related layers pillared by oxybis(benzoate) and Kagome-related layers pillared by trimellitate ligands. In all of the preparation, the reactions appear to have thermodynamic control as a function of the temperature. The isolation of low-dimensional structures in manganese oxybis(benzoate) at moderate time and temperature indicates possible kinetic control. The formation of reactive low-dimensional phases has been rationalized by considering the local charge distribution around the Mn site and also invoking a possible dissolution-recrystalization mechanism.

Item Type: Journal Article
Publication: Inorganic Chemistry
Publisher: ACS Publications
Additional Information: Copyright belongs to ACS Publications.
Department/Centre: Division of Chemical Sciences > Solid State & Structural Chemistry Unit
Date Deposited: 29 Oct 2009 08:54
Last Modified: 19 Sep 2010 04:52
URI: http://eprints.iisc.ac.in/id/eprint/16510

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