Cu-II-Azide Polymers of Cu-3 and Cu-6 Building Units: Synthesis,Structures, and Magnetic Exchange Mechanism

Mukherjee, Sandip and Gole, Bappaditya and Chakrabarty, Rajesh and Mukherjee, Partha Sarathi (2009) Cu-II-Azide Polymers of Cu-3 and Cu-6 Building Units: Synthesis,Structures, and Magnetic Exchange Mechanism. In: Inorganic chemistry, 48 (23). pp. 11325-11334.

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Abstract

Two new neutral copper-azido polymers [Cu-3(N-3)(6)(tmen)(2)](n)(1)and [Cu-6(N-3)(12)(deen)(2)](n) (2) [tmen = N,N,N, N-tetramethylethylenediamine and deen = N,N-diethylethylenediamine] have been synthesized by using lower molar equivalents of the chelating diamine ligands with Cu(NO3)(2)center dot 3H(2)O and an excess of NaN3. The single crystal X-ray structure shows that in the basic unit of the 1D complex 1, the three Cu-II ions are linked by double end-on azido bridges with Cu-N-EO-Cu angles on both sides of the magnetic exchange critical angle of 108 degrees. Complex 2 is a 3D framework of a basic u-6 cluster. Cryomagnetic susceptibility measurements over a wide range of temperature exhibit dominant ferromagnetic behavior in both the complexes. Density functional theory calculations (B3LYP functional) have been performed on the trinuclear unit to provide a qualitative theoretical interpretation of the overall ferromagnetic behavior shown by the complex 1.

Item Type:	Journal Article
Publication:	Inorganic chemistry
Publisher:	Amer chemical soc
Additional Information:	copyright of this article belongs to Amer chemical soc.
Keywords:	End-to-end; transition-metal-complexes; single-molecule magnets; dinuclear copper(ii) complexes; high-spin molecules; crystal-structure; magnetostructural correlations; ground-state; ferromagnetic interaction; coordination polymers.
Department/Centre:	Division of Chemical Sciences > Inorganic & Physical Chemistry
Date Deposited:	05 Jan 2010 05:57
Last Modified:	19 Sep 2010 05:53
URI:	http://eprints.iisc.ac.in/id/eprint/25160

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