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https://www.ias.ac.in/article/fulltext/jcsc/126/03/0763-0769

Dinuclear mercury(II) iodide; tripodal amine; Schiff base bridge; X-ray structure; luminescence.

Two dinuclear mercury(II) iodide complexes of the types [(L1)Hg(𝜇-I)HgI₃] (1) and [Hg₂(L2) (I)₄]·H₂O (2) [L1 = tris(2-aminoethyl)amine and L2 = N,N'-(bis-(pyridin-2-yl)benzylidene)diethylenetriamine] have been synthesized and characterized usingmicroanalytical, spectroscopic, thermal and other physicochemical results. Structures of both the compounds are solved by X-ray diffraction measurements. Structural analyses show that one mercury (II) centre in 1 adopts a distorted tetrahedral geometry with an HgI₄ chromophore surrounded by four iodides, while the other has a distorted trigonal bipyramidal environment with an HgN₄I chromophore bound by four N atoms of L1 and one bridging iodide. Pentadentate Schiff base (L2) in 2 shows unusual binucleating bis(bidentate) behaviour to bind two different mercury(II) centres—Hg1 with an HgN₃I₂ chromophore in a distorted square pyramidal geometry and Hg2 with an HgN₂I₂ chromophore in a tetrahedral environment. Weak intermolecularN-H…I hydrogen bonds in 1 and cooperative C-H$\ldots$𝜋 and $\pi\ldots \pi$ interactions in 2 promote dimensionalities. The Schiff base complex, 2, shows intraligand ($\pi-\pi^\ast$) fluorescence in DMF solution at room temperature, whereas compound 1 containing tripodal amine is fluorescent-inactive.

Subhasis Roy¹ Soumi Chattopadhyay¹ Somnath Choubey¹ Kishalay Bhar¹ Partha Mitra² Barindra Kumar Ghosh¹

1. Department of Chemistry, The University of Burdwan, Burdwan 713 104, India
2. Department of Inorganic Chemistry, Indian Association for the Cultivation of Science, Kolkata 700 032, India

Published

May 2014

Manuscript received

8 August 2013

Manuscript revised

9 December 2013

Accepted

22 December 2013

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