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.