Abstract
From reaction of tris-(1,10-phenanthroline)nickel(II) nitrate (1) with different nitroaromatics, inclusion complex of 4-nitrophenol [Ni(phn)3](NO3)2·(Hnp)·2H2O (2) and mixed anionic nitro-aromatic complexes [Ni(phn)3]2(dnp)3(NO3)·11H2O (3) and [Ni(phn)3](nba) (NO3)3·11H2O (4) where (phn=1,10-phenanthroline, Hnp=4-nitrophenol, dnp=2,4-dinitrophenolate, nba=3-nitrobenzoate) are prepared and characterized. 2,4-Dinitrophenolate in complex 3 as well as 3-nitrobenzoate in complex 4, have oxygen-π interactions involving oxygen atom/s of nitro groups with the π-cloud of 1,10-phenanthroline rings and the complexes are non-fluorescent but complex 1 and inclusion complex 2 are weakly fluorescent. Complexes 3 and 4 are examples of mixed anionic complexes having odd numbers of dissimilar uni-negative anions distributed over two complex di-positive cations. Isothermal calorimetric titrations have shown that association constants of 4-nitrophenol, 2,4-dinitrophenol, 3-nitrobenzoic acid with the complex 1 at 27°C are 514M−1, 924M−1, 1040M−1 respectively.
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