American Chemical Society
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Structures, Magnetic Properties, and Photoluminescence of Dicarboxylate Coordination Polymers of Mn, Co, Ni, Cu Having N‑(4-Pyridylmethyl)-1,8-naphthalimide

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journal contribution
posted on 2014-09-03, 00:00 authored by Jayanta K. Nath, Abhishake Mondal, Annie K. Powell, Jubaraj B. Baruah
Supramolecular interactions of N-(4-pyridylmethyl)-1,8-naphthalimide (L) and flexibility of intervening units of dicarboxylate ligands contribute to formation of different types of coordination polymers such as [MnL2(Adp)­(H2O)2]n·2nH2O (1), [CoL2(Fum)­(H2O)2]n·2nH2O (2), [CoL2(Adp)­(H2O)2]n·2nH2O (3), [NiL(Fum)­(H2O)3]n·H2O (4), [CuL2(Fum)]n·nH2O (5), [CuL(Mal)]n (6), and [Cu3L6(Adp)3(H2O)3]n (7) (where Adp = adipate, Fum = fumarate, and Mal = malonate). These coordination polymers are structurally characterized. Coordination polymers 1 and 3 are isostructural having three-dimensional (3D) supramolecular layer-like structures. Coordination polymer 2 forms a two-dimensional (2D) supramolecular network through C–H···π and O···π interactions. Coordination polymer 4 forms H-bonded 3D chainlike supramolecular architecture. Coordination polymer 5 forms a 3D supramolecular sheet-like structure, whereas coordination polymer 6 and coordination polymer 7 forms a 2D lamellar structure through π···π and C–H···π interactions. Manganese coordination polymer 1 shows weak antiferromagnetic interactions between chains at low temperature and also exhibits single chain magnetic behavior. Coordination polymers 2 and 3 show saturation value of magnetic moment at 2 K and 7 T, which are lower than the spin-only Co­(II) ion. Coordination polymer 4 show spin-only values for Ni­(II) ion. The room-temperature χMT value for coordination polymer 5 is close to the spin-only value for two Cu­(II) ions. With lowering of the temperature, the χMT value remains constant to 35 K, from where the value begins to decrease to a minimum at 2 K. For copper coordination polymer 6 value of χMT smoothly decreases with lowering of the temperature to attain a quasi plateau between 80 K and 35 K, and it further sharply increases at 2 K. Coordination polymer 7 shows spin-only Cu­(II) ion. These coordination polymers in solid state show quenching of fluorescence emission of ligand L, as well as a shift of emission toward a shorter wavelength.