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Two pentacoordinated dinuclear copper(II) compounds of the type [Cu2(bpbd)2(dca)](ClO4/PF6)3 (1/2) [bpbd = N,N′-(bis-(pyridin-2-yl)benzylidene)-1,4-butanediamine; dca = dicyanamide] have been synthesized and characterized on the basis of microanalytical, spectroscopic, thermal and other physicochemical results. Single crystal X-ray diffraction measurements of 1 and 2 have been made to define their coordination spheres as well as intermolecular interactions. Structural analyses reveal that 1 and 2 have two copper(II) centers bound by four N atoms of bpbd and the metal centers are connected by a single μ1,5 dca bridge. Both the copper(II) centers in 1 have distorted trigonal bipyramidal geometry; whereas, in 2 one copper(II) center has a distorted trigonal bipyramidal geometry and the other adopts a distorted square pyramidal environment. In the crystalline state, individual 0D units in 1 and 2 are self-assembled with C—H···π interactions promoting dimensionalities. Both complexes show intraligand 1(π—π*) fluorescence in DMF solutions at room temperature. Variable-temperature (300–2 K) magnetic susceptibility studies reveal that long μ1,5 dca bridges mediate very weak antiferromagnetic interactions. [Copyright &y& Elsevier]

Highlights: [•] Two dinuclear cadmium(II) dicarboxylate compounds with polyamine/Schiff base are isolated and characterized. [•] X-ray structures show interesting variations in coordination numbers, geometries and superstructures. [•] Thermogravimetric analyses reveal their thermal stability and decomposition pattern. [•] Fluorescence studies in DMF solution illustrate ligand based π–π* emission. [ABSTRACT FROM AUTHOR]

Abstract: A series of pentacoordinated mono-/dinuclear compounds, [Zn(L)(Br)]PF6 (1), [Zn(L)(NCS)]ClO4 (2) and [Zn2(L)2(μ-tp)](ClO4/PF6)2 (3/4) [L=N,N′-(bis(pyridin-2-yl)benzylidene)-1,3-propanediamine, tp=terephthalate dianion], have been synthesized using one-pot reactions of the building components. All the complexes are characterized using microanalytical, spectroscopic and other physicochemical results. Structures of 1–4 are solved by single crystal X-ray diffraction measurements. Structural analyses reveal that each zinc(II) center in 1 and 3 adopts a distorted trigonal bipyramidal geometry with ZnN4Br and ZnN4O chromophores, respectively, whereas zinc(II) centers in 2 and 4 have a distorted square pyramidal geometry with ZnN5 and ZnN4O chromophores, respectively. Intermolecular CBr, CF and CO hydrogen bondings along with Cπ and π⋯π interactions as the case in 1–4 lead to different crystalline aggregates. The compounds show intraligand π–π* fluorescence in solid states and in DMF solutions at room temperature. [Copyright &y& Elsevier]

Abstract: A 1D coordination polymer [Hg2(L)Br4] n (1) and one dinuclear compound [Hg2(L)I4] (2) [L=N,N′-(bis(pyridin-2-yl)benzylidene)ethane-1,2-diamine] are isolated using a 2:1M ratio of HgBr2/HgI2 and Schiff base (L) in methanol–acetonitrile solution mixture and X-ray crystallographically characterized. Structural analyses show that in 1 1D chain is formed through binucleating bis(bidentate) bridging behavior of L and asymmetric Hg-(μ-Br)2-Hg bridges in an alternate fashion; one terminal bromide unit completes the distorted square pyramidal geometry around each mercury(II). In 2, two mercury(II) centers are connected by bis(bidentate) bridging behavior of L and two iodides bound to each metal(II) center remain as terminal resulting in a discrete dinuclear entity with distorted tetrahedral geometry. Weak intermolecular Hg⋯I and I⋯I interactions in 2 promote dimensionality. In DMF solutions, 1 and 2 display intraligand 1(π–π∗) fluorescence. [Copyright &y& Elsevier]

Abstract: Two dinuclear cadmium(II) compounds of the types [Cd(L)(μ-Cl)]2(PF6)2 (1) and [Cd(L)(μ1,5-dca)]2(ClO4)2.0.66MeOH (2) [L=N,N′-(bis(pyridin-2-yl)benzylidene)-1,3-propanediamine; dca=dicyanamide] have been synthesized and characterized on the basis of microanalytical, spectroscopic and other physicochemical results. X-ray structural studies show that in 1 and 2 each hexacoordinated cadmium(II) adopts a distorted octahedral geometry with CdN4Cl2 (1)/CdN6 (2) chromophore ligated through four N atoms of L along with two chlorides in 1 forming a four-membered Cd–(Cl)2–Cd rhombohedral bridging loop and two nitrile N atoms of two μ1,5 dicyanamides in 2 affording a larger 12-membered Cd–(NCNCN)2–Cd ring with boat conformation. In the crystalline state, individual units in 1 are packed through multiple weak CF hydrogen bonds and Cπ and π ⋯π interactions affording a 2D sheet structure. The dinuclear units in 2 are engaged in weak intermolecular CO and CN hydrogen bondings to give a 2D continuum, which is further stabilized by π⋯π interactions through pyridine rings of L. In DMF solutions, 1 and 2 show high-energy intraligand 1(π–π *) fluorescence at room temperature. [ABSTRACT FROM AUTHOR]