| Abstract |
A series of copper(II) aminoalcohol derivatives [Cu-2(mu-dmea)(2)(mu-nda)(H2O)(2)](n)center dot 2nH(2)O (1), [Cu-2(mu-Hmdea)(2)(mu-nda)](n)center dot 2nH(2)O (2), [Cu-2(mu-Hbdea)(2)(mu-nda)](n)center dot 2nH(2)O (3), and [Cu-2(H(4)etda)(2)(mu-nda)]center dot nda. 4H(2)O (4) were generated by aqueous medium self-assembly at similar to 25 degrees C from copper(II) nitrate, various aminoalcohols [N,N -dimethylethanolamine (Hdmea), N-methyldiethanolamine (H(2)mdea), N-butyldiethanolamine (H(2)bdea), or N,N,N ,Ni-tetrakis(2-hydroxyethyl)ethylenediamine (H(4)etda) for 1-4, respectively], sodium hydroxide, and 2,6-naphthalenedicarboxylic acid (H(2)nda). They were isolated as crystalline solids and fully characterized by IR and electron paramagnetic resonance spectroscopy, electrospray ionization mass spectrometry (ESI-MS(+/-)), thermogravimetric, elemental, and single-crystal X-ray diffraction analyses. The latter revealed that 1-3 are one-dimensional (1D) coordination polymers assembled from dicopper(II) aminoalcohol blocks and mu-nda linkers, whereas 4 is a discrete zero-dimensional (OD) dimer composed of two [Cu(H(4)etda)](2+) fragments interlinked by the mu-nda moiety. In spite of some structural similarities, the main distinctive features of 1-4 arise from the different H-bonding patterns driven by the crystallization H2O molecules, thus giving rise to a further extension of the structures [1D -> 3D (1, 2), 1D -> 2D (3), or 0D -> 3D (4)] into distinct supramolecular networks. Their topological analysis disclosed very complex multinodal nets with unique (1, 2, 4) or rare (3) topologies, which, upon further simplification, furnished a binodal 4,6-connected net with the sqc513 topology in 1, a trinodal 3,4,6-connected net with the 3,4,6L6 topology in 3, and trinodal 3,4,6- or 3,4,8-connected nets with undocumented topologies in 2 and 4, respectively. The magnetic susceptibility studies of 1-3 indicate a strong antiferromagnetic coupling between the Cu-II atoms through the mu-alkoxo bridges [J = -470(2), -100(2), and -590(1) cm(-1), respectively], which was described by the Bleaney-Bowers dinuclear model. In contrast, 4 is devoid of any significant magnetic interaction within the dicopper(II) units. |
