Long-range electronic coupling in various oxidation states of a C4-linked tris(beta-diketonato)ruthenium dimer.
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Biomedical subjects
Publications and source records attributed to Cheng-Yong Su.
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Two tripodal ligands, bis(2-benzimidazolylmethyl)(2-pyridylmethyl)amine (L(1)) and bis(2-pyridylmethyl)(2-benzimidazolylmethyl)amine (L(2)), were synthesized. With the third chromophoric ligand antipyrine (Antipy), three series of lanthanide(III) complexes were prepared: [LnL(1)(Antipy)(3)](ClO(4))(3) (series A), [LnL(1)(Antipy)Cl(H(2)O)(2)]Cl(2)(H(2)O)(2) (series B), and [LnL(2)(NO(3))(3)] (series C). The nitrate salt of the free ligand H(2)L(1).(NO(3))(2) and six complexes were structurally characterized: Pr(3+)A, Y(3+)A, Eu(3+)B, Eu(3+)C, Gd(3+)C and Tb(3+)C, in which the two A and three C complexes are isomorphous. Crystallographic studies showed that tripodal ligands L(1) and L(2) exhibited a tripodal coordination mode and formed 1:1 complexes with all lanthanide metal ions. The coordination numbers of the lanthanide metal ions for the A, B, and C complexes were 7, 8, and 10, respectively. Conductivity studies on the B and C complexes in methanol showed that, in the former, the coordinated Cl(-) dissociated to give 3:1 electrolytes and, in the latter, two coordinated NO(3)(-) ions dissociated to give 2:1 electrolytes. Detailed photophysical studies have been performed on the free ligands and their Gd(III), Eu(III), and Tb(III) complexes in several solvents. The results show a wide range in the emission properties of the complexes, which could be rationalized in terms of the coordination situation, the (3)LC level of the complexes, and the subtle variations in the steric properties of the ligands. In particular the Eu(3+)A and Tb(3+)A complexes, in which the central metal ions were wholly coordinated by chromophoric ligands of one L(1) and three antipyrine molecules, had relatively higher emission quantum yields than their corresponding B and C complexes.
Two complexes of the achiral tripodal ligand tris(1-benzimidazolylethyl)amine (nteb), viz., [Mn(nteb)(2)(H(2)O)(2)](ClO(4))(2).CH(3)OH, 1, and [Ag(2)(nteb)(2)](CF(3)CO(2))(2).2H(2)O, 2, have been synthesized and characterized by IR, (1)H NMR, and EPR spectroscopy (1), electrospray mass spectrometry, thermogravimetric analysis, and X-ray crystallography. Compound 1 contains chiral complex cations due to the same handedness of two nteb ligands (deltadelta or lambdalambda) but crystallizes as a racemate, while 2 contains a dinuclear mesocate because of the opposite handedness (deltalambda) of two nteb ligands. Crystal data for 1: space group P(-)1 with a = 9.471(4) A, b = 16.884(7) A, c = 19.906(8) A, alpha = 77.930(7) degrees, beta = 88.063(7) degrees, gamma = 89.706(7) degrees, V = 3111(2) A(3), and Z = 2. Crystal data for 2: space group P(-)1 with a = 9.3390(12) A, b = 10.2168(13) A, c = 16.382(2) A, alpha = 75.721(3) degrees, beta = 87.857(3) degrees, gamma = 71.738(3) degrees, V = 1437.2(3) A(3), and Z = 1. In 1, water serves as an auxiliary ligand, connected to one imidazole N atom of each nteb ligand through a H-bridge; the cationic complexes are associated intermolecularly via pi.pi interactions. In contrast to 1, the coordination to the Ag(+) ions in 2 occurs in a heterochiral manner and produces a dinuclear mesocate.
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Two 3D supramolecular complexes [Cu(2)(trans-oxpn)(phth)](n)().2nH(2)O, 1, and [Cu(2)(trans-oxpn)(&mgr;-OH)(&mgr;-H(2)O)](n)()Br(n)().2nH(2)O, 2 [H(2)oxpn = N,N'-bis(3-aminopropyl)oxamide, phth = phthalate], were synthesized and characterized by single-crystal X-ray crystallography, thermal analyses, and magnetic measurements. 1 crystallizes in the monoclinic space group P2(1)/c with a = 8.578(2) Å, b = 15.596(2) Å, c = 15.657(2) Å, beta = 101.29(2) degrees, Z = 4; 2 crystallizes in the trigonal space group R&thremacr;c with a = 15.266(2) Å, b = 15.266(2) Å, c = 34.953(5) Å, and Z= 18. The neutral 2D sheetlike coordination polymer [Cu(2)(trans-oxpn)(phth)](n)() in 1 contains alternate trans-oxamidate and phthalate bridges and then is joined together by H(2)O molecules via the hydrogen bond linkage Cu(oxpn).H(2)O.H(2)O.(oxpn)Cu to produce a 3D supramolecular structure. The cationic chains [Cu(2)(trans-oxpn)(&mgr;-OH)(&mgr;-H(2)O)](n)()(n)()(+) in 2 contain alternate trans-oxamidate, &mgr;-OH, and &mgr;-H(2)O bridges and are arranged in three directions, intersecting with one another to yield an extended network via the interchain hydrogen bonds formed by metal-coordinated OH(-) with the linkages Cu(oxpn)-OH.OH-Cu(oxpn). Magnetic calculations showed the presence of antiferromagnetic exchange interactions for both complexes. The 2D magnetic coupling system of 1 was simplified into interacting dimers Cu(trans-oxpn)Cu, with the coupling via phth as an interdimer interaction and the data were interpreted with a modified Bleaney-Bowers equation leading to J = -456.7 cm(-)(1) and theta = 22.0 K. 2 was analyzed qualitatively by an alternating chain model taking into account the interchain interaction in a molecular model with J(1) = -309.6 cm(-)(1), J(2) = -63.5 cm(-)(1), and theta = -12.9 K, where J(1) and J(2) denote the coupling constants of the bridges oxamidate and &mgr;-OH, respectively.
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