Complexes of formulation [Cu(Tp(Ph))(L)](ClO(4)) (1-4), where Tp(Ph) is anionic tris(3-phenylpyrazolyl)borate and L is N,N-donor heterocyclic base, viz. 2,2'-bipyridine (bpy, 1), 1,10-phenanthroline (phen, 2), dipyridoquinoxaline (dpq, 3), and dipyridophenazine (dppz, 4), are prepared from a reaction of copper(II) acetate.hydrate with KTp(Ph) and L in CH(2)Cl(2) and isolated as perchlorate salts. The complexes are characterized by analytical, structural, and spectral methods. The crystal structures of complexes 1-4 show the presence of discrete cationic complexes having the metal, Tp(Ph), and L in a 1:1:1 ratio and a noncoordinating perchlorate anion. The complexes have a square-pyramidal 4 + 1 coordination geometry in which two nitrogens of L and two nitrogens of the Tp(Ph) ligand occupy the basal plane and one nitrogen of Tp(Ph) binds at the axial site. Complexes 3 and 4 display distortion from the square-pyramidal geometry. The Cu-N distances for the equatorial and axial positions are approximately 2.0 and 2.2 A, respectively. The phenyl groups of Tp(Ph) form a bowl-shaped structure that encloses the [CuL] moiety. The steric encumbrance is greater for the bpy and phen ligands compared to that for dpq and dppz. The one-electron paramagnetic complexes (mu approximately equal to 1.8 mu(B)) exhibit axial EPR spectra in CH(2)Cl(2) glass at 77 K giving g(parallel) and g(perpendicular) values of approximately 2.18 (A(parallel) = 128 G) and approximately 2.07. The data suggest a [d(x(2)-y(2))](1) ground state. The complexes are redox-active and display a quasireversible cyclic voltammetric response for the Cu(II)/Cu(I) couple near 0.0 V versus SCE with an i(pc)/i(pa) ratio of unity in CH(2)Cl(2) or DMF-0.1 M TBAP. The E(1/2) values of the couple vary in the order 4 > 3 > 2 > 1. A profound effect of steric encumbrance caused by the Tp(Ph) ligand is observed in the reactivity of 1-4 with the calf thymus (CT) and supercoiled (SC) DNA. Complexes 2-4 show similar binding to CT DNA. The propensity for the SC DNA cleavage varies as 4 > 3 > 2. The bpy complex does not show any significant binding or cleavage of DNA. Mechanistic investigations using distamycin reveal minor groove binding for 2 and 3 and a major groove binding for 4. The scission reactions that are found to be inhibited by hydroxyl radical scavenger DMSO are likely to proceed through sugar hydrogen abstraction pathways.

We report a new synthesis process of colloidal indium (In) doped zinc oxide (ZIO) nanocrystals by a hot injection technique. By fine tuning the synthesis we reached the same nucleation temperature for indium oxide and zinc oxide which helped us to study a dopant precursor dependent In incorporation into the ZnO matrix by using different In sources. The dopant induced shape evolution changes the hexagonal pyramid structured ZnO to a platelet like structure upon 8% In doping. The introduction of trivalent In(3+) into the ZnO lattice and consequent substitution of divalent Zn(2+) generates free electrons in the conduction band which produces a plasmonic resonance in the infrared region. The electron concentration controls plasmon frequency as well as the band gap of host ZnO. The variation of the band gap and the modification of the conduction band have been explained by the Burstein-Moss effect and Mie's theory respectively. The In dopant changes the defect chemistry of pure ZnO nanocrystals which has been studied by photoluminescence and other spectroscopic measurements. The nanocrystals are highly stable in the organic medium and can be deposited as a crack free thin film on different substrates. Careful ligand exchange and thermal annealing of the spin cast film lead to a good conductive film (720 Ω per square to 120 Ω per square) with stable inherent plasmonic absorption in the infrared and 90% transmittance in the visible region. A temperature induced metal-semiconductor transition was found for doped ZnO nanocrystals. The transition temperature shifts to a lower temperature with increase of the doping concentration.

Colloidal trivalent gallium (Ga) doped zinc oxide (ZnO) hexagonal nanocrystals have been prepared to introduce more carrier concentration into the wide band gap of ZnO. The dopant (Ga) modifies the morphology and size of ZnO nanocrystals. Low content of Ga enhances the optical band gap of ZnO due to excess carrier concentration in the conduction band of ZnO. The interaction among free carriers arising from higher concentration of Ga gives rise to narrowing of the band gap. Surface plasmon resonance absorption appears in the infrared region due to excessive carrier concentration. A broad emission band consists of blue, yellow and green colors associated with different native defects of ZnO. Intrinsic defects and extrinsic dopant Ga control the defect related emission spectrum in the visible region. Replacement of Zn by Ga induces a room temperature metallic state in a degenerate semiconductor. Cationic disorder leads to metal-semiconductor transition at low temperature strongly dependent on the concentration of Ga. Pure semiconducting behavior up to about 80 K is observed for the highest amount of Ga. Temperature dependent metal-semiconductor transition has been interpreted by localization of charge carriers due to disorder arising from random Ga substitution.

Dicopper(II) complexes [Cu 2 L(O 2 CC 6 H 4 -o-NH 2 )] (1) and [Cu 2 L(O 2 CC 6 H 4 -p-NH 2 )] (2) are prepared from a reaction of [Cu 2 -L(O 2 CMe)] with the corresponding aminobenzoic acid and a base in MeOH, where L is a trianionic pentadentate Schiff base ligand N,N 0 -(2-hydroxypropane-1,3-diyl)bis(salicylaldimine). The complexes are structurally characterized by X-ray crystallography. The crystal structures show the presence of an asymmetrically dibridged {Cu 2 II (l-OR)(l-O 2 CR)} core where the endogenous monoatomic bridging alkoxo group is derived from the Schiff base and the aminobenzoate ligand displays syn-syn bridging mode. The CuÁ Á ÁCu separation and Cu-OR-Cu bond angle in 1 and 2 are 3.472(1) Å , 131.02(18)°and 3.511(1) Å , 132.20(17)°, respectively. The o-aminobenzoate complex is discrete dimeric nature. The pendant o-amino group is involved in an intramolecular hydrogen bonding interaction with one carboxylate oxygen atom. The crystal structure of the p-aminobenzoate species 2 shows the formation of a one-dimensional polymeric chain resulting from the axial binding of the pendant p-amino group to one copper center belonging to another dimeric unit. Magnetic studies show that both the complexes are antiferromagnetic in nature giving a singlet-triplet energy separation of À130 and À150 cm À1 for 1 and 2, respectively. The 1D chain complex 2 magnetically behaves like the discrete dimeric complex 1.