Oligoaniline-Functionalized terpyridine ligands and their ruthenium(II) complexes: synthesis, spectroscopic property and redox behaviors

A series of oligoaniline-functionalized mono- and bis-topic terpyridine ligands, i.e. C6H5[N(R)C6H4](n)TPY (R = H, butyl, tert-butyloxycarbonyl; n = 1-4; TPY = 2,2':6',2"-terpyridyl) and TPYC6H4[N(R)C6H4](m)TPY (R = H, tert-butyloxycarbonyl; m = 2, 4), and the corresponding monoand bis-nuclear ruthenium(II) complexes have been synthesized and verified. The spectroscopic results indicate that two kinds of pi-pi* transitions from TPY and oligoaniline fragments of ligands strongly shift to lower energy, and the metal-to-ligand charge-transfer transition ((MLCT)-M-1) bands of all obtained complexes are considerably red-shifted (Delta lambda(max) = 22-64 nm) and their intensities become much more intense (approximately 4-6 times), compared with those of the reported complex [Ru(TPY)(2)](2+). Moreover, the spectroscopic properties of the ligands and complexes with longer oligoaniline units (n = 3, 4) are markedly influenced by the external stimulus, such as the oxidation and proton acid doping.

Synthesis, characterization and electrophosphorescent properties of mononuclear platinum(II) complexes based on 2-phenylbenzoimidazole derivatives

The rational design, synthesis and characterization of five phosphorescent platinum complexes [(C boolean AND N) Pt(acac)] [Hacac = acetylacetone, HC boolean AND N = 1-methyl-2-(4-fluorophenyl)benzoimidazole (H-FMBI), 1-methyl-2-phenylbenzoimidazole (H-MBI), 1,2-diphenyl-benzoimidazole (H-PBI), 1-(4-(3,6-di-t-butylcarbazol-9-yl)) phenyl-2-phenylbenzoimidazole (t-BuCz-H-PBI), and 1-(4-(3,6-di-(3,6-di-t-butyl-carbazol-9-yl))carbazol-9-yl) phenyl-2-phenylbenzoimidazole (t-BuCzCz-H-PBI)] have been discussed. The crystal structure of (MBI) Pt(acac) shows a nearly ideal square planar geometry around Pt atom and the weak intermolecular interactions with pi-pi spacing of 3.55 angstrom. All of the complexes emit green phosphorescence from the metal-to-ligand charge-transfer (MLCT) excited state with high quantum efficiency (0.08-0.17) at room temperature.

Synthesis, photophysical and electrophosphorescent properties of mononuclear Pt(II) complexes with arylamine functionalized cyclometalating ligands

Four cyclometalated Pt(II) complexes, i.e., [(L-2)PtCl] (1b), [(L-3)PtCl] (1c), [(L-2)PtC CC6H5] (2b) and [(L-3)PtC CC6H5] (2c) (HL2 = 4-[p-(N-butyl-N-phenyl)anilino]-6-phenyl-2,2'-bipyridine and HL3 = 4-[p(-N,N'-dibutyl-N'-phenyl)phenylene-diamino]-phenyl-6-phenyl-2,2'-bipyridine), have been synthesized and verified by H-1 NMR, C-13 NMR and X-ray crystallography. Unlike previously reported complexes [(L-1)PtCl] (1a) and [(L-1)PtC CC6H5] (2a) (HL1 = 4,6-diphenyl-2,2'-bipyridine), intense and continuous absorption bands in the region of 300-500 nm with strong metal-to-ligand charge transfer ((MLCT)-M-1) (d pi(Pt) -> pi*(L)) transitions (epsilon similar to 2 x 10(4) dm(3) mol (1) cm (1)) at 449-467 nm were observed in the UV-Vis absorption spectra of complexes 1b, 1c, 2b and 2c.

catena-Poly[[[di-mu-acetato-kappa O-4 : O '-bis[(acetato-kappa O-2,O ')manganese(II)]]-di-mu-4,4 '-bipyridine-kappa N-4 : N '] monohydrate

The title compound, {[Mn-2(CH3CO2)(4)(C10H8N2)(2)](H2O)-H-.}(n), is a one-dimensional coordination polymer with a ladder-like structure. Two Mn-II atoms, each coordinated by a chelating acetate ligand, are bridged by two bidentate acetate ligands to form a centrosymmetric [Mn-2(CH3CO2)(4)] unit. Two 4,4'-bipyridine ligands link the [Mn-2(CH3CO2)(4)] units through Mn-N bonds to generate a molecular ladder. The water O atom lies on a crystallographic twofold rotation axis.

Synthesis, structure and luminescence properties of zinc (II) complexes with terpyridine derivatives as ligands

Five zinc (II) complexes (1-5) with 4 '-phenyl-2,2 ':6 ',2 ''-terpyridine (ptpy) derivatives as ligands have been synthesized and fully characterized. The para-position of phenyl in ptpy is substituted by the group (R), i.e. tert-butyl (t-Bu), hexyloxy (OHex), carbazole-9-yl (Cz), naphthalen-1-yl-phenyl-amine-N-yl (NPA) and diphenyl amine-N-yl (DPA), with different electron-donating ability. With increasing donor ability of the R, the emission color of the complexes in film was modulated from violet (392 nm) to reddish orange (604 nm). The photoexcited luminescence exhibits significant solvatochromism because the emission of the complexes involves the intra-ligand charge transfer (ILCT) excited state. The electrochemical investigations show that the complexes with stronger electro-donating substituent have lower oxidation potential and then higher HOMO level. The electroluminescence (EL) properties of these zinc (II) complexes were studied with the device structure of ITO/PEDOT/Zn (II) complex: PBD:PMMA/BCP/AlQ/ LiF/Al. Complexes 3, 4 and 5 exhibit EL wavelength at 552, 600 and 609 nm with maximum current efficiency of 5.28, 2.83 and 2.00 cd/A, respectively.

Syntheses, crystal structures and properties of two Cu(II) coordination polymers: Cu(C3N2H4)(2)(HL)(2) andCU(C3N2H4)(2)L with C3N2H4 = imidazole, H2L = adipic acid

The reactions of freshly prepared Cu(OH)(2).xH(2)O and Cu(OH)(2-2y)(CO3)(y).zH(2)O precipitates with imidazole and adipic acid in CH3OH/H2O at pH = 5.4 yielded CU(C3N2H4)(2)(HL)(2) 1 and CU(C3N2H4)(2)L 2, respectively. Complex 1 consists of ribbon-like polymeric chains (1)(infinity)[CU(C3N2H4)(2)(HL)(4/2)], in which the octahedrally coordinated Cu atoms are doubly bridged by bis-monodentate hydrogen adipato ligands. The interchain N-H...O hydrogen bonding interactions are responsible for supramolecular assembly of the polymeric chains into open 3D frameworks and two-fold interpenetration of the resulting open frameworks completes the crystal structure of 1. Within complex 2, the Cu atoms are penta-coordinated to form CuN2O3 square pyramids and condensed into CU2N4O4 dimers, which are doubly bridged by twisted bis-monodentate adipato ligands into polymeric chains (1)(infinity)([CU(C3N2H4)(2)](2)L-4/2) with 4- and 18-membered rings progressing alternatively. The polymeric chains are assembled due to interchain N-H...O hydrogen bonding interactions. The thermal and magnetic behaviors of 1 and 2 is discussed.

Preparation of linear alpha-olefins to high-molecular weight polyethylenes using cationic alpha-diimine nickel(II) complexes containing chloro-substituted ligands

A series of alpha-diimine nickel(II) complexes containing chloro-substituted ligands, [(Ar)N=C(C10H6)C=N(Ar)]NiBr2 (4a, Ar = 2,3-C6H3Cl2; 4b, Ar = 2,4-C6H3Cl2; 4c, Ar = 2,5-C6H3Cl2; 4d, Ar = 2,6-C6H3Cl2; 4e, Ar = 2,4,6-C6H2Cl3) and [(Ar)N=C(C10H6)C=N(Ar)](2)NiBr2 (5a, Ar = 2,3-C6H3Cl2; 5b, Ar = 2,4-C6H3Cl2; 5c, Ar = 2,5-C6H3Cl2), have been synthesized and investigated as precatalysts for ethylene polymerization. In the presence of modified methylaluminoxane (MMAO) as a cocatalyst, these complexes are highly effective catalysts for the oligomerization or polymerization of ethylene under mild conditions. The catalyst activity and the properties of the products were strongly affected by the aryl-substituents of the ligands used. Depending on the catalyst structure, it is possible to obtain the products ranging from linear alpha-olefins to high-molecular weight polyethylenes.

Synthesis, crystal structure, spectroscopy and electroluminescence of zinc(II) complexes containing bidentate 2-(2-pyridyl)quinoline derivative ligands

Three bidentate ligands, 4-phenyl-2-(2-pyridyl)-quinoline (ppq), 6-(carbazol-9-yl)-4-phenyl-2-(2-pyridyl)-quinoline (cpq) and 6-diphenylamino-4-phenyl-2-(2-pyridyl)-quinoline (dpq) and their zinc(II) complexes, have been designed and synthesized. The crystal structure of [Zn(ppq)(2)Cl]PF6 shows that the central zinc atom is coordinated with one chloride and four nitrogen atoms from two ligands. The introduction of an electron-donating substituent such as carbazole or an aromatic amine group at the 6-position of the quinoline moiety can generate colored tunable Zn complexes, and the photoluminescence (PL) wavelength was modulated from 418 nm for [Zn(ppq)(2)Cl]PF6 to 591 nm for [Zn(cpq)(2)Cl]PF6 and 638 nm for [Zn(dpq)(2)Cl]PF6 in CH2Cl2 solution. The electroluminescence spectrum of [Zn(dpq)(2)Cl]PF6 exhibits pure red light emission with the Commission Internationale de L'Eclairage (CIE) coordinates (0.63, 0.36) and a maximum at 648 nm.

catena-Poly[[[di-mu-acetato-kappa O-4 : O '-bis[(acetato-kappa O-2,O ')manganese(II)]]-di-mu-4,4 '-bipyridine-kappa N-4 : N '] monohydrate]

The title compound, {[Mn-2(CH3CO2)(4)(C10H8N2)(2)](H2O)-H-.}(n), is a one-dimensional coordination polymer with a ladder-like structure. Two Mn-II atoms, each coordinated by a chelating acetate ligand, are bridged by two bidentate acetate ligands to form a centrosymmetric [Mn-2(CH3CO2)(4)] unit. Two 4,4'-bipyridine ligands link the [Mn-2(CH3CO2)(4)] units through Mn-N bonds to generate a molecular ladder. The water O atom lies on a crystallographic twofold rotation axis.

New neutral nickel(II) complexes bearing pyrrole-imine chelate ligands: synthesis, structure and norbornene polymerization behavior

New neutral nickel(II) complexes bearing nonsymmetric bidentate pyrrole-imine chelate ligands (4a-d), [2-(ArNCH)C4H3N]Ni(PPh3)Ph [Ar=2,6-diisopropylphenyl (a), 2-methyl-6-isopropylphenyl (b), 2,6-diethylphenyl (c), 2-tert-butylphenyl (d)], have been prepared in good yields from the sodium salts of the corresponding ligands and trans-Ni(PPh3)(2)(Ph)Cl, and the structure of complex 4a has been confirmed by X-ray crystallographic analysis. These neutral Ni(II) complexes were investigated as catalysts for the vinylic polymerization of norbornene. Using modified methylaluminoxane (MMAO) as a cocatalyst, these complexes display very high activities and produce great mass polymers. Catalyst activity of up to 4.2 x 10(7) g (mol Ni h)(-1) and the viscosity-average molecular weight of polymer of up to 9.2 x 10(5) g mol(-1) were observed. Catalyst activity, polymer yield, and polymer molecular weight can be controlled over a wide range by the variation of reaction parameters such as Al-Ni ratio, norbornene-catalyst ratio, monomer concentration, polymerization reaction temperature and time.

Self-immobilized catalysts for ethylene polymerization: neutral, single-component salicylaldiminato phenyl nickel(II) complexes bearing allyl substituents

A new family of self-immobilized ethylene polymerization catalysts, derived from neutral, single-component salicylaldiminato phenyl nickel complexes, is described.

The efficient syntheses of three novel bridging phenanthroline ligands and their binuclear ruthenium(II) complexes

Three bridging ligands (L) and their binuclear phenanthroline ruthenium(II) complexes {[Ru(1,10-phenanthroline)(2)](2)(L)}(PF6)(4) were synthesized and characterized by IR, H-1 NMR, and elemental analysis, where L are 1,8-adipoylamido-bis(1,10-phenanthroline-5-yl) (L-1), 1,11-azelaoylamidobis(1, 10-phenanthroline-5-yl) (L-2), and p-phthaloylamido-bis(1,10-phenanthroline-5-yl) (L-3).

Synthesis, 2D NMR, electrochemistry and luminescence of ruthenium(II) complexes with 2,2 '-bipyridine and 5-(omega-bromoalkylamido)-1,10-phenanthroline

The efficient synthesis of 5-(5-bromovaleramido)-1,10-phenanthroline, 5-(6-bromohexanamido)-1,10-phenanthroline, and 5-(11-bromoundecanamido)-1,10-phenanthroline are described, which reacted with cis-Ru(bpy)(2)Cl-2. 2H(2)O and sodium hexafluorophosphate to form Ru(bpy)(2)[phen-NHCO(CH2)(n)Br](PF6)(2) (n = 4, 5 or 10; phen = 1,10-phenanthroline). The intricate H-1 NMR spectra at low field of these complexes were completely assigned in virtue of H-1-H-1 COSY technique. Cyclic voltammetry was used to study electrochemical behaviours of these complexes, and their luminescent properties were investigated with fluorescent spectra.

Kinetics of electrocatalytic ascorbic acid at ultramicroelectrode modified by Eastman-AQ polymer containing tris(2,2-'-bipyridine) osmium(III/II) complexes as electron-transfer centers

The theoretical model[17] of an ultramicroelectrode modified with a redox species film is used as the diagnostic tool to characterize the catalytic oxidation of ascorbic acid at carbon fiber ultramicrodisk electrodes coated with an Eastman-AQ-Os(bpy)(3)(2+) film. The electrocatalytic behavior of ascorbic acid at the ultramicroelectrode modified by an Eastman-AQ polymer containing tris(2,2'-bipyridine) osmium(III/II) as mediators is described. In order to determine the five characteristic currents quantitatively, the radius of the ultramicroelectrode and the concentration of ascorbic acid are varied systematically. The kinetic zone diagram has been used to study the electrocatalytic system. This system with 0.5-2.75 mM ascorbic acid belongs to SR + E case, and the concentration profiles of the catalyst in the film are given in detail. Finally, optimizing the design of catalytic system is discussed.