Synthesis, crystal structures and spectroscopic properties of copper(I) complexes containing beta-dialdiminato supporting ligands

Two mononuclear neutral copper(I) complexes, Cu(L-1)PPh3 (1), Cu(L-2)(PPh3)(2) (2) ([L-1](-) = [{N((C6H3Pr2)-Pr-i-2,6)C(H)}(2)CPh](-); [L-2](-) = [{N(C6H5)C(H)}(2)CPh](-)) have been synthesized and structurally characterized by X-ray crystallography. In complex 1, the copper(I) atom is in a distorted three-coordinate trigonal planar environment, whereas in complex 2 with the less sterically hindered beta-dialdiminato ligand, the copper(I) atom is the centre of a four-coordinate distorted tetrahedron. At room temperature complexes 1 and 2 in a film of PMMA exhibit green emission at 543 and 549 nm with lifetimes of 5.28 and 5.32 ns, respectively.

Hydrothermal synthesis and crystal structure of a sulfur-bridged binuclear copper(II) coordination polymer generated by a spontaneous reduction

A simultaneous reduction SO42- to S2- by 2,5-pyridinedicarboxylate under hydrothermal conditions produced a new binuclear copper(II) coordination polymer [CuS(4,4'-bipy)](n) (4,4-bipy = 4,4'-bipyridine) (1). Single crystal X-ray analysis revealed that compound I consisted of sulfur-bridged binuclear copper(II) units with Cu-Cu bonding which were combined with 4,4-bipy to generate a three-dimensional network constructed from mutual interpenetration of two-dimensional (6,3) nets. Crystal data for 1:C10H8CuN2S, tetragonal 14(1)/acd, a = 14.0686(5) Angstrom, b = 14.0686(5) Angstrom, c = 38.759(2) Angstrom, Z = 32. Other characterizations by elemental analysis, IR, EPR and TGA analysis were also described in this paper.

Novel luminescent iminephosphine complex of copper(I) with high photochemical and electrochemical stability

Luminescent heteroleptic Cu-I complexes based on asymmetrical iminephosphine ligands exhibit improved electrochemical and photochemical stability as compared to the analogous complexes based on traditional diimine or diphosphine ligands.

Nickel(II) and copper(II) complexes containing 2-(2-(5-substitued isoxazol-3-yl)hydrazono)-5,5-dimethylcyclohexane-1,3-dione ligands: Synthesis, spectral and thermal characterizations

Two new hydrazone chelating ligands, 2-(2-(5-methylisoxazol-3-yl)hydrazono)-5,5-dimethylcyclohexane-1,3-dione (HL1) and 2-(2-(5-tert-butylisoxazol-3-yl)hydrazono)-5,5-dimethylcyclohexane- 1,3-dione (HL2), and their nickel(II) and copper(II) complexes were synthesized using the procedure of diazotization, coupling and metallization. Their structures were postulated based on elemental analysis, H-1 NMR, ESI-MS, FT-IR spectra and UV-vis electronic absorption spectra. Smooth films of these complexes on K9 glass substrates were prepared using spin-coating and their absorption properties were evaluated. The thermal properties of the metal(II) complexes were investigated by thermogravimetry (TG) and differential thermogravimetry (DTG). Different thermodynamic and kinetic parameters namely activation energy (E

One-pot synthesis and self-assembly of colloidal copper(I) sulfide nanocrystals

A simple one-pot method is developed to prepare size-and shape-controlled copper(I) sulfide (Cu2S) nanocrystals by thermolysis of a mixed solution of copper acetylacetonate, dodecanethiol and oleylamine at a relatively high temperature. The crystal structure, chemical composition and morphology of the as-obtained products are characterized by powder x-ray diffraction (PXRD), x-ray photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES), transmission electron microscopy (TEM) and scanning electron microscopy (SEM). The morphology and size of the Cu2S nanocrystals can be easily controlled by adjusting the reaction parameters. The Cu2S nanocrystals evolve from spherical to disk-like with increasing reaction temperature. The spherical Cu2S nanocrystals have a high tendency to self-assemble into close-packed superlattice structures. The shape of the Cu2S nanodisks changes from cylinder to hexagonal prism with prolonged reaction time, accompanied by the diameter and thickness increasing. More interestingly, the nanodisks are inclined to self-assemble into face-to-face stacking chains with different lengths and orientations. This one-pot approach may extend to synthesis of other metal sulfide nanocrystals with different shapes and sizes.

咪唑衍生物为配体的铜(I)配合物合成及光物理性质

本论文以咪唑衍生物为配体,合成了新型Cu(I)中性配合物和对应的离子型配合物，考察了它们的光物理和电化学性质。具体工作如下： 设计与合成了分别以2-(2'-吡啶基)苯并咪唑(Hpbm)和2-(2'-喹啉基)苯并咪唑(Hqbm)为配体的Cu(I)中性配合物和四氟硼酸根为抗衡离子的离子型配合物。配合物的晶体结构表明中心铜离子均为扭曲的四面体配位构型，中性配合物的咪唑环中的键长趋于平均化。所有配合物在20wt%浓度的PMMA薄膜中的最大发射处于518.5-597.5nm之间，发光效率为0.097-0.249, 磷光寿命为11.7-25.9µs。中性配合物与对应的离子型配合物相比，其紫外可见吸收光谱发生红移，光致发光光谱发生蓝移。 以2, 2'-联苯并咪唑为配体(H2dbm)，设计和合成了双核和单核Cu(I)配合物，其中双核配合物Cu2(dbm)(PPh3)4在二氯甲烷溶液和PMMA (20 wt%)薄膜中均表现为蓝光发射，在20wt%浓度的PMMA薄膜中的最大发射为448.5和475.5nm。单核离子型配合物[Cu(Hdbm)(PPh3)]2[BF4]在20wt%浓度的PMMA薄膜中的最大发射分别为511，发光效率分别为0.150, 磷光寿命分别为12.0。

An Efficient Ullmann-Type C-O Bond Formation Catalyzed by an Air-Stable Copper(I)-Bipyridyl Complex

An efficient O-arylation of phenols and aliphatic alcohols with aryl halides was developed that uses an air-stable copper(I) complex as the catalyst. This arylation reaction can be performed in good yield in the absence of Cs2CO3. A variety of functional groups are compatible with these reaction conditions with low catalyst loading levels.

Copper(I)-Catalyzed Aryl Bromides To Form Intermolecular and Intramolecular Carbon-Oxygen Bonds

A highly efficient Cu-catalyzed C-O bond-forming reaction of alcohol and aryl bromides has been developed. This transformation was realized through the use of copper(I) iodide as a catalyst, 8-hydroxyquinoline as a ligand, and K3PO4 as a base. A variety of functionalized substrates were found to react under these reaction conditions to provide products in good to excellent yields.

Novel heteroleptic Cu-I complexes with tunable emission color for efficient phosphorescent light-emitting diodes

A series of orange-red to red phosphorescent heteroleptic Cu-I complexes (the first ligand: 2,2 '-biquinoline (bq), 4,4 '-diphenyl2,2 '-biquinoline (dpbq) or 3,3 '-methylen-4,4 '-diphenyl-2,2 '-biquinoline (mdpbq); the second ligand: triphenylphosphine or bis[2-(diphenylphosphino)phenyl]ether (DPEphos)) have been synthesized and fully characterized. With highly rigid bulky biquinoline-type ligands, complexes [Cu(mdpbq)(PPh3)(2)](BF4) and [Cu(mdpbq)(DPEphos)](BF4) emit efficiently in 20 wt % PMMA films with photoluminescence quantum yield of 0.56 and 0.43 and emission maximum of 606 nm and 617 nm, respectively. By doping these complexes in poly(vinyl carbazole) (PVK) or N-(4-(carbazol-9-yl)phenyl)-3,6-bis(carbazol-9-yl) carbazole (TCCz), phosphorescent organic light-emitting diodes (OLEDs) were fabricated with various device structures. The complex [Cu(mdpbq)(DPEphos)](BF4) exhibits the best device performance. With the device structure of ITO/PEDOT/ TCCz:[Cu(mdpbq)(DPEphos)](BF4) (15 wt %)/TPBI/LiF/Al (III), a current efficiency up to 6.4 cd A(-1) with the Commission Internationale de L'Eclairage (CIE) coordinates of (0.61, 0.39) has been realized. To our best knowledge, this is the first report of efficient mononuclear Cu complexes with red emission.

Highly efficient green phosphorescent organic light-emitting diodes based on Cu-I complexes

Mononuclear Cu-I complexes with mixed ligands are used to fabricate green phosphorescent organic light-emitting diodes. The electroluminescence (EL) maximum at 524 nm coincides well with its photoluminescent (PL) spectrum in poly(methyl methacrylate) film (see Figure). A maximum current efficiency of 10.5 cd A(-1) at 105 cd m(-2) and a maximum brightness up to 1663 cd m(-2) are

Highly efficient electroluminescence from green-light-emitting electrochemical cells based on Cu-I complexes

The complexes [Cu(dnpb)(DPEphos)](+)(X-) (dnpb and DPEphos are 2,9-di-n-butyl-1,10-phenanthroline and bis[2-(diphenyl-phosphino)phenyl]ether, respectively, and X- is BF4-, ClO4-, or PF6-) can form high quality films with photoluminescence quantum yields of up to 71 +/- 7%. Their electroluminescent properties are studied using the device-structure indium tin oxide (ITO)/complex/metal cathiode. The devices emit green light efficiently, with an emission maximum of 523 nm, and work in the mode of light-emitting electrochemical cells. The response time of the devices greatly depends on the driving voltage, the counterions, and the thickness of the complex film. After pre-biasing at 25 V for 40 s, the devices turn on instantly, with a turn-on voltage of ca. 2.9 V. A current efficiency of 56 cd A(-1) and an external quantum efficiency of 16% are realised with Al as the cathode. Using a low-work-function metal as the cathode can significantly enhance the brightness of the device almost without affecting the turn-on voltage and current efficiency. With a Ca cathode, a brightness of 150 cd m(-2) at 6 V and 4100 cd m(-2) at 25 V is demonstrated. The electroluminescent performance of these types of complexes is among the best so far for transition metal complexes with counterions.

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).

The oxidative demethylation of 24-membered hexa-aza macrocyclic bicopper(I) complex - The mimicking for monooxygenase

By [2 + 2] Schiff base condensation of 5 - bromo - 2 - methoxylbenzene - 1,3 - dicarboxaldehyde with diethylenetriamine, a new hexaaza 24 - membered macrocyclic ligand was obtained,which formed a macrocyclic binuclear copper(I) complex in the presence of [Cu . (CH3CN)(4)]ClO4. When the copper(I) complex was oxidized in air or oxygen, a new macrocyclic binuclear copper( II) complex was obtained. The copper( II.) complex was characterized by several methods and its oxidized products was characterized by H-1 NMR. The results show that during oxidation, a methoxyl group in the ligand ring broke; and the phenoxy - and water - bridged Cu(II) complex formed. In oxidation of monooxygenase such as ligninase, oxidative demethylation also happened. Therefore this work mimicked this process for the first time by using macrocyclic complex. The quantity of absorbed oxygen and the absorption rate of oxygen were determined.