Synthesis, luminescence properties and energy transfer of binary and ternary rare earth complexes with aromatic acids and 1,10-phenanthroline

A series of binary and ternary rare earth (Gd, Eu, Tb) complexes with ortho hydroxyl benzoic acid, para aminobenzoic acid, nicotinic acid and 1,10-phenanthroline were synthesized. Phosphorescence spectra and lifetimes of Gd complexes were measured and the lowest triplet state energies of gadolinium binary complexes and the intramolecular energy transfer efficiencies were determined. The luminescence properties and energy transfer process of Eu3+and Tb3+ complexes were discussed.     

STUDY ON POLYMER—Ru-Co—BIMETALLIC COMPLEXES CATALYSTS Ⅰ. SYNTHESIS OF CATALYSTS AND THEIR USE FOR THE HYDROFORMYLATION

Six kinds of polymer ligands, supported on SiO_2, containing coordinating atoms P, S and N respectively, have been synthesized. The Ru(Ⅲ)-Co(Ⅱ) bimetallic complexes of these polymer ligands have been obtained and examined as catalysts for the hydroformylation of cyclohexene. The effects of reaction temperature, pressure and Co/Ru ratio etc. on the activities of catalysts were investigated in detail. The catalysts are all polymer-noncarbonyl-metal complexes, easily to be prepared, active and stable. From the experimental results it can be suggested that under reaction conditions such polymer-noncarbonyl-metal complexes convert "in situ" to polymer-carbonyl-metal complexes, thus become active catalysts. The course of this conversion is supposed as a preliminary approach.     

Off-on-off Luminescent Switching of a Novel Ru(II) Complex

There has been explosive interest in the synthesis and applications of novel Ru(II) polypyridyl complexes with respect to molecular sensors1,2, switches3, and sensitizers of Gr鋞zel solar cells based on nanocrystalline TiO24. Here we report a novel Ru(II) complex, which can serve as pH-induced remarkable off-on-off luminescent switch. Scheme 1 The acid-base equilibria of the complex UV-vis absorption and emission spectroscopic pH titration experiments of the Ru complex wit…     

Molecular ferroelectrics for efficient perovskite solar cells

During the past decade,the power conversion efficiencies(PCEs)of organic-inorganic hybrid perovskite solar cells(PSCs)have exceeded 25%[1],which is expected to be one of the candidates for the next generation of thin-film photovoltaic technology.Fundamentally speaking,the performance of PSCs mainly depends on the light absorption capacity,defect passivation and photo-induced exciton separation and extraction of perovskite films.Under the light illumination,photo-induced excitons were separated and extracted by the built-in electric field of PSCs.     

不同配体对钌多吡啶配合物与DNA的作用和荧光性质的影响

Two polypyridyl ligands DCHIP (2-hydro-3，5-dichlorophenyl-imidazo[4，5-f][1，10] phenanthroline)，MDHIP(2，4-dihydrophenyl-imidazo[4，5-f][1，10]phenanthroline) and their ruthenium(Ⅱ) complexes [Ru(phen)₂MDHIP]²⁺ and [Ru(phen)₂DCHIP]²⁺ were prepared. Their DNA-binding properties were studied by spectroscopic methods and viscosity measurements. The results indicated that the complexes both bound to DNA by partial intercalation mode， but [Ru(phen)₂DCHIP]²⁺ exhibited stronger binding affinity for DNA than [Ru(phen)₂MDHIP]²⁺ due to the different planarities and steric effects of ligands. On the other hand， after binding to DNA， the fluorescence intensity of [Ru(phen)₂MDHIP]²⁺ decreased， while the fluorescence intensity of [Ru(phen)₂ DCHIP]²⁺ increased.     

Theoretical study on second-order nonlinear optical properties of 1,10-phenanthroline Ru(Ⅱ) complexes

The dynamic first hyperpolarizabilities of a series of 1,10-phenanthroline Ru(Ⅱ) complexes were carried out using density functional theory(DFT).The results indicate that these complexes have large second-order nonlinear optical(NLO) responses.Specially,complex 6b has a maximal first hyperpolarizability βtot value.The first hyperpolarizabilities can be tuned by changing the ancillary ligand,introducing electron-acceptor group NO2 and/or increasing π-conjugation on phenanthroline.Calculations on absorption spectra demonstrate that the second-order NLO responses of complexes in series a are ascribed to the intraligand charge transfer(ILCT),while the complexes in series b exhibit metal-to-ligand charge transfer(MLCT) and ligand-to-ligand charge transfer(LLCT) transition at relatively low-energy absorptions.     

DNA structure, binding mechanism and biology functions of polypyridyl complexes in biomedicine

There is considerable research interest and vigorous debate about the DNA binding of polypyridyl complexes including the electron transfer involving DNA. In this review, based on the fluorescence quenching experiments, it was proposed that DNA might serve as a conductor. From the time-interval CD spectra, the different binding rates of A- and A-enantiomer to calf thymus DNA were observed. The factors influencing the DNA-binding of polypyridyl complexes, and the potential bio-functions of the complexes are also discussed.     

The synthesis and crystal structure of metal complexes S-alkyl-N-(ferrocenyl-1-methyl-methylidene)-dithiocarbazate and the study on their quenching the luminescence ofruthenium(bipyridine)_~3(2+)

The cobalt, nickel, copper, zinc and cadmium complexes of S-methyl-N-(ferrocenyl-l-methyl-methylidene)-dithiocarbazate (H-LSM) and S-benzyl-N-(ferrocenyl-l-methyl-methylidene)-dithiocarbazate (H-LSB) were synthesized and the crystal structure of Cd[Fe-C(CH3) = NNCSS. (CH3)]2 was solved by X-ray diffraction. The crystal is in the orthorhombic system with space group Pbca, cell parameters a=19.741(3), b=19.924(5), c=15.452(4) A, and the final factors of R=0.032. The study on quenching the luminescence of Ru(bpy)3 by those complexes showed that bimolecular quenching constants obtained from the Stern-Vohner constant and the excited-state lifetime were related to the redox potential of the quencher. Linear relationship is shown in the plot of logkq vs. E1/2(Q+/Q). The main factor which influences the quenching rate constant and the redox potential is the coordinating ability of the metal in the complex.     

Preparation,Characterization and Thermal Decomposition Kinetics of the Complexes [Dy(p-NBA)_3Phen]_2·3H_2O and [Dy(m-NBA)_3Phen]_2·4H_2O

The title complexes [Dy(p-NBA)3Phen]2·3H2O(I) and [Dy(m-NBA)3Phen]2·4H2O(Ⅱ) were synthesized, in the two molecular formulas of which NBA is nitrobenzoate and Phen is 1,10-phenanthroline. The characterizations of the complexes were carried out by means of elemental analysis, UV, IR, XRD and molar conductivity. The thermal decomposition of the two complexes were studied under the non-isothermal condition by DSC, TG-DTG and IR methods in detail. The kinetic parameters of the dehydration process were also obtai...     

Organic solar cells for indoor power generation

正During last decades, organic solar cells (OSCs) have achieved remarkable advancements via extensive studies on the optimization of photovoltaic donor/acceptor (D/A) materials, device fabrication, and the D/A bulk heterojunction morphologies. Power conversion efficiencies (PCEs) up to～16%for single junction cells and over 17%PCEs were successfully demonstrated for tandem OSC devices [1,2].OSCs may find real industrial applications soon, including     

Synthesis and Anticancer Activity of a New Di-nuclear Ruthenium Arene Compound with Thiosemicarbazones

A new di-nuclear ruthenium arene compound containing thiosemicarbazone ligands, [Ru(η~6-cymene)(TSC)Cl]_2(PF_6)_2(2), was synthesized and characterized by ~1H NMR, HR-ESI-MS, and elemental analysis. Furthermore, the complete structure of 2 was determined by single-crystal X-ray diffraction analysis. Density functional theory(DFT) calculations with B3LYP functional and LANL2DZ(for Ru)/6-31G*(for other atoms) basis sets were carried out for the reactions involving complexes 1 and 2 in order to understand the formation of the complexes. The in vitro anticancer activities of the compound were investigated against five human cancer cell lines(SGC-7901, CNE-2, HepG2, KB and HeLa), and the IC_(50) values are 39.5, 45.8, 49.8, 54.5 and 61.8 μM, respectively.     

氮掺杂碳纳米管负载的Ru和Pd催化剂上异丙醇的转化(英文)

Ru and Pd (2 wt%) loaded on pure and on Ndoped carbon nanotubes (NCNTs) were prepared and tested using the isopropyl alcohol decomposition reaction as probe reaction. The presence of nitrogen functionalities (pyridinic, pyrrolic, and quaternary nitrogen) on the nitrogen doped support induced a higher metal dispersion: Pd/NCNT (1.8 nm) Pd/CNT (4.9 nm), and Ru/NCNT (2.4 nm) Ru/CNT (3.0 nm). The catalytic activity of the supports was determined first. Isopropyl alcohol conversion produces acetone on CNTs while on NCNTs it led to both dehydration and dehydrogenation products. At 210 °C and in the presence of air, the isopropyl alcohol conversion was higher on the NCNTs (25%) than on the CNTs (11%). The Pd loaded catalysts were more active and more selective than the Ru ones. At 115 °C, the Pd catalysts were 100% selective towards acetone for a conversion of 100%, whereas the Ru catalysts led to dehydration and dehydrogenation products. The nitrogen doping induced the appearance of redox properties when oxygen is present in the reaction mixture.     

Recent progress in functionalized electrophosphorescent iridium(Ⅲ) complexes

Iridium(Ⅲ) complexes are one of the most important electrophosphorescent dyes with tunable emissions in the range of visible and near infrared lights,high photoluminescence yields and short lifetimes for high-efficiency organic light-emitting diodes(OLED) with 100% exciton harvesting.This review summarizes the recent development of electroluminescent Ir~(3+) complexes functionalized with host-featured carrier-transporting groups,with emphasis on correlations between functionalization,optoelectronic properties and device performance.According to the introducing approaches,the complexes were sorted with conjugated and aliphatic linkages,as well as the types of functional groups.The modification effect on physical properties and the state-of-the-art device performances were discussed.     

Spacial Structure of Cationic Phosphorus Ligand-Ru （Ⅱ） Halide Complexes-by DFT Study

The full-parameter geometry optimization of cationic （ S ） - BINAP - Ru （ Ⅱ ） halide complex was performed by DFT method using B3LYP, PW91 and PBE potentials with several basis sets. PW91 with 3-21G / SDD basis sets is found to be the most suitable method with consideration of both precision and efficiency. The dihedral angles （ θ ） of the binaphthyl or biphenyl with different phosphorus ligand - Ru （ Ⅱ ） halide complexes were found changing from 59.9 to 79.3 degree, while the natural bite angle （ βn ） of those complexes only changes from 87.4 to 90.3 degree. It is different from the common view of asymmetric organic chemists＇ that θ directly influences βn.     

Tuning the Excited—state Properties of Cyclometalated Platinum（Ⅱ）Complexes of 6—Pheny1—2,2’bipyridine by Ancillary Acetylide Ligand

A series of luminescent cyclometalated platinum(Ⅱ）complexes,(C^N^N)Pt(C≡CR)[HC^N^N=4-(4-tolyl)-6-phenyl-2,2’-bipyridine;R=4-chlorophenyl(1),phenyl(2) and 4-tolyl(3)],were synthesized,and their spectroscopic properties have been examined.These complexes are brightly emissive both in fluid solution and in the solid state,attributed to triplet metal-to-ligand charge transfer(^3MLCT)state.The excited state energy can be tuned by ancillary acetylide ligands.The emission lifetimes in dichloromethand solution at room temperature were up to 1.64 μs and the emission quantum yields were in the range of 0.03-0.15.     

Synthesis of New Ruthenium（Ⅱ）Bipyridyl Complexes and Studies on Their Photophysical and Photoelectrochemical Properties

Two new mixed-ligand ruthenium(Ⅱ） complexes,Ru(dcbpy)-(LL)NCS)2[where dcbpy=4,4‘-dicarboxyl-2,2‘‘-bipyridine,LL=4,4‘-bis(N-methyl-anilinomethyl)-2,2‘‘-bipyridine(2)],were synthesized,and the tphotophysical properties of these complexes were studied.The metal-to-ligand charge transfer (MLCT) transitions of these complexes exhibited solvatochromic effect due to the existence of NCS ligands.The MLCT energies also strongly depend on the pH values of the solutions because of protonation and deprotonation of the carboxyl groups.The pKa values of the ground state,4.0 for 1 and 3.8 for 2,were obtained from the titration curves.The photoelectrochemical properties of 1 and 2 as sensitizers in sandwich-type solar cells have been studied.Complex 1 exhibited better photoelectrochemical behavior than complex 2 as expected.It was proved that the design of mixed-ligand complex by introducing electron donating group in one of the ligands should be a promising approach.     

New Copper（Ⅱ） and Nickel（Ⅱ） Complexes of 4-Morpholinoacetophenone Thiosemicarbazone： Structural, Electrochemical and Antimicrobial Studies

4-Morpholinoacetophenone thiosemicarbazone, MAPT, and its nickel（Ⅱ） and copper（Ⅱ） complexes have been prepared and characterized by elemental analysis, magnetic susceptibility, spectral methods （FT-IR, ^1H NMR） and cyclic voltammetry. Electrochemical behaviors of the complexes have been studied by cyclic voltammetry in DMF media showing metal centered reduction processes for both of them. The redox properties, nature of the electrode processes and the stability of the complexes were discussed. [Cu（MAPT）2]Cl2 complex shows Cu（Ⅱ）/Cu（Ⅰ） couple and quasi-reversible wave associated with the Cu（Ⅲ）/Cu（Ⅱ） process. The reduction/oxidation potential values depend on the structures of complexes. Also, the antimicrobial activities of these complexes were determined against S. aureus, E. coli and B. subtilis.     

四种钌（Ⅱ）配合物的中心离子电化学行为的比较

The electrochemical behavior of mononuclear and symmetrical binuclear ruthenium（Ⅱ） complexes [Ru1:Ru(bpy)2DIPB(ClO4)2,Ru2:(bpy)2 Ru(DIPB)Ru(bpy)2(ClO4)4,Ru3:Ru(phen)2DIPB(ClO4)2 and Ru4:(phen)2 Ru(DIPB)Ru (phen)2(ClO4)4] containing binuclear ligand 2,2′-bipyridine(bpy),1,10-phenanthroline(phen) and bridging ligand 1,4-di-[2-imidazo[4,5-f][1,10] phenanthroine benzene(DIPB) on a platinum electrode and the intermetallic interaction of binuclear complexes have been investigated using cyclic voltammetry,cyclic ac voltammetry and differential capacitance techniques,etc.In acetonitrile solution with a concentration of 0.1 mol穌m-3 TBAP,the central ions in four complexes all display single 1e and 2e reversible oxidation- reduction waves on the cyclic voltammograms,with apparent diffusion coefficients of the mononuclear complexed cations being larger than that of the binuclear ones.The apparent diffusion coefficients for complexed cations with auxiliary ligands bpy are also found to be larger than that with ligands phen.It appears that the overlapping of two continuous single-electron processes by cyclic ac voltammetry and differential capacitance techniques occurs during the redox processes of the central ions binuclear complexes.The results show that a weak electronic interaction exits between the two central ruthenium ions in binuclear complexes.     

Toward high-efficiency perovskite solar cells with one-dimensional oriented nanostructured electron transport materials

The unique advantages of one-dimensional(1D) oriented nanostructures in light-trapping and chargetransport make them competitive candidates in photovoltaic(PV) devices. Since the emergence of perovskite solar cells(PSCs), 1D nanostructured electron transport materials(ETMs) have drawn tremendous interest. However, the power conversion efficiencies(PCEs) of these devices have always significantly lagged behind their mesoscopic and planar counterparts. High-efficiency PSCs with 1D ETMs showing eff...     

SPECTROSCOPIC STUDIES ON A HETEROMETALLOBINUCLEAR COMPLEX IN WHICH Ru(BPY)_3~(2+)WAS COVALENTLY ATTACHED TO N_i~-(CYCLAM)~(2+)

The spectroscopic properties for a recently synthesized hetero-metallo-binuclear complex Ru(bpy)_2 (bpy-cyclam-Ni)~(4+)(3)and its related complexes 1 and 2were investigated by UV-vis and emission spectral methods.A drastic quenching offluorescence from the Ru(bpy)_3~(2+) subunit by the covalently attached quencher sub-unit Ni(cyclam)~(2+) was observed for complex 3,and the mechanism was discussed.