Synthesis and Photochemical Properties of a New Substituted Phenol Covalently Linked to Ruthenium （Ⅱ） Tris-bipyridine Containing Four Ester Groups as Sensitizer

As photosensitizer for solar cell, a new ruthenium (Ⅱ) complex with four ester groups had been synthesized, in which a phenol substituted by {[(2-hydroxy-5-tert-butylbenzyl)(pyridyl-2-methyl)amino]methyl} is covalently linked to ruthenium (Ⅱ) tris-bipyridine. The structures of the new compounds were confirmed by NMR and ESI-MS spectra. The electrochemical and photochemical properties were also studied.     

New Type High Efficient Quasi-Solid-State Ionic Liquid Electrolyte for Dye-Sensitized Solar Cells

For the fist time the preparation of a mostly solid-state high efficiem electro-conductive material comprising 1-methyl-3-propylimidazolium iodide （MPII）, benzimidazole （BI）, iodine and lithium iodide was reported. In this electrolyte, BI acts as not only additives but also gelators. With its significant electrochemical properties, an overall efficiency of 3.07% was achieved under AM 1.5 （100 mW/cm^2）.     

Guanidinium Iodides-based Ionic Liquids： Synthesis and Application for Dye-sensitized Solar Cells（DSSCs）

A series of guanidinium ionic liquids(GILs) was designed, synthesized, and used as electrolytes for dye-sensitized solar celIs(DSSCs). The effect of electrolytes containing GILs on the photovoltaic performance of DSSCs was investigated. It is demonstrated that these GILs are promising for being used as electrolytes for DSSCs and a conversion efficiency of 4.1% can be obtained under AM 1.5 sun light irradiation.     

Tris（2,2＇-bipyridyl） Ruthenium（Ⅱ） Doped Silica Film Modified Indium Tin Oxide Electrode and Its Electrochemiluminescent Properties

An approach was reported to synthesize silica hybridized ruthenium bipyridyl complex through amidation reaction by covalent attachment of bis（bipyridyl）-4,4＇-dicarboxy-2,2＇-bipyridyl-ruthenium to （3-aminopropyl）-triethoxysilane. The hybrid complex then was gelatinized through acid catalytic hydrolysis method and a sol-gel modified indium tin oxide electrode was prepared via spin coating technique. As prepared indium tin oxide electrode possesses good stability therein with excellent electrochemiluminescence behavior.     

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.     

Synthesis and Crystal Structure of a Ruthenium（Ⅱ） Compound of Dinitrogen

The title compound [Ru（bph）（PPh3）2（N2）]·（PF6）·1.5CH2Cl2 （bph = N-（benzoyl）- N＇-（picolinylidene）-hydrazine） has been prepared and characterized by X-ray diffraction analysis. It crystallizes in the monoclinic system, space group P21/n with a = 13.5201（6）, b = 15.5078（6）, c = 25.0656（13） A, β= 100.257（3）°, C50.50H43Cl3F6N5OP3Ru, Mr= 1150.23, V= 5171.4（4） A3, Z = 4, F（000） = 2332, Dc = 1.477 g/cm^3 and ,μ（MoKa） = 0.615 mm^-1. The structure was refined to R = 0.0524 and wR = 0.1398 for 8060 observed reflections （I 〉 2σ（I））. The Ru-N2 and N-N bond distances are 1.919（4） and 1.133（5）A, respectively.     

Synthesis of a Polymer—bound Sensitizer and its Application in the Photoisomeriz

A polymer-bound photosensitizer was synthesized by the reaetion of Merritield resin with 9-anthraeenemethanol in the presence of potassium hydride.The photoisomerization of trans-vitamin D3 to cis-vitamin D3 was earried out with this polymer-bound photosensitizer in ethanol and toluene solutions.The experiment results demonstrate that this solid photosensitizer is efficient for the photoismerization and easy for separation from the reaetion mixtures.     

DNA Binding Properties and Cytotoxic Activities of Two Trinuclear Ruthenium（Ⅱ） Polypyridyl Complexes

The interactions between two trinuclear Ru（II） complexes and calf thymus DNA（CT DNA） were studied via absorption spectroscopy, reverse salt titrations, binding stoichiometry, DNA melting experiments, as well as viscosity measurement. The results indicate that complexes 1 and 2 bind to DNA via the interaction of the planar π-delocalized system of the complexes with intrinsic binding constants of 4.18 × 10^5 and 3.85 × 10^6 L/tool, respectively, and non-electrostatic binding free energy makes a predominant contribution to the binding free energy. The in vitro cytotoxic activity of complexes 1 and 2 was evaluated by the MTT[3-（4,5-dimethylthiazol-2-yl）-2,5-diphenyl- 2H-tetrazolium bromide] method. Complex I shows higher anticancer potency than complex 2 against four tumor cell lines. Further mechanism study indicates that complexes 1 and 2 can cause cell cycle arrest in the G2/M phase.     

Preparation and Characterization of A New Dinuclear Ruthenium Complex with BDPX Ligand and Its Catalytic Hydrogenation Reactions for Cinnamaldehyde

Introduction Recently, dinuclear Ru complexes containing chelating bidentate phosphines (either chiral or non-chiral) have attracted more and more attention owing to their effective ability for catalytic hydrogenation of olefins and carbonyl groups under mild conditions. A great number of dinuclear Ru complexes with bidentate phosphines have been obtained.1-10 In 1985 Ikariya et al.1 prepared a chiral binuclear ruthenium complex [Ru2Cl4(BINAP)2]NEt3 by the reaction of (S)-BINAP with [R…     

Synthesis of N,N,N-4,4＂-Di-（4-methylphenyl）-2,2＇：6＇,2＂- terpyridine-N,N,N-tris（isothiocyanato） Ruthenium（Ⅱ） and Application to Colorimetric Hg^2＋ Sensor

A terpyridine derivative DPTP [di-（4-methylphenyl）-2,2＇：6＇,2＂-terpyridine] was conveniently synthesized from 2-bromopyridine via halogen-dance reaction, Kharash coupling and Stille coupling reaction. Then its corresponding ruthenium complex Ru-DPTP [N,N,N-4,4＇＇-di-（4-methy,phenyl）-2,2＇：6＇,2＂-terpyridine-N,N,N-tris（is,-thi,cyanat,）- ruthenium（H） ammonium] was obtained and fully characterized by IR, UV-Vis, ESI MS and elemental analysis. The MLCT absorption band of Ru-DPTP was blue-shifted from 570 to 500 nm upon addition of Hg^2＋. Among a series of surveyed metal ions, the complex showed a unique recognition to Hg^2＋, indicating that it can be used as a selective colorimetric sensor for Hg^2＋.     

Cyclometalated Ruthenium(II) Complexes Featuring Tridentate Click‐Derived Ligands for Dye‐Sensitized Solar Cell Applications

A series of heteroleptic bis(tridentate) Ru^II complexes featuring N^C^N‐cyclometalating ligands is presented. The 1,2,3‐triazole‐containing tridentate ligands are readily functionalized with hydrophobic side chains by means of click chemistry and the corresponding cyclometalated Ru^II complexes are easily synthesized. The performance of these thiocyanate‐free complexes in a dye‐sensitized solar cell was tested and a power conversion efficiency (PCE) of up to 4.0 % (J_sc=8.1 mA cm^?2, V_oc=0.66 V, FF=0.70) was achieved, while the black dye ((NBu₄)₃[Ru(Htctpy)(NCS)₃]; Htctpy=2,2′:6′,2′′‐terpyridine‐4′‐carboxylic acid‐4,4′′‐dicarboxylate) showed 5.2 % (J_sc=10.7 mA cm^?2, V_oc=0.69 V, FF=0.69) under comparable conditions. When co‐adsorbed with chenodeoxycholic acid, the PCE of the best cyclometalated dye could be improved to 4.5 % (J_sc=9.4 mA cm^?2, V_oc=0.65 V, FF=0.70). The PCEs correlate well with the light‐harvesting capabilities of the dyes, while a comparable incident photon‐to‐current efficiency was achieved with the cyclometalated dye and the black dye. Regeneration appeared to be efficient in the parent dye, despite the high energy of the highest occupied molecular orbital. The device performance was investigated in more detail by electrochemical impedance spectroscopy. Ultimately, a promising Ru^II sensitizer platform is presented that features a highly functionalizable “click”‐derived cyclometalating ligand.     

Synthesis and Characterization of Heteroleptic Ru(II) Complexes Based on 4,4′‐Bis((E)‐styryl)‐2,2′‐bipyridine as Ancillary Ligand and Application for Dye‐Sensitized Solar Cells

Heteroleptic Ru(II) complexes were designed based on 4,4′‐bis((E)‐styryl)‐2,2′‐bipyridine (bsbpy) as an ancillary ligand for dye‐sensitized solar cells (DSSCs), and those Ru(II) sensitizers, [Ru(L)(bsbpy)(NCS)₂][TBA] (TBA; tetrabutylammonium), were synthesized according to a typical one‐pot reaction of [RuCl₂(p‐cymene)]₂ with the corresponding anchoring ligands (where L = 4,4′‐dicarboxy‐2,2′‐bipyridine (dcbpy), 4,4′‐bis((E)‐carboxyvinyl)‐2,2′‐bipyridine (dcvbpy), 4,7‐dicarboxy‐1,10‐phenanthroline (dcphen), or 4,7‐bis((E)‐carboxyvinyl)‐1,10‐phenanthroline (dcvphen)). The new Ru(II) dyes, [Ru(L)(bsbpy)(NCS)₂][TBA] that incorporated vinyl spacer(s) into ancillary and/or anchoring ligand displayed red‐shifted bands over the overall UV/VIS region relative to the absorption spectra of N719 . A combination of bsbpy ancillary and dcphen anchoring ligand showed the best result for the overall power conversion efficiency (η); i.e., a DSSC fabricated with [Ru(dcphen)(bsbpy)(NCS)₂][TBA] exhibited a power conversion efficiency (η) of 2.98% (compare to N719 , 4.82%).     

Application of the Organic Photosensitizers Bearing Two Carboxylic Acid Groups to Dye‐Sensitized Solar Cells

Three electron donor‐?? bridge‐electron acceptor (D‐π‐A) organic dyes bearing two carboxylic acid groups were applied to dye‐sensitized solar cells (DSSC) as sensitizers, in which one triphenylamine or modified triphenylamine and two rhodanine‐3‐acetic acid fragments act as D and A, respectively. It was found that the introduction of t‐butyl or methoxy group in the triphenylamine subunit could lead to more efficient photoinduced intramolecular charge transfer, thus improving the overall photoelectric conversion efficiency of the resultant DSSC. Under global AM 1.5 solar irradiation (73 mW·cm^?2), the dye molecule based on methoxy‐substituted triphenylamine achieved the best photovoltaic performance: a short circuit photocurrent density (J_sc) of 12.63 mA·cm^?2, an open circuit voltage (V_oc) of 0.55 V, a fill factor (FF) of 0.62, corresponding to an overall efficiency (η) of 5.9%.     

A Promising Candidate with D‐A‐A‐A Architecture as an Efficient Sensitizer for Dye‐Sensitized Solar Cells

A series of metal‐free organic dyes with electron‐rich (D) and electron‐deficient units (A) as π linkers have been studied theoretically by means of density functional theory (DFT) and time‐dependent DFT calculations to explore the effects of π spacers on the optical and electronic properties of triphenylamine dyes. The results show that Dye 1 with a structure of D‐A‐A‐A is superior to the typical C218 dye in various key aspects, including the maximum absorption (λ_max=511 nm), the charge‐transfer characteristics (D/Δq/t is 5.49 Å/0.818 e^?/4.41 Å), the driving force for charge‐carrier injection (ΔG_inject=1.35 eV)/dye regeneration (ΔG_regen=0.27 eV), and the lifetime of the first excited state (τ=3.1 ns). It is thus proposed to be a promising candidate in dye‐sensitized solar cell applications.     

Molecular Dyads Comprising Metalloporphyrin and Alkynylplatinum(II) Polypyridine Terminal Groups for Use as a Sensitizer in Dye‐Sensitized Solar Cells

A new class of molecular dyads comprising metalloporphyrin‐linked alkynylplatinum(II) polypyridine complexes with carboxylic acids as anchoring groups has been designed and synthesized. These complexes can sensitize nanocrystalline TiO₂ in dye‐sensitized solar cell (DSSC) studies. The photophysical, electrochemical, and luminescence properties of the complexes were studied and their excited‐state properties were investigated by nanosecond transient absorption spectroscopy, with the charge‐separated [Por^.??{(C?C)Pt(tBu₃tpy)}^.+] state observed upon excitation. Excited‐state redox potentials were determined; the electrochemical data supports the capability of the complexes to inject an electron into the conduction band of TiO₂. The complexes sensitize nanocrystalline TiO₂ and exhibited photovoltaic properties, as characterized by current–voltage measurements under illumination of air mass 1.5 G sunlight (100 mWcm^?2). A DSSC based on one of the complexes showed a short‐circuit photocurrent of 10.1 mAcm^?2, an open‐circuit voltage of 0.64 V, and a fill factor of 0.52, giving an overall power conversion efficiency of 3.4 %.