Oxidation of Alcohols Catalyzed by Ruthenium Complexes with Iodosylbenzene as Oxidant

Five ruthenium complexes such as Phen-Ru-Phen, Phen-Ru-Bipy, Phen-Ru-Quin, Quin-Ru-Quin and Bipy-Ru-Quin (where Phen=1, 10-phenanthroline, Quin=8-hydroxyquinoline, Bipy=2, 2′-bipyridine) were synthesized and used as catalysts for the oxidation of benzylic and primary aliphatic alcohols with iodosylbenzene as oxidant. The oxidations were carried out at room temperature, affording the corresponding aldehydes and ketones with high selectivity.

New Ruthenium Complexes of Fullerene C60&C70

The new complexes [Ru(NO)(PPh3)]2(h2-Cm)(m=60 1 or 70 2) have been prepared by heating a solution of C60(or C70) with [Ru(NO)2(PPh3)2] in toluene. They have been characterized by elemental analysis, IR, UV/VIS, XPS, 13C and 31P NMR spectroscopy. The photovaltaic effect for the new compounds has been studied.

Highly efficient oxidation of alcohols using Oxone~ as oxidant catalyzed by ruthenium complex under mild reaction conditions

Aromatic and alkyl alcohols were oxidized to the corresponding aldehydes or ketones at room temperature with high conversion and selectivity using Oxone （2KHSOs-KHSO4.K2SO4） as oxidant catalyzed by ruthenium complex Quin-Ru-Quin （where Quin = 8-hydroxyquinoline）. The reaction time is very short and the preparation of complex is simple.

Synthesis and Structural Characterization of a Ruthenium Complex:trans-RuCl_2(COD)Py_2

A new ruthenium complex trans-RuCl2（COD）Py2 has been synthesized and characterized by elemental analysis, IR, IH NMR and single-crystal X-ray diffraction. Crystal data： trans- RuCl2（COD）Py2, Mr = 438.35, monoclinic, space group P21/c, a = 8.9116（9）, b = 14.6175（15）, c = 13.7582（14）A, β = 101.994（1）°, V= 1753.1（3）A^3, Z= 4, Dc= 1.661 g/cm^3, F（000）= 888,μ = 1.199 mm^-1, R = 0.0376 and wR = 0.0789 for 2492 observed reflections with I 〉 2σ（I）.

Quantitative Structure Anti-Cancer Activity Relationship (QSAR) of a Series of Ruthenium Complex Azopyridine by the Density Functional Theory (DFT) Method

A series of ruthenium azopyridine complexes have recently been investigated due to their potential cytotoxic activities against renal cancer (A498), lung cancer (H226), ovarian cancer (IGROV), breast cancer (MCF-7) and colon cancer (WIDR). Thus, in order to predict the cytotoxic potentials of these compounds, quantitative structure-activity relationship studies were carried out using the methods of quantum chemistry. Five Quantitative Structure Activity Relationship (QSAR) models were obtained from the determined quantum descriptors and the different activities. The models present the following statistical indicators: regression correlation coefficient R2 = 0.986 - 0.905, standard deviation S = 0.516 - 0.153, Fischer test F = 106.718 - 14.220, correlation coefficient of cross-validation = 0.985- 0.895 and = 0.010 - 0.001. The statistical characteristics of the established QSAR models satisfy the acceptance and external validation criteria, thereby accrediting their good performance. The models developed show that the variation of the free enthalpy of reaction , the dipole moment μ and the charge of the ligand in the complex Ql, are the explanatory and predictive quantum descriptors correlated with the values of the anti-cancer activity of the studied complexes. Moreover, the charge of the ligand is the priority descriptor for the prediction of the cytotoxicity of the compounds studied. Furthermore, QSAR models developed are statistically significant and predictive, and could be used for the design and synthesis of new anti-cancer molecules.

Transformations of biomass-based levulinate ester into γ-valerolactone and pyrrolidones using carbon nanotubes-grafted N-heterocyclic carbene ruthenium complexes

As a renewable biomass-based compound with wide applications in food additives,fine chemical synthesis and fuels,γ-valerolactone(GVL)has attached much attention.While,pyrrolidones are widely used in pharmaceutical,agrochemical,material industrial and other chemical production.In this research,we demonstrated transformations of biomass-based ethyl levulinate(EL)into GVL and pyrrolidones by using heterogeneous catalysts(CNT-Ru-1)with N-heterocyclic carbene ruthenium(NHC-Ru)complex grafted on multi-walled carbon nanotube(CNT).The Ru catalyst showed high efficiency on EL hydrogenation to GVL with both EL conversion and GVL yield exceeding 99%.Moreover,the Ru catalyst readily promoted reductive amination of EL in the presence of various amines for pyrrolidone synthesis.Finally,the Ru catalyst was also applicable to hydrogenation of various carbonyl compounds for the synthesis of the corresponding alcohols with excellent catalytic performance.The research provides insight for heterogenizing the homogeneous noble metal-based catalysts with high catalytic active for biomass-based transformations.

Half-sandwich Ruthenium Complexes with Naphthalene-based Schiff Base Ligands:Syntheses,Characterization and Catalytic Activities for the Reduction of Nitroarenes

Three half-sandwich ruthenium（II） p-cymene complexes containing naphthalenebased Schiff base ligands [Ru（p-cymene）LCl]（2 a～2 c） have been synthesized and characterized. Both Schiff-base ligands and ruthenium complexes were fully characterized by ^1H and ^13C NMR spectra, mass spectrometry and infrared spectrometry. The molecular structure of ruthenium complex 2 b was confirmed by single-crystal X-ray diffraction methods. For the complex： C（24H23ClN2ORu, Mr = 524.02, monoclinic, space group P21/c, a = 12.3888（4）, b = 17.3296（6）, c = 20.7744（7）A°, β = 92.8000（10）°, V = 4454.8（3） A°^3, Z = 8, Dc = 1.563 g/cm^3, μ = 0.936 mm^-1, F（000） = 2128, S = 1.154, the final R = 0.0309 and w R = 0.0703. Moreover, these ruthenium complexes are active catalysts for the hydrogenation of nitroarenes to aromatic anilines in the presence of sodium tetrahydroborate（NaBH4） reducing agent.

Interfacial engineering by multifunctional ruthenium complex for CsPbI_(2)Br perovskite solar cells with a fill factor over 0.82

The interface is of paramount importance in heterostructures,as it can be considered as a device in accordance with Kroemer’s dictum.In perovskite solar cells(PSCs),optimizing the interface between the perovskite layer and the hole transport layer is known to be an effective method for enhancing PSC device performance.Herein,a metal ruthenium complex coded as C101 is introduced to the perovskite(CsPbI_(2)Br)/hole transport layer(PTAA)interface as a“charge driven motor”to selectively extract holes from CsPbI_(2)Br and then transfer them to PTAA,minimizing the voltage loss in PSCs.More significantly,the introduction of C101 layer effectively passivates the surface of CsPbI_(2)Br film and reduces the defect density of CsPbI_(2)Br film due to the covalent bond between the CsPbI_(2)Br and the–C=O group in C101.The photovoltaic performance of CsPbI_(2)Br PSCs is enhanced by 23.60%upon the introduction of C101 interfacial layer,with the champion CsPbI_(2)Br PSC exhibiting a power conversion efficiency of 14.96%in a reverse scan,a short-circuit current of 15.84 mA·cm^(−2),an open-circuit voltage of 1.15 V,and a fill factor of 82.03%.Additionally,the introduction of C101 simultaneously enhances the humidity tolerance of CsPbI_(2)Br PSCs.

Electro‑copolymerized film of ruthenium catalyst and redox mediator for electrocatalytic water oxidation

Electro-copolymerized film containing ruthenium complexes as electron-transfer(or redox)mediators and water-oxidation catalysts by an oxidative copolymerization method is presented.The addition of the redox mediator significantly improved the electrocatalytic water-oxidation activity and reduced the overpotential to 220 mV.The prepared electrode showed a water-oxidation catalytic rate constant kobs of 31.7 s^(-1)and an initial turnover frequency of 1.01 s^(-1)in 1000 s by potential electrolysis at 1.7 V applied bias vs NHE(normal hydrogen electrode).The kinetic isotope effect study suggests that the catalytic water oxidation reaction on the electrode surface occurs via a bimolecular coupling mechanism.

Electropolymerized films of redox-active ruthenium complexes for multistate near-infrared electrochromism,ion sensing,and information storage

This paper summarizes our recent progress on the preparations and applications of electropolymerized thin films of redox-active ruthenium complexes.Thin films of vinyl-functionalized diruthenium or ruthenium-amine conjugated complexes are prepared by reductive electropolymerization.The resulting films are useful for multistate near-infrared electrochromism,ion sensing,and mimicking flip-flop and flip-flap-flop logic gates.The oxidative electropolymerization of diruthenium complexes with two distal triarylamine units affords electropolymers with an alternating diruthenium and tetraphenylbenzidine structural unit.The applications of the resulting films in multistate near-infrared electrochromism and resistive memory are discussed.

Electronic Structures, DNA-binding, SAR, and Spectral Properties of Ruthenium Methylimidazole Complexes [Ru（MeIm）4L]^2＋（L=iip,tip,2ntz）

Theoretical studies on the electronic and geometric structures, the trend in DNA-binding affinities as well as the the structure-activity relationship （SAR） of a series of water-soluble Ru（II） methylimidazole complexes, i.e. [Ru（Mehn）4iip]^2＋ （1） （MeIm=l-methylimidazole, iip=2-（1H-imidazo-4-group）-lH-imidazo[n,5-f][1,10]phenanthroline）, [Ru（MeIm）4tip]^2＋ （2） （tip=2-（thiophene-2-group）-lH-imidazo[4,5-f] [i,10]phenanthroline）, and [Ru（Melm）42ntz]^2＋ （3） （2ntz=2-（2-nitro-l,3-thiazole-5-group）-lH-imidazo[4,5-f][1,10]phenanthroline）, were car- ried out using the density functional theory （DFT）. The electronic structures of these Ru（II） complexes were analyzed on the basis of their geometric structures optimized in aqueous solution, and the trend in the DNA-binding constants （Kb） was reasonably explained. The results show that the replacement of imidazole ligand by thiophene ligand can effectively improve the DNA-binding affinity of the complex. Meanwhile, it was found that introduc- ing the stronger electronegative N atom and NO2 group on terminal loop of intercalative ligand can obviously reduce the complex＇s LUMO and HOMO-LUMO gap energies. Based on these findings, the designed complex [Ru（MeIm）42ntz]^2＋ （3） can be expected to have the greatest Kb value in complexes 1-3. In addition, the structure-activity relationships and antitumor mechanism were also carefully discussed, and the antimetastatic activity of the designed complex 3 was predicted. Finally, the electronic absorption spectra of this series of complexes in aqueous solution were calculated, simulated and assigned using DFT/TDDFT methods as well as conductor-like polarizable continuum model （CPCM）, and were in good agreement with the experimental results.

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

A new anionic dinuclear ruthenium complex bearing 1, 2-his(diphenylphosphinomethyl)benzene (BDPX) [NH2Et2][{RuCl (BDPX)}2(μ-Cl)3] (1) was synthesized and its structure was determined by an X-ray crystallo-graphic analysis. This result indicated that complex 1 consisted of an anion dinuclear BDPX-Ru and a cationic di-ethylammonium. The crystal belonged to monoclinic system, C2/c space group with a=3.3552(7) nm, b= 1.8448(4) nm, c=2.4265(5) nm, β= 101.89(3)° and Z=8. The catalytic hydrogenation activities and selectivities of complex 1 for cinnamaldehyde were investigated.

Cyclometalated Ruthenium Complexes of 1,2,3-Triazole-containing Ligands： Synthesis, Structural Studies, and Electronic Properties

Six bis-tridentate and two tris-bidentate cyclometalated ruthenium complexes with a 1,2,3-triazole-containing ligand have been prepared and characterized. Single-crystal X-ray analyses of complexes [（MeOptpy）Ru（Budtab）]-（PF6） and [（Mebip）Ru（Budtab）]（PF6） are presented, where MeOptpy is 4′-p-methoxyphenyl-2,2′：6′,2＂-terpyridine, Budtab is the 2-deprotonated form of 1,3-di（N-n-butyl-l,2,3-triazol-4-yl）benzene, and Mebip is bis（N-methyl-ben-zimidazolyl）pyridine. The electronic properties of these complexes are probed by spectroscopic and electrochemical analyses. Time-dependent density functional theory calculations have been performed to assist the assignment of the absorption spectra.

Synthesis and Catalytic Activity of a Two-core Ruthenium Carbene Complex: a Unique Catalyst for Ring Closing Metathesis Reaction

The reaction of a ruthenium carbide complex RuCl2（C：）（PCy3）2 with [H（Et2O）x]＋[BF4]- at a molar ratio of 1：2 produced a two-core ruthenium carbene complex, {[RuCl（=CHPCy3）（PCy3）]2（μ-Cl）3}＋·[BF4]-, in the form of a yellow-green crystalline solid in a yield of 94%. This two-core ruthenium complex is a selective catalyst for ring closing metathesis of unsubstituted terminal dienes. More importantly, no isomerized byproduct was observed for N-substrates when the two-core ruthenium complex was used as the catalyst at an elevated temperature（137 °C）, indicating that the complex is a chemo-selective catalyst for ring closing metathesis reactions.

Synthesis and Characterization of Ferroceneterminated Ruthenium Phenylacetylide Complexes with Alligator Clips

Ferrocene-terminated trans-Ru(dppm)2 (dppm=Ph2PCH2PPh2)-containing molecular wires with alligator clips were prepared. They are suitable for self-assembly on gold electrode to investigate the influence of metal incorporation on the electron transportation property of the molecular wires.

Near infrared electrochromicvariable optical attenuator based on ruthenium complexand polycrystalline tungsten oxide

A near infrared (NIR) electrochromic attenu-ator based on a dinuclear ruthenium complex and polycrys-talline tungsten oxide was fabricated and characterized. The results show that the use of the NIR-absorbing ruthenium complex as a counter electrode material can improve the device performance. By replacing the visible electrochromic ferrocene with the NIR-absorbing ruthenium complex, the optical attenuation at 1550 nm was enhanced from 19.1 to 30.0 dB and color efficiency also increased from 29.2 to 121.2 cm2/C.

A Ternary Ruthenium（II） 2,2′ ：6′,2″-Terpyridine Complex Having Intramolecular Tr-Tr Stacking Interaction with Ancillary Benzyl Groups of the Mixed Ligand

A new ruthenium（II） complex with two different types oftridentate ligands was synthesized, 2,2′：6′,2″-terpyridine （tpy） and 2,6-Bis（（N-benzyl）aminomethyl）pyridine （bbap）： [Ru（tpy）（bbap）]2＋ （1）. This compound was designed to form intramolecular π-π stacking interaction between tpy and substituted benzyl groups of bbap. The single-crystal X-ray diffraction analysis revealed that 1 crystallized with orthorhombic space group Aea2 and the ruthenium center has a distorted octahedral coordination geometry with fully chelated tpy and bbap ligands. Simultaneously, in the crystal structure of 1, the central part of ligating tpy was stacked and sandwiched with a pair of capped benzyl substituent groups of bbap, the nearest atomic distance being N...C = 3.28 A.

环2-(4-三氟甲基)苯基吡啶钌亚硝酰配合物的合成与光敏NO释放

由环金属钌配合物[Ru(bpy)_(2)(4-CF3ppy)]PF_(6)(bpy=2,2′-二联吡啶,4-CF_(3)Hppy=2-(4-三氟甲基)苯基吡啶))合成了一个新的钌亚硝酰配合物[Ru(bpy)(4-CF_(3)ppy)(CH_(3)CN)NO](PF_(6))_(2)(配合物1),并通过NMR、MS和IR表征确认其结构.结果表明:配合物1中属于NO^(+)特征伸缩振动峰出现在1911 cm^(-1)处,并在电化学中呈现显著的Ru^(Ⅱ)NO+→Ru^(Ⅱ)NO·和Ru^(Ⅱ)NO·→Ru^(Ⅱ)NO-两步连续还原过程,表明其中存在Ru^(Ⅱ)-NO+.此外,光照下吸收光谱的显著变化显示了该配合物光敏NO释放的可能性,并由EPR光谱确认.通过Griess试剂测定发现:因─CF_(3)引入,配合物1的光敏NO释放量明显高于[Ru(bpy)(ppy)(CH_(3)CN)NO]^(2+)和[Ru(bpy)(4-OCH_(3)ppy)(CH3CN)NO]^(2+),这一结果与模拟计算的Ru核与NO^(+)的结合能大小一致.故吸电子基团的引入更有利于Ru^(Ⅱ)-NO^(+)的NO光敏释放,配合物1可作为光敏NO供体.

基于荧光猝灭原理的比率式光纤溶解氧传感器研究

溶解氧浓度的准确测定在医疗应用、海洋监测、工农业生产等领域中,起到至关重要的作用。本篇论文提出了一种比率式光纤溶解氧传感器,以四乙氧基硅烷(TEOS)和正辛基三乙氧基硅烷(Octyl-triEOS)为前驱体的有机改性硅酸盐(ORMOSILs)作为载体基质,选用三(4,7-联苯-1,10-邻菲啰啉)二氯化钌(Ru(dpp)_(3)^(2+))为氧敏感染料,选用7-氨基-4-(三氟甲基)香豆素(AFC)为参比染料。吸收光谱表明,氧敏感染料和参比染料可以被中心波长为405nm的光源激发。发射光谱表明,氧敏感染料和参考染料的发射波长没有光谱重叠,因此可以使用比率法测量溶解氧浓度。通过溶胶-凝胶工艺制备的ORMOSILs将氧敏感染料和参比染料固定在塑料光纤端部,从而形成复合氧敏感薄膜,对传感膜的厚度和疏水性进行了表征,传感膜的厚度为569μm,水接触角为81°。将该传感器在水溶液中进行了测试,在光源激发下,氧敏感染料和参考染料在605和490nm处有明显的发射峰,随着溶解氧浓度的增加,氧敏感染料的荧光强度降低,而参比染料的荧光强度稳定在某一数值,通过测量氧敏感染料与参比染料的比率,达到检测氧浓度的目的。采用Stern-Volmer方程对溶解氧浓度和荧光强度比进行线性拟合,该传感器在0~20.05mg·L^(-1)溶解氧范围内,Stern-Volmer拟合度可达98.22%,灵敏度可达0.4334/[O_(2)],从饱和氮溶液到饱和氧溶液传感器的响应时间为12s,从饱和氧溶液到饱和氮溶液传感器的恢复时间为144s,引入非对称因子ASY表明传感时间的不对称性。对传感器的光稳定性和重复性进行了测试,比率式光纤传感器可以克服光源波动,相对单荧光强度传感有更强的稳定性。

手性钌(Ⅱ)配合物与DNA作用性质的计算研究

理论考察了手性钌(Ⅱ)配合物1和2与DNA作用性质.首先,构建了手性钌(Ⅱ)配合物1、2与DNA对接模型,并对对接模型进行了优化,通过计算得到的手性钌(Ⅱ)配合物1、2与DNA的结合能,解释了手性钌(Ⅱ)配合物1、2与DNA键合力大小次序,即K_(b)(Λ-1)<K_(b)(Δ-1)<K_(b)(Λ-2)<K_(b)(Δ-2).另外,通过计算得到的电子转移活化能及自然电荷解释了手性钌(Ⅱ)配合物1和2裂解DNA的效率次序,即K_(b)(Λ-1)φ(Δ-2)>φ(Λ-1)>φ(Δ-1).最后,通过计算得到的对接模型的分子轨道分析了光裂解DNA的原因.