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 con...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.展开更多
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 ...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.展开更多
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, ...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.展开更多
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...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.展开更多
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, monoclin...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）.展开更多
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) an...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.展开更多
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,ag...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.展开更多
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 co...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.展开更多
CONSPECTUS:Luminescent nano/micro molecular crystals with well-defined shapes and morphologies have exhibited great potential for various photonic applications.The molecular orientation and packing greatly influence t...CONSPECTUS:Luminescent nano/micro molecular crystals with well-defined shapes and morphologies have exhibited great potential for various photonic applications.The molecular orientation and packing greatly influence the optical and electronic characters of the crystals.Noncovalent intermolecular interactions can not only determine the growth direction but also induce the formation of polymorphs,bringing more possibilities for the property optimization and functional applications.Besides,light-harvesting energy transfer(LHEnT)is a vital process in natural photosynthesis,the mimic of which provides a simple and practical means for solar energy conversion and the preparation of luminescent materials.With an energy donor and acceptor pair with suitable energy levels and similar molecular size and solubility,it is convenient to fabricate LHEnT molecular crystals with tunable optoelectronic and emission properties by dispersing acceptors into the donor lattices.展开更多
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 comp...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.展开更多
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 ana...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.展开更多
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 lay...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.展开更多
A novel method for synthesis of quinazoline through the hydrogen transfer/annulation reaction using 2-nitrobenzyl alcohol and benzylamine as starting materials is presented.The reaction is catalyzed by a ruthenium(II)...A novel method for synthesis of quinazoline through the hydrogen transfer/annulation reaction using 2-nitrobenzyl alcohol and benzylamine as starting materials is presented.The reaction is catalyzed by a ruthenium(II)complex bearing a N-heterocyclic carbene nitrogen phosphine(CNP)ligand.The pronouncedα-donating capacity of the carbene within the CNP ligand of the catalyst plays a crucial role in stabilizing the catalytically active species.Additionally,the hemilability of the nitrogen facilitates the creation of coordination vacancies,which are essential for the activation of reaction substrate molecules.The synergistic interplay between these two functionalities markedly enhances catalytic efficiency.This catalytic system shows the significant catalytic activity and selectivity,along with a broad substrate adaptability.All substrates yield the target product in good to excellent yields with the maximum yield reaching 95%.Control experiments have substantiated that benzaldehyde and phenylmethanimine may serve as intermediates in the reaction,thereby reinforcing the role of benzylamine as both a hydrogen donor and a nitrogen source in the process.展开更多
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（Bud...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.展开更多
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]-,...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.展开更多
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 incor...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.展开更多
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 rutheniu...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.展开更多
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）. T...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.展开更多
An air and moisture stable ruthenium（Ⅲ） formate complex[Ru（HCO2）Cl2]n has been synthesized and examined in the epoxidation of substituted styrenes.X-ray crystallographic data of this complex were determined and s...An air and moisture stable ruthenium（Ⅲ） formate complex[Ru（HCO2）Cl2]n has been synthesized and examined in the epoxidation of substituted styrenes.X-ray crystallographic data of this complex were determined and showed that the formate ligand coordinates to the ruthenium centers in a μ~2-η~2 fashion（syn,syn）.Its asymmetric unit contains one Ru（Ⅲ） ion together with the half of a formate ligand and one chloride anion,which are bridged between the metal centers,forming a 1-D chain coordination polymer.This electron deficient helical coordination polymer was employed in the epoxidation of parafluorostyrene,affording the epoxide product in 92%yield.Natural chirality of this coordination polymer is applicable in asymmetric epoxidation reactions.展开更多
Catalytic hydrogenation of SBS was performed for the first time in polyether molten salt with Ru/TPPTS complex as catalyst. Experimental results showed that the hydrogenation degree can be enhanced significantly by th...Catalytic hydrogenation of SBS was performed for the first time in polyether molten salt with Ru/TPPTS complex as catalyst. Experimental results showed that the hydrogenation degree can be enhanced significantly by the addition of triphenylphosphine (TPP). When the molar ratio of TPP, TPPTS and Ru is 2:5:1, 89% hydrogenation degree can be achieved after 12 h under reaction conditions of 5.0 MPa and 150°C. The ionic liquid containing catalyst can be reused three times without obvious changes in the catalytic selectivity and activity.展开更多
基金the National Natural Science Foundation of China(Nos.21271176,21472196,21521062,and 21501183)the Strategic Priority Research Program of the Chinese Academy of Sciences(No.XDB 12010400)for funding support
文摘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.
基金financially supported by the National Natural Science Foundation of China(No.20174031).
文摘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.
基金support of this work by the Doctor programe of Higher Education of China(No.98038410)Natural Science Foundation of Fujian(No.E0110001)Self-select program of Xiamen University.
文摘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.
基金National Natural Science Foundation of China(No.20774074 and 20674063)Specialized Research Fund for the Doctoral Program of Higher Education(No.20050736001).
文摘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.
文摘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）.
文摘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.
基金the financial support from the National Natural Science Foundation of China(U1810111,51872124 and21676116)Natural Science Foundation of Guangdong Province,China(2018B030311010)+1 种基金the Fundamental Research Funds for the Central Universities(21617431)Key Laboratory of Biomass Chemical Engineering of Ministry of Education,Zhejiang University(2018BCE002)
文摘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.
基金financially supported by the National Nature Science Foundation of China(21102004)Natural Science Foundation of Anhui Province(1708085MB44)the Natural Science Foundation of the Anhui Higher Education Institutions(KJ2016A845)
文摘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.
基金the National R&D Program of China(2023YFE0125200)National Natural Science Foundation of China(grants 22305251,22090021,and 21925112)for funding support。
文摘CONSPECTUS:Luminescent nano/micro molecular crystals with well-defined shapes and morphologies have exhibited great potential for various photonic applications.The molecular orientation and packing greatly influence the optical and electronic characters of the crystals.Noncovalent intermolecular interactions can not only determine the growth direction but also induce the formation of polymorphs,bringing more possibilities for the property optimization and functional applications.Besides,light-harvesting energy transfer(LHEnT)is a vital process in natural photosynthesis,the mimic of which provides a simple and practical means for solar energy conversion and the preparation of luminescent materials.With an energy donor and acceptor pair with suitable energy levels and similar molecular size and solubility,it is convenient to fabricate LHEnT molecular crystals with tunable optoelectronic and emission properties by dispersing acceptors into the donor lattices.
基金ACKNOWLEDGMENTS This work was supported by the National Natural Science Foundation of China （No.20903027）, the Natural Science Foundation of Guangdong Province of China （No.9452402301001941）, the Medical Scientific Research Foundation of Guangdong Province of China （No.B2013297）, and the University Student in Guangdong Province Innovation and Entrepreneurship Train ing Program （No.1057112019 and No.1057112013）.
文摘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.
文摘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.
基金supported by the National Natural Science Foundation of China(52103223)the Natural Science Basic Research Program of Shaanxi(2023-JC-YB-413)+2 种基金the Natural Science Foundation of Heilongjiang Province of China(YQ2023E027)the Fundamental Research Funds for the Central Universities(3072024XX2616)the Key Laboratory of Functional Molecular Solids,Ministry of Education(FMS20230010).
文摘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.
文摘A novel method for synthesis of quinazoline through the hydrogen transfer/annulation reaction using 2-nitrobenzyl alcohol and benzylamine as starting materials is presented.The reaction is catalyzed by a ruthenium(II)complex bearing a N-heterocyclic carbene nitrogen phosphine(CNP)ligand.The pronouncedα-donating capacity of the carbene within the CNP ligand of the catalyst plays a crucial role in stabilizing the catalytically active species.Additionally,the hemilability of the nitrogen facilitates the creation of coordination vacancies,which are essential for the activation of reaction substrate molecules.The synergistic interplay between these two functionalities markedly enhances catalytic efficiency.This catalytic system shows the significant catalytic activity and selectivity,along with a broad substrate adaptability.All substrates yield the target product in good to excellent yields with the maximum yield reaching 95%.Control experiments have substantiated that benzaldehyde and phenylmethanimine may serve as intermediates in the reaction,thereby reinforcing the role of benzylamine as both a hydrogen donor and a nitrogen source in the process.
文摘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.
基金Supported by the National Natural Science Foundation of China(No.20872108)
文摘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.
基金This work was supported by the National Natural Science Foundation of China No. 20074036.
文摘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.
基金This work was supported by the Natural Sciences and Engineering Research Council of Canada References.
文摘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.
文摘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.
文摘An air and moisture stable ruthenium（Ⅲ） formate complex[Ru（HCO2）Cl2]n has been synthesized and examined in the epoxidation of substituted styrenes.X-ray crystallographic data of this complex were determined and showed that the formate ligand coordinates to the ruthenium centers in a μ~2-η~2 fashion（syn,syn）.Its asymmetric unit contains one Ru（Ⅲ） ion together with the half of a formate ligand and one chloride anion,which are bridged between the metal centers,forming a 1-D chain coordination polymer.This electron deficient helical coordination polymer was employed in the epoxidation of parafluorostyrene,affording the epoxide product in 92%yield.Natural chirality of this coordination polymer is applicable in asymmetric epoxidation reactions.
基金This work was financially supported by the National Natural Science Foundation of China(NO. 204760l5).
文摘Catalytic hydrogenation of SBS was performed for the first time in polyether molten salt with Ru/TPPTS complex as catalyst. Experimental results showed that the hydrogenation degree can be enhanced significantly by the addition of triphenylphosphine (TPP). When the molar ratio of TPP, TPPTS and Ru is 2:5:1, 89% hydrogenation degree can be achieved after 12 h under reaction conditions of 5.0 MPa and 150°C. The ionic liquid containing catalyst can be reused three times without obvious changes in the catalytic selectivity and activity.
