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1.
A series of metal‐free compounds, ie, planar triprotonated triazine, triazineH3Cl(PF6)2 ( 1 ), planar triprotonated triazineH3Br(PF6)2 ( 2 ), and nonplanar monoprotonated triazineHPF6 ( 3 ), were prepared. Abbreviations used are triazine = tri‐2‐pyridyltriazine. Ruthenium complexes [RuCl(bpy)(L)](PF6), [RuCl(bpy)(L)](PF6)2, and [Ru(L)2](PF6)2 were also prepared, where bpy is 2,2′‐bipyridine and L's are triazine ( 4 ) and monoprotonated triazine ( 5 ), respectively. Ruthenium complexes [Ru(triazine)2](PF6)2 ( 6 ) were also prepared and crystallized. The X‐ray crystal structures of the 3 compounds 1 , 2 , and 3 and the complex 6 were determined. They were also characterized by electrospray ionization mass spectrometry, UV‐vis spectroscopy, and density functional theory calculations.  相似文献   

2.
Three ruthenium(II) polypyridyl complexes, [Ru(phen)2(mip)](ClO4)2 (1) (phen =1,10-Phenanthroline), [Ru(bpy)2(mip)](ClO4)2 (2) (bpy = 2,2’bipyridyl) and [Ru(dmb)2(mip)](ClO4)2 (3) (dmb = 4, 4′-dimethyl 2, 2′-bipyridine), were synthesized with an intercalative ligand mip (2-morpholino-1H-imidazo[4,5-f][1, 10]phenanthroline) and characterized by 1H, 13C–NMR, IR, UV-vis, mass spectra and elemental analysis. pH effect, ion selectivity (cations, anions) and solvent sensitivity of complexes were studied. The interaction of these complexes with DNA was performed using absorption, emission spectroscopy and viscosity measurements. The experimental results indicated that the two complexes interacted with calf thymus DNA (CT-DNA) by intercalative mode. BSA (Bovine Serum Albumin) protein binding of these complexes was studied by UV-visible and fluorescence techniques. The binding capacity of these complexes was explained theoretically by molecular docking method.  相似文献   

3.
Copper(I) complexes of the formula [Cu(L)(PPh3)2]X (1–4) (X = Cl(1), ClO4(2), BF4(3) and PF6(4)) [where L = N-(2-{[(2E)-2-(4-nitrobenzylidenyl)hydrazinyl]carbonyl}phenyl)benzamide; PPh3 = triphenylphosphine] have been prepared by the condensation of N-[2-(hydrazinocarbonyl)phenyl]benzamide with 4-nitrobenzaldehyde followed by the reaction with CuCl, [Cu(MeCN)4]ClO4, [Cu(MeCN)4]BF4 and [Cu(MeCN)4]PF6 in presence of triphenylphosphine as a coligand. Complexes 1–4 were then characterized by elemental analyses, FTIR, UV-visible and 1H NMR spectroscopy. Mononuclear copper(I) complexes 1–4 were formed with L in its keto form by involvement of azomethine nitrogen and the carbonyl oxygen along with two PPh3 groups. A single crystal X-ray diffraction study of the representative complex [(Cu(L)(PPh3)2]CIO4 (2) reveals a distorted tetrahedral geometry around Cu(I). Crystal data of (2): space group = C2/c, a = 42.8596 (9) Å, b = 14.6207 (3) Å, c = 36.4643 (7) Å, V = 20,653.7 (7) Å3, Z = 16. Complexes 1–4 exhibit quasireversible redox behaviour corresponding to a Cu(I)/Cu(II) couple. All complexes show blue-green emission as a result of fluorescence from an intra-ligand charge transition (ILCT), ligand to ligand charge transfer transition (LLCT) or mixture of both. Significant increase in size of the counter anion shows marked effect on quantum efficiency and lifetime of the complexes in solution.  相似文献   

4.
Abstract

A series of Ru(II) complexes have been synthesized, and their electronic spectra and NMR spectroscopy properties were characterized. the chemical shifts of aromatic protons of [Ru(bpy)3] (PF6)2, [Ru(phen)3](ClO4)2 and [Ru(bqdi)3](PF6) move downfield, but the resonance peaks of cis-Ru(bpy)2Cl2 shift upfield. Within the visible spectra of the ruthenium(II) complexes appear a relatively high oscillator strength which is referred to as the π(Ru)→? (ligands) transition.  相似文献   

5.
Ru(II) complexes with weak ligand fields may undergo light-induced ligand dissociation, and the resulted Ru(II) aqua complexes may bind with biomolecules such as DNA, showing potential as photoactivated chemotherapy (PACT) agents. However, Ru(II) complexes with efficient PACT activity are still rare. Some Ru(II) complexes exhibit efficient photoinduced ligand dissociation but poor cytotoxicity. It is speculated that the low nuclear accumulation levels may account for their low PACT efficacy. In order to confirm this hypothesis, the almost noncytotoxic [Ru(7-OCH3-dppz)(4-OCH3-py)4](PF6)2 (Ru1) is loaded on nucleus-targeted C5N2 nanoparticles (NPs). Compared with the free Ru1, Ru1–C5N2 NPs exhibit significantly increased cellular uptake and nuclear accumulation. Therefore, Ru1–C5N2 NPs show efficient PACT activity toward various cancer cell lines (including cisplatin-resistant one) with half maximal inhibitory concentration (IC50) values of 0.18 × 10−6–0.29 × 10−6 m and phototoxicity index (IC50dark/IC50light) values above 137 under both normoxic and hypoxic conditions. Moreover, Ru1–C5N2 NPs also exhibit efficient PACT activity toward cisplatin-resistant 3D multicellular tumor spheroids upon two-photon irradiation (800 nm). The same strategy is also feasible to greatly improve the PACT activity of [Ru(7-OCH3-dppz)(py)4]2+, which itself only has a medium effect. The results may provide new sights for developing efficient Ru(II) PACT agents.  相似文献   

6.
The preparation and oxygen sensing properties of optical materials based on two trinuclear starburst ruthenium(II) complexes: [Ru3(bpy)6(TMMB)]6+ (1) and [Ru3(phen)6(TMMB)]6+ (2) (bpy=2,2′-bpyridine, phen=1,10-phenathroline, TMMB=1,3,5-tris[2-(2′-pyridyl)benzimidazoyl]methylbenzene) assembled in two mesoporous silicate (MS) are described in this paper. The luminescence of Ru complexes/silicate assemble materials can be quenched by molecular oxygen with good sensitivity (I0/I1>5 for 2/MS and I0/I1>3 for 1/MS), indicating that trinuclear starburst Ru(II) complexes/MS systems are sensitive to oxygen molecules.  相似文献   

7.
Some nickel(II) and zinc(II) complexes of the type [Ni(L)(phen/bipy)]X (1a–6a) and [Zn(L) (phen/bipy)]X (1b–6b) (where L = 2-{(E)-[(4-trimethylsilylethynylphenyl)imino]methyl}-4-(4-nitro phenylethynyl)phenol; phen = 1, 10-phenanthroline, bipy = 2, 2´-bipyridine; X = ClO4 ?, BF4 ?, PF6 ?) have been prepared and characterized on the basis of elemental analyses, FTIR, 1H NMR and mass spectral studies. The molecular structure of L was determined by single crystal X-ray diffraction studies. The electrochemical behaviour of the Ni(II) complexes indicate that the phen complexes appears at more positive potential as compared to those for bipy complexes, as a consequence of its strong π-acidic character. TGA was carried out to study the thermal behavior of the complexes. Room temperature luminescence is observed for all complexes corresponds to π → π* ILCT transition. The size of the counter anion and heterocyclic coligands phen and bipy shows marked effect on emission properties of the complexes.  相似文献   

8.
A novel zerovalent ruthenium complex with a π-acidic ligand, Ru(η6-cyclooctatriene)(η2-dimethyl fumarate)2 (1), was prepared from Ru(η4-cyclooctadiene)(η6-cyclooctatriene) [Ru(cod)(cot)]. Complex 1 or Ru(cod)(cot) catalyzes various new carbon-carbon bond-forming reactions that include the [2 + 2] cycloaddition of alkenes and alkynes via ruthenacycles, the creation of a new hydrocarbon, pentacyclo[6.6.0.02,6.03,13.010,14]tetradeca-4,11-diene [PCTD], by dimerization of 2,5-norbornadiene via C-C bond cleavage, and the codimerization of alkynes and/or alkenes. Complex 1 was shown to be an excellent mother complex for various zerovalent ruthenium complexes. Complex 1 reacts with amines, phosphines or water to give new zerovalent ruthenium complexes with the ligands. The resulting aqua complexes have a water ligand with an oxygen atom that is a chiral center, i.e., ruthenium complexes with a ‘chiral water’ ligand were prepared and fully characterized.  相似文献   

9.
The luminescent properties of the complexes [PdBt(μ-Cl)]2, [PdEnBt]ClO4, and [PdBryBt]PF6 (where Bt is 2-(phenyl)benzothiazolate-N,C2′-ion, En is 1,2-(diamine)ethane, and Bpy is 2,2′-bipyridyl) are studied and a qualitative diagram of their electronically excited states is presented.  相似文献   

10.
The He(II) spectra of the unsubstituted metallocenes {M(η-C5H5)2}, M  V, Cr, Mn, Fe, Co, Ni and Ru, and of {Mn(η-C5H4Me)2} are reported; both He(I) and He(II) spectra of some decamethylmetallocenes {M(η-C5Me5)2}, where M  Mg, V, Cr, Mn, Fe, Co and Ni, are also given. Intensity changes between the He(I) and He(II) spectra are shown to provide a reliable guide to band assignment. A ligand field treatment of the decamethylmanganocene cation, including limited configuration interaction, gives values for Δ2, B and C; these values are also in good agreement with the photoelectron spectra of {M(η-C5Me5)2} where M  V, Cr and Fe. Overlap between the ligand and metal “d” band structures prevents complete assignment in the cases of Co and Ni.  相似文献   

11.
Nanoparticles of two silver(I) coordination polymers (CPs), [Ag2(L1)2(DCTP)]n (1) and [Ag2(L2)(DCTP)]n (2) (L1 = 1,3-bis(5,6-dimethylbenzimidazol-1-ylmethyl)benzene, L2 = 1,4-bis(benzimidazol-1-yl)-2-butene, H2DCTP = 2,5-dichloroterephthalic acid), were synthesized by the sonochemical approach and hydrothermal method. Both CPs were characterized by elemental analysis, IR spectra, single-crystal X-ray diffraction, scanning electron microscopy (SEM), and thermogravimetric analyses (TGA). CP 1 exhibits a 2D 4-connected sql net with the point symbol {44.62}. While CP 2 displays a 2D 3,4-connected 3,4L13 net with the point symbol {4.62}2{42.62.82}. The structural diversity indicates that semi-rigid bis(benzimidazole) co-ligands play important roles in tuning the structures of the mixed Ag(I) CPs. The ultrasound irradiation time, temperature, and power showed significant effects on the morphology and growth process of the nanoparticles of two silver(I) CPs. The luminescence and photocatalytic properties of the nanoparticles of CPs 12 on the degradation of methyl blue (MB) were also investigated in detail.  相似文献   

12.
Infrared and Raman spectra (10–3100 cm?1) of the layered ZnPSs compound and of intercalates with [Co(η5 ? C5H5)2+] and [Cr(η6 ? C6H6)2+] cations in the polycrystalline state have been recorded 300–10 K temperature range. A complete assignment of the spectra is proposed in terms of PSs group motions, Zn2+ ion translations and [Co(η5 ? C5H5)2+] or [Cr(η6 ? C6H6)2+] internal vibrations. New low frequency for the [Co(η5-C5H5)2+] intercalate at low temperature are assigned to librational and torsional modes of C5H5 rings. Moreover, the preresonance Raman spectra of this intercalate show a selective enhancement for the metal-ligand vibrations when the charge transfer band of the cobalticenium is approached. One concludes that guest molecules are intercalated under their cationic form, are weakly interacting with the host lattice and seem to be dynamically disordered at room temperature.  相似文献   

13.
Recently, we have discovered a new type of first order phase transition around 120 K for (n-C3H7)4N[FeIIFeIII(dto)3] (dto=C2O2S2), where the charge transfer transition between FeII and FeIII occurs reversibly. In order to elucidate the origin of this peculiar first order phase transition. Detailed information about the crystal structure is indispensable. We have synthesized the single crystal of (n-C3H7)4N[CoIIFeIII(dto)3] whose crystal structure is isomorphous to that of (n-C3H7)4N[FeIIFeIII(dto)3], and determined its detailed crystal structure. Crystal data: space group P63, a=b=10.044(2) Å, c=15.960(6) Å, α=β=90°, γ=120°, Z=2 (C18H28NS6O6FeCo). In this complex, we found a ferromagnetic transition at Tc=3.5 K. Moreover, on the basis of the crystal data of (n-C3H7)4N[CoIIFeIII(dto)3], we determined the crystal structure of (n-C3H7)4N[FeIIFeIII(dto)3] by simulation of powder X-ray diffraction results.  相似文献   

14.
Intramolecular electron spin exchange (IESE) in two nitroxide biradicals, R6–C≡C–C≡C–R6 (1) and R6–C≡C–p-C6H4–C≡C–R6 (2), is studied as a function of temperature and solvent properties. The effect of molecular solvents and ionic liquids (ILs, [1-methyl-3-butylimidazolium]+[PF6]?, bmimPF6, and [1-methyl-3-octylimidazolium]+[BF4]?, omimBF4) on the IESE in magnetically diluted solutions is investigated. Changes in electron paramagnetic resonance spectra are analyzed and the thermodynamic parameters of these changes are calculated. Geometry optimization and D-tensor calculations of biradicals 1 and 2 were carried out on the DFT/UB3LYP/cc-pVdz and DFT/ROPBE/N07D levels of theory. The probable differences in biradical behavior are discussed.  相似文献   

15.
The three Ru(II) complexes of [Ru(phen)2dppca]2+ (1) [Ru(bpy)2dppca]2+ (2) and [Ru(dmb)2dppca]2+ (3) (where phen = 1,10 phenanthroline, bpy = 2,2-bipyridine, dmb = 2 ,2-dimethyl 2′,2′-bipyridine and polypyridyl ligand containing a single carboxylate functionality dppca ligand (dipyridophenazine-11-carboxylic acid) have been synthesized and characterized. These complexes have been shown to act as promising calf thymus DNA intercalators and a new class of DNA light switches, as evidenced by UV-visible and luminescence titrations with Co2+ and EDTA, steady-state emission quenching by [Fe(CN)6]4− and KI, DNA competitive binding with ethidium bromide, viscosity measurements, and DNA melting experiments. The results suggest that 1, 2, and 3 complexes bind to CT-DNA through intercalation and follows the order 1 > 2 > 3. Under irradiation at 365 nm, the three complexes have also been found to promote the photocleavage of plasmid pBR322 DNA.  相似文献   

16.
Three novel lanthanide 1-D chain coordination polymers, namely {[Tb(μ2-L)2(η2-NO3)(CH3OH)(H2O)]·0.5CH3OH·0.5H2O}n (1), {[Dy(μ2-L)2(η2-NO3)(CH3OH)(H2O)]·H2O}n (2) and {[Ce(μ2-L)2(η2-NO3)(H2O)3]·H2O}n (3) (HL=N-benzoyl-N′-(4-benzoxy)thiourea), have been prepared and characterized by IR spectroscopy, elemental analysis and single-crystal X-ray diffraction. The luminescence properties and themostabilities of polymers 1-3 have been determined as well.  相似文献   

17.
The cyclometalated complexes [Pt(С^N)En]PF6 and [Ir(C^N)2En]PF6 ((C^N) are deprotonated forms of 2-phenylbenzothiazole or 2-naphthylbenzothiazole and En is ethylenediamine) are studied by 1Н NMR, IR, electronic absorption, and emission spectroscopy, as well as by voltammetry. Metalation of heterocyclic ligands leads to the formation of five-membered {M(C^N)} cycles in the composition of squareplanar Pt(II) complexes and octahedral Ir(III) complexes of the cis-С,С structure. A bathochromic shift of the metal-to-cyclometalated ligand charge transfer bands and a decrease in the potential difference between the single-electron waves of metal-centered oxidation and ligand-centered reduction of complexes upon substitution of 2-phenylbenzothiazole by 2-naphthylbenzothiazole and of Pt(II) by Ir(II) are shown. The phosphorescence of complexes in the visible region is assigned to the radiative transition from the metal-modified intraligand electronic excited state.  相似文献   

18.
We have carried out 99/101Ru and 63/65Cu nuclear magnetic resonance experiments in order to investigate magnetic and electronic properties of the magnetic superconductor RuSr2RECu2O8 (RE=Gd, Eu and Y). The two kinds of 99/101Ru signals were observed in the magnetically ordered state for each system, suggesting a charge segregation of Ru5+ (S=3/2) and Ru4+ (S=1) ions in the RuO2 layers. The internal field at the Cu sites is revealed to be of the order of kilo Oe, indicating weak magnetic interactions between the CuO2 and RuO2 planes. The temperature dependence of nuclear spin-lattice relaxation time T1 of 63Cu in RE=Y shows a ‘spin gap’ like behavior, suggesting the system is under-doped.  相似文献   

19.
The new ligand 4-(isopropylbenzaldehyde)imidazo[4,5-f ][1,10]phenanthroline (ippip) and its complexes [Ru(phen)2(ippip)]2+(1),[Co(phen)2(ippip)]3+(2),[Ru(bpy)2(ippip)]2+(3),[Co(bpy)2(ippip)]3+(4)(bpy=2,2-bipyridine) and (phen=1,10-phenanthroline) were synthesized and characterized by ES+-MS, 1H and 13C NMR. The DNA binding properties of the four complexes were investigated by different spectrophotometric methods and viscosity measurements. The results suggest that complexes bind to calf thymus DNA (CT-DNA) through intercalation. When irradiated at 365 nm, the complexes promote the photocleavage of pBR322 DNA, and complex 1 cleaves DNA more effectively than 2, 3, 4 complexes under comparable experimental conditions. Furthermore, photocleavage studies reveal that singlet oxygen (1O2) plays a significant role in the photocleavage.  相似文献   

20.
矫玉秋  赵昆  卢贵武 《物理学报》2008,57(3):1592-1598
用密度泛函(DFT)方法优化了配合物H3PAuPh(a),(H3PAu)2(1,4-C6H4)2(b)的基态的几何结构,并用含时密度泛函方法计算了它们的吸收光谱.结果表明配合物ab的最低能量吸收谱线的波长分别为257.5 nm和307.6 nm,皆具有C(2p)→Au(6p)电荷转移参与下的pπ 关键词: 激发态 光谱 密度泛函 3')" href="#">AuPH3  相似文献   

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