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1.
Five mono‐nuclear silver(I) complexes with the ligand 2,9‐dimethyl‐1,10‐phenanthroline, namely [Ag(DPEphos)(dmp)]BF4 ( 1 ), [Ag(DPEphos)(dmp)]CF3SO3 ( 2 ), [Ag(DPEphos)(dmp)]ClO4 ( 3 ), [Ag(DPEphos)(dmp)]NO3 ( 4 ), and [Ag(dppb)(dmp)]NO3 · CH3OH ( 5 ) {DPEphos = bis[2‐(diphenylphosphanyl)phenyl]ether, dppb = 1,2‐bis(diphenylphosphanyl)benzene, dmp = 2,9‐dimethyl‐1,10‐phenanthroline} were characterized by X‐ray diffraction, IR, 1H NMR, 31P NMR and fluorescence spectroscopy. Their terahertz (THz) time‐domain spectra were also studied. In these complexes the silver(I), which is coordinated by two kinds of chelating ligands, adopts four‐coordinate modes to generate mono‐nuclear structures. In complexes 1 , 3 – 5 , offset π ··· π weak interactions exist between the neighboring benzene rings. In the 31P NMR spectra, there exist splitting signals (dd), which can be attributed to the coupling of the 107,109Ag–31P. All the emission peaks of these complexes are attributed to ligand‐centered excited states.  相似文献   

2.
In an effort to explore the effect of ancillary ligands on the spectral properties and overall G‐quadruplex DNA binding behavior, two new ruthenium(II) complexes [Ru(phen)2(dppzi)]2+ ( 1 ) and [Ru(dmp)2(dppzi)]2+ ( 2 ) (phen=1,10‐phenanthroline, dmp=2,9‐dimethyl‐1,10‐phenanthroline, dppzi=dipyrido[3,2‐a:2′,3′‐c]phenazine‐10,11‐imidazole) were prepared. Complex 1 can emit luminescence in the absence and presence of G‐quadruplexes DNA. However, with ?CH3 substituent on the 2‐ and 9‐positions of the phen ancillary ligand, no detectable luminescence is observed for complex 2 in any organic solvent or in the absence and/or presence of G‐quadruplex DNA. Experimental and molecular docking studies indicated that both complexes interacted with the human telomeric repeat AG3(T2AG3)3 (22AG) G‐quadruplex with the stoichiometric ratio of 1:1, but the two complexes showed different G‐quadruplex DNA binding affinity. Complex 1 binds to the G‐quadruplexes DNA more tightly than complex 2 does. Our results demonstrate that methyl groups on the phen ancillary ligand significantly affect the spectral properties and the overall DNA binding behavior of the complexes. Such difference in spectral properties and DNA binding affinities of these two complexes can be reasonably explained by DFT/TD‐DFT calculations. This work provides guidance not only on exploring the G‐quadruplexes DNA binding behavior of complexes, but also understanding the unique luminescence mechanism.  相似文献   

3.
The novel 1,10‐phenanthroline‐2,9‐dicarboxylate containing Chromium(III) complex, (pydaH)[Cr(phendc)2] · 5H2O, was synthesized using proton‐transfer compound LH2, (pydaH2)2+(phendc)2?, (pyda: 2,6‐pyridinediamine; phendcH2: 1,10‐phenanthroline‐2,9‐dicarboxylic acid) and thoroughly characterized by elemental analysis, IR spectroscopy, X‐ray crystallography and cyclic voltammetry. The complex crystallizes in the monoclinic space group P21/n with four formula units in the unit cell. The unit cell dimensions are: a = 13.962(3) Å, b = 14.529(3) Å, c = 16.381(3) Å and β = 106.691(4)°. In this complex, 1,10‐phenanthroline‐2,9‐dicarboxylate acts as a tridentate ligand and the lattice is composed of anionic hexacoordinated complex, [Cr(phendc)2]?, 2,6‐pyridiniumdiamine counter ion, (pydaH)+, and five lattice water molecules. Crystallographic characterization revealed that the resulting supramolecular structure is strongly stabilized by complicated network of hydrogen bonds between the crystallization water molecules, counter ion and both coordinated and uncoordinated carboxylate groups. There is no relevant π‐π interaction for this anionic complex between pyda or phendc moieties. The electrochemical studies indicated over potential for both the cathodic and anodic peaks of the complex with respect to the free Cr3+ ion, as a consequence of the energy requirement for rearrangement of the ligand at electrode surface.  相似文献   

4.
Four novel mononuclear ruthenium(II) complexes [Ru(dmb)2L]2+ [dmb = 4,4′‐dimethyl‐2,2′‐bipyridine, L = imidazo‐[4,5‐f][1,10]phenanthroline (IP), 2‐phenylimidazo‐[4,5‐f][1,10]phenanthroline (PIP), 2‐(4′‐hydroxyphenyl)imidazo‐[4,5‐f] [1,10] phenanthroline (HOP), 2‐(4′‐dimethylaminophenyl) imidazo‐[4, 5‐f] [1,10] phenanthroline (DMNP)] were synthesized and characterized by ES‐MS, 1H NMR, UV‐vis and electrochemistry. The nonlinear optical properties of the ruthenium(II) complexes were investigated by Z‐scan techniques with 12 ns laser pulse at 540 nm, and all of them exhibit both nonlinear optical (NLO) absorption and self‐defocusing effect. The corresponding effective NLO susceptibility |x3| of the complexes is in the range of 2.68 × 10?12‐4.57 × 10?12 esu.  相似文献   

5.
One group of ligands used in transition metal complexes is synthesized by derivatizing 1,10‐phenanthroline. These metal complexes are of interest for study in the field of photovoltaic devices and solar fuels. Previous strategies for obtaining the 5,6‐diones of substituted 1,10‐phenanthrolines do not work for 2,9‐diphenyl‐1,10‐phenanthroline due to undesired products resulting from oxidation of the phenyl substituents. However, 2,9‐diphenyl‐1,10‐phenanthroline‐5,6‐dione can be obtained in reasonable yield by oxidation with BrO3? in weak aqueous acid. The resulting dione can be converted directly to the 5,6‐dialkoxy product upon two electron reduction in aprotic solvent followed by treatment with appropriate alkylating agents.  相似文献   

6.
Three new lanthanide phenoxyacetate complexes with 1,10‐phenanthroline. [Nd(POA)3 (phen)]2 · 2C2H5OH (1), [Eu(POA)3‐ (phen)]2 · 2C2H5OH (2) and [Sm(POA)2(DMSO)(phen)]2‐ (ClO4)2 (3) (POA= phenoxyacetate, phen = 1,10‐phenanthroline, DMSO = dimethyl sulfoxide), were synthesized and characterized by elemental analyses, IR, UV‐vis and FAB‐MS spectra. Their structures were determined by single crystal X‐ray diffraction analysis. In complexes 1 and 2, the carboxylate groups are bonded to Ln3+ ion in three modes: the chelating bidentate, the bridging bidentate and the bridging tridentate. In complex 3, the carboxylate groups are bonded to Sm3+ ion only involved in one mode: the bridging bidentate. The luminescence behavior of complex 2 was also studied by means of emission spectra.  相似文献   

7.
Treatment of 2‐chloro‐ or 2,9‐dichloro‐1,10‐phenanthroline with aqueous HBr or aqueous H2SO4 at 120°C yielded 1,10‐phenanthroline‐2(1H)‐one or 1,10‐dihydro‐1,10‐phenanthroline‐2,9‐dione, respectively. The hydrolysis of 2,9‐dichloro‐1,10‐phenanthroline with 37% aqueous HC1 led to the half hydrolyzed amide and the bis‐amide. Under comparable reactions conditions, using aqueous HBr, H2SO4 or HC1, 2‐chloropyridine was found to be hydrolytically stable. On the other hand, 2‐chloro‐ or 2,9‐dichloro‐1,10‐phenanthroline on heating with 57% aqueous HI afforded the HI salts of 2‐iodo‐ or 2,9‐diiodo‐1,10‐phenanthroline, which could be isolated. These salts on treatment with aqueous ammonium hydroxide led to good yields of 2‐iodo‐ and 2, 9‐diiodo‐1,10‐phenanthroline, respectively. Treatment of 2‐chloropyridine with 57% aqueous HI under similar reaction conditions led to 2‐iodopyridine in a 10% conversion.  相似文献   

8.
Two rare metal coordination complexes of yttrium(III) including 1,10‐phenanthroline, Y(phen)2(NO3)3 and (phenH)2[Y2(pydc)3(NO3)2·6H2O] (phen=1,10‐phenanthroline, pydc=2,6‐pyridinedicarboxylate), and a proton transfer compound (phenH+)2(pydc2?) were synthesized and characterized by elemental analysis, molar conductance, infrared spectra (IR), nuclear magnetic resonance (NMR) and thermal analysis. The proposed structures of yttrium complexes were exhibited. The in vitro biological activities of the newly synthesized complexes have also been investigated against Bacillus coli, Staphylococcus aureus and Candida albicans. The results showed that yttrium(III) complexes including 1,10‐phenanthroline exhibited better antibacterial/antifungal activity than their ligands and corresponding compounds.  相似文献   

9.
Two new ruthenium(II) complexes, [Ru(dmp)2(APIP)](ClO4)2 (1) (APIP?=?2-(2-aminophenylimidazo[4,5-f][1,10]phenanthroline), dmp?=?2,9-dimethyl-1,10-phenanthroline) and [Ru(dmp)2(HAPIP)](ClO4)2 (2) (HAPIP?=?2-(2-hydroxyl-5-aminophenyl)imidazo[4,5-f][1,10]phenanthroline), were synthesized and characterized. The DNA-binding properties of these complexes were investigated by absorption titration, viscosity measurements, and photoactivated cleavage. The DNA-binding constants for 1 and 2 have been determined to be 2.3 (±?0.3)?×?104 (mol?L?1)?1 and 3.3 (±?0.4)?×?104 (mol?L?1)?1. The results indicate that 1 and 2 interact with DNA through intercalative mode. The cytotoxicities of 1 and 2 were assessed against BEL-7402, HepG-2 and MCF-7 cell lines using standard MTT assay. The apoptosis induced by these complexes was studied with the acridine orange/ethidium bromide staining method. The antioxidant activity on hydroxyl radical was also investigated.  相似文献   

10.
Polypyridyl ligand 9a,13a‐dihydro‐4,5,9,14‐tetraaza‐benzo[b]triphenylene‐11‐yl)‐phenyl‐methanone (BDPPZ) and its complexes [Ru(bpy)2BDPPZ]2+, [Ru(dmb)2BDPPZ]2+ and [Ru(phen)2BDPPZ]2+ (where bpy = 2,2′‐bipyridine, dmb = 4,4′‐dimethyl‐2,2′‐bipyridine, phen = 1,10‐phenanthroline) have been synthesized and characterized by elemental analysis, IR, UV–vis, 1H‐NMR, 13C‐NMR and mass spectra. The DNA‐binding properties of the complexes were investigated by absorption, emission, melting temperature and viscosity measurements. Experimental results indicate that the three complexes can intercalate into DNA base pairs. Photo activated cleavage of pBR‐322 DNA by the three complexes was also studied. Further, all three Ru(II) complexes synthesized were screened for their antimicrobial activity. Copyright © 2009 John Wiley & Sons, Ltd.  相似文献   

11.
A novel 1D PbII coordination polymer containing Pb2‐(μ‐N3)2 unit [Pb(dmp)(N3)2]n (dmp =  2,9‐dimethyl‐1,10‐phenanthroline) has been prepared and characterized. Single‐crystal X‐ray diffraction analyses show that the coordination number for PbII ions is six, PbN6, with “stereochemically active” electron lone pairs and the coordination sphere being hemidirected. The single‐crystal X‐ray data show the chains interact with each other through the π–π stacking interactions, which create a 3D framework. The structure of title complex has been optimized by density functional theory. Structural parameters and IR spectra for the complex are in agreement with the crystal structure.  相似文献   

12.
Circularly polarized luminescence (CPL) was observed from [Eu(dppda)2]? (dppda=4,7‐diphenyl‐1,10‐phenanthroline‐2,9‐dicarboxylic acid) and [Eu(pzpda)2]? (pzpda=pyrazino[2,3‐f][1,10]phenanthroline‐7,10‐dicarboxylic acid) in aqueous solutions containing various amino acids. The selectivity of these complexes towards amino acids enabled them to be used as chiral sensors and their behavior was compared with that of [Eu(pda)2]? (pda=1,10‐phenanthroline‐2,9‐dicarboxylic acid). As these EuIII complexes have achiral D2d structures under ordinary conditions, there were no CPL signals in the emission assigned to f–f transitions. However, when the solutions contained particular amino acids they exhibited detectable CPL signals with glum values of about 0.1 (glum=CPL/2 TL; TL=total luminescence). On examining 13 amino acids with these three EuIII complexes, it was found that whether an amino acid induced a detectable CPL depended on the EuIII complex ligands. For example, when ornithine was used as a chiral agent, only [Eu(dppda)2]? exhibited intense CPL in aqueous solutions of 10?2 mol dm?3. Steep amino acid concentration dependence suggested that CPL in [Eu(dppda)2]? and [Eu(pzpda)2]? was induced by the association of four or more amino acid molecules, whereas CPL in [Eu(pda)2]? was induced by association of two arginine molecules.  相似文献   

13.
Two novel chiral ruthenium(II) complexes, Δ‐[Ru(bpy)2(dmppd)]2+ and Λ‐[Ru(bpy)2(dmppd)]2+ (dmppd = 10,12‐dimethylpteridino[6,7‐f] [1,10]phenanthroline‐11,13(10H,12H)‐dione, bpy = 2,2′‐bipyridine), were synthesized and characterized by elemental analysis, 1H‐NMR and ES‐MS. The DNA‐binding behaviors of both complexes were studied by UV/VIS absorption titration, competitive binding experiments, viscosity measurements, thermal DNA denaturation, and circular‐dichroism spectra. The results indicate that both chiral complexes bind to calf‐thymus DNA in an intercalative mode, and the Δ enantiomer shows larger DNA affinity than the Λ enantiomer does. Theoretical‐calculation studies for the DNA‐binding behaviors of these complexes were carried out by the density‐functional‐theory method. The mechanism involved in the regulating and controlling of the DNA‐binding abilities of the complexes was further explored by the comparative studies of [Ru(bpy)2(dmppd)]2+ and of its parent complex [Ru(bpy)2(ppd)]2+ (ppd = pteridino[6,7‐f] [1,10]phenanthroline‐11,13 (10H,12H)‐dione).  相似文献   

14.
A series of nitrogen ligand (L)/copper complexes of the type [CuIL]+, [CuIIL(X)]+ and [CuIL2]+ (X = Cl, BF, acac, CH3COO and SO3CF) was studied in the gas phase by electrospray ionization mass spectrometry. The following ligands (L) were employed: 1,12‐diazaperylene (dap), 1,1′‐bisisoquinoline (bis), 2,2′‐bipyridine (bpy), 1,10‐phenanthroline (phen), 2,11‐disubstituted 1,12‐diazaperylenes (dap), 3,3′‐disubstituted 1,1′‐ bisisoquinoline (bis), 5,8‐dimethoxy‐substituted diazaperylene (meodap), 6,6′‐ dimethoxy‐substituted bisisoquinoline (meobis) and 2,9‐dimethyl‐1,10‐phenanthroline (dmphen). Collision‐induced decomposition measurements were applied to evaluate the relative stabilities of the different copper complexes. The influence of the spatial arrangement of the ligands, of the type of substituents and of the counter ion of the copper salts employed for the complexation was examined. Correlations were found between the binding constants of the [ML2]+ complexes in solution and the relative stabilities of the analogous complexes in the gas phase. Furthermore, complexation with the ligands 2,11‐dialkylated 1,12‐diazaperylenes [alkyl = ethyl (dedap) and isopropyl (dipdap)] was studied in the solvents CH3OH and CH3CN. Copyright © 2010 John Wiley & Sons, Ltd.  相似文献   

15.
Two new complexes, [Ru(phen)2(ppd)]2+ ( 1 ) and [Ru(phen)(ppd)2]2+ ( 2 ) (ppd=pteridino[6,7‐f] [1,10]phenanthroline‐11,13(10H,12H)‐dione, phen=1,10‐phenanthroline) were synthesized and characterized by ES‐MS, 1H‐NMR spectroscopy, and elemental analysis. The intercalative DNA‐binding properties of 1 and 2 were investigated by absorption‐spectroscopy titration, luminescence‐spectroscopy studies, thermal denaturation, and viscosity measurements. The theoretical aspects were further discussed by comparative studies of 1 and 2 by means of DFT calculations and molecular‐orbital theory. Photoactivated cleavage of pBR322 DNA by the two complexes were also studied, and 2 was found to be a much better photocleavage reagent than 1 . The mechanism studies revealed that singlet oxygen and the excited‐states redox potentials of the complex may play an important role in the DNA photocleavage.  相似文献   

16.
The structure of bis(1,10‐phenanthroline‐κ2N,N′)(thio­sulfato‐κ2O:S)­manganese(II) methanol solvate, [Mn(S2O3)(C12H8N2)2]·CH3OH, is made up of Mn2+ centers coordinated to two bidentate phenanthroline (phen) groups and an S,O‐chelating thio­sulfate anion, forming monomeric entities. The structure of catena‐poly­[[di­aqua(2,9‐di­methyl‐1,10‐phen­anthro­line‐κ2N,N′)­manganese(II)]‐μ‐thio­sulfato‐κ2O:S], [Mn(S2O3)(C14H12N2)(H2O)2]n, is polymeric, consisting of Mn(dmph)(H2O)2 units (dmph is 2,9‐di­methyl‐1,10‐phenanthroline) linked by thio­sulfate anions acting in an S,O‐chelating manner.  相似文献   

17.
Two ruthenium(II) complexes [Ru(MeIm)4(L)]2+ (L?=?2-(imidazo-4-group)-1H-imidazo-[4,5-f][1,10]phenanthroline, 2-(thiophene-2-group)-1H-imidazo[4,5-f][1,10]phenanthroline, MeIm?=?1-methylimidazole) have been synthesized according to literature and structurally characterized. The interaction of the complexes with calf thymus DNA has been explored using electronic absorption titration, competitive binding experiment, circular dichroism, thermal denaturation, and viscosity measurements. The results show that both complexes could bind DNA in a intercalation mode and the DNA-binding affinity of [Ru(MeIm)4(tip)]2+ (K b?=?(7.2?±?0.3)?×?105?(mol?L?1)?1) is greater than that of [Ru(MeIm)4(iip)]2+ (K b?=?(6.1?±?0.2)?×?105?(mol?L?1)?1).  相似文献   

18.
Three biphenyl‐3,5‐dicarboxylic acid (H2 L ) based coordination polymers, namely, [Mn3( L )3(2,2′‐bpy)2]n ( 1 ), {[Mn( L )(phen)] · (MeOH)}n ( 2 ), and [Mn( L )(dipt)]n ( 3 ), (2,2′‐bpy = 2,2′‐bipyridine, phen = 1,10‐phenanthroline, and dipt = 2,9‐dimethyl‐1,10‐phenanthroline) were synthesized and characterized by single‐crystal X‐ray diffraction and analyses of their magnetic properties. 1 is a trinuclear manganese structure with a 2D motifs, which can join by hydrogen bond bridges to give 3D supramolecular architectures. 2 has a dinuclear center forming a 1D supramolecular ladder chain. The mononuclear complex 3 displays 1D metal‐organic chains driven by μ2‐ L linkers. Their structural differences were investigated, revealing that the influence of steric hindrance on the structures of acid‐based coordination polymers is realized through changing the N‐heterocyclic ancillaries of diverse steric hindrance. Obviously, with decreasing of the steric hindrance of the N‐donor ligand, complexes 1 – 3 show structures from 1D to 2D and mononuclear to multinuclear. Magnetic susceptibility measurements indicate that 1 and 2 have dominating antiferromagnetic couplings between metal ions, whereas compound 3 is paramagnetic.  相似文献   

19.
The new ligand 2′-(3″,4″-methylene-dioxyphenyl)imidazo[4′,5′-f] [1,10]phenanthroline (mip) and its Ru(II) complexes [Ru(2,9-dmp)2(mip)]2+ (1) (2,9-dmp = 2,9-dimethyl-1,10-phenanthrolline) and [Ru(4,7-dmp)2(mip)]2+ (2) (4,7-dmp = 4,7-dimethyl-1,10-phenanthrolline) were synthesized and characterized. The binding properties of the two complexes to calf-thymus DNA (CT-DNA) were investigated by different spectrophotometric methods and viscosity measurements. Both 1 and 2 bind to CT-DNA in an intercalative mode, but with different binding strengths. Complex 2 can emit luminescence in the Tris buffer at ambient temperature, however, complex 1 showed no fluorescence emission, neither alone nor in the presence of CT-DNA. The circular-dichroism signal of the dialysate of the racemic complex against CT-DNA suggests that complexes 1 and 2 interact enantioselectively with CT-DNA. Furthermore, complexes 1 and 2 have been found to be an efficient photosensitiser for cracking DNA plasmid. Theoretical calculations for 1 and 2 were also carried out applying the density functional theory (DFT) method and applied to explain some obtained experimental observations.  相似文献   

20.
Two differently hydrated crystal forms of the title compound, viz. bis­(acetato‐κ2O,O′)(2,9‐di­methyl‐1,10‐phenanthroline‐κ2N,N′)­mercury(II), [Hg(C2H3O2)2(C14H12N2)] or [HgAc2(dmph)] [dmph is 2,3‐di­methyl‐1,10‐phenantroline (neocuproine) and Ac is acetate], (I), and tris­[bis­(acetato‐κ2O,O′)(2,9‐di­methyl‐1,10‐phenanthroline‐κ2N,N′)­mercury(II)] hexadecahydrate, [Hg(C2H3O2)2(C14H12N2)]3·16H2O or [HgAc2(dmph)]3·16H2O, (II), are presented. Both structures are composed of very simple monomeric units, which act as the building blocks of complex packing schemes stabilized by a diversity of π–π and hydrogen‐bonding interactions.  相似文献   

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