Redox-active organic compounds have received much attention as high-capacity electrodes for rechargeable batteries.However,the high solubility in organic electrolytes during charge and discharge processes hinders the ...Redox-active organic compounds have received much attention as high-capacity electrodes for rechargeable batteries.However,the high solubility in organic electrolytes during charge and discharge processes hinders the practical exploitation of organic compounds.This study presents a cobalt-based metal–organic coordination compound with bifunctional coordinated water(Co-MOC-H_(2)O)for sodium-ion storage.The coordinated water enhances interactions between sodium ions and nitrogen atoms in organic ligands through chelation,activating the inert sodium-ion storage sites(C=N).Moreover,the stable hydrogen bonded framework formed by the coordinated water molecules prevents the active organic compounds from dissolving into the electrolyte,thereby enhancing cycling stability.With the bifunctional coordinated water molecules,the Co-MOC-H_(2)O electrode delivers a high capacity of 403 mAh g^(-1)at 0.2 A g^(-1)over 600 cycles and exhibits a capacity retention of 77.9%at 2 A g^(-1)after 1100 cycles.This work highlights the crucial role of the coordinated water molecules in constructing high capacity and long-life sodium-ion storage materials.展开更多
<span style="font-family:Verdana;">The present work describes the synthesis of a novel heterocyclic azo dye by </span><span style="font-family:Verdana;">general diazonization of 2...<span style="font-family:Verdana;">The present work describes the synthesis of a novel heterocyclic azo dye by </span><span style="font-family:Verdana;">general diazonization of 2-amino-4,5-dimethylthiazole followed by the di</span><span style="font-family:Verdana;">azo-</span><span><span><span style="font-family:;" "=""> </span></span></span><span><span><span style="font-family:;" "=""><span style="font-family:Verdana;">coupling of the resulting diazonium ion with 5-methyl-2-(propan-2-</span><span><span style="font-family:Verdana;">yl)phenol to obtain ligand </span><b><span style="font-family:Verdana;">L</span></b><span style="font-family:Verdana;">. This was characterized using Fouri</span></span><span style="font-family:Verdana;">er-transformed infrared and electronic spectrophotometry. Ligand </span><b><span style="font-family:Verdana;">L </span></b><span style="font-family:Verdana;">was further coordinated with five </span><span style="font-family:Verdana;">metal ions, M:L, 1:2 </span></span></span></span><span style="font-family:Verdana;"><span style="font-family:Verdana;"><span style="font-family:Verdana;">[</span></span></span><span style="font-family:Verdana;"><span style="font-family:Verdana;"><span style="font-family:Verdana;">M</span></span></span><span><span><span style="font-family:;" "=""> </span></span></span><span style="font-family:Verdana;"><span style="font-family:Verdana;"><span style="font-family:Verdana;">= Cu(II), Mn(II), Zn(II), Ni(II) and Co(II)</span></span></span><span style="font-family:Verdana;"><span style="font-family:Verdana;"><span style="font-family:Verdana;">]</span></span></span><span style="font-family:Verdana;"><span style="font-family:Verdana;"><span style="font-family:Verdana;">. The </span></span></span><span><span><span style="font-family:;" "=""><span style="font-family:Verdana;">coordination compounds obtained were characterized by electronic, IR spectrophotometry, magnetic susceptibility and percentage metal analyses. The results obtained suggested that a thiazoylazo dye was obtained as ligand </span><b><span style="font-family:Verdana;">L</span></b><span style="font-family:Verdana;">. It was proposed that two molecules of the solvent coordinated to the metal ion in addition with the ligands to give an octahedral geometry for copper(II), manganese(II) and nickel(II) complexes. On the other hand, square planar </span><span style="font-family:Verdana;">geometry was suggested for zinc(II) and cobalt(II) complexes. The an</span><span style="font-family:Verdana;">ti-infla</span></span></span></span><span style="font-family:Verdana;"><span style="font-family:Verdana;"><span style="font-family:Verdana;">- </span></span></span><span><span><span style="font-family:;" "=""><span style="font-family:Verdana;">mmatory activity of the ligand and coordination compounds was evaluated using four </span><i><span style="font-family:Verdana;">in</span></i> <i><span style="font-family:Verdana;">vitro</span></i><span style="font-family:Verdana;">-based assays viz: </span><span><span style="font-family:Verdana;">xanthine oxidase and lipoxygenase inhibition assay, membrane stability and protein denaturation assay. The synthesized compounds generally exhibited good anti-inflammatory activity in all </span><span style="font-family:Verdana;">the assays carried out. However, the reference standards, in this instance,</span><span style="font-family:Verdana;"> were more effective in the case of xanthine oxidase, lipoxygenase and protein denaturation inhibitory assays. For the membrane stability study, the </span><span><span style="font-family:Verdana;">coordination compounds and ligand </span><b><span style="font-family:Verdana;">L </span></b><span style="font-family:Verdana;">elicited more potent anti-inflammatory</span></span><span style="font-family:Verdana;"> activity than the standard drug.</span></span></span></span></span>展开更多
In this work,we have reported the synthesis and spectroscopic characterization of captopril(Cap)coordination compounds:Cu(Cap)·2H 2O,Cr(Cap)·H 2O,Zn(Cap)·3H 2O and Mg(Cap)4.Herein,it is worthily mention...In this work,we have reported the synthesis and spectroscopic characterization of captopril(Cap)coordination compounds:Cu(Cap)·2H 2O,Cr(Cap)·H 2O,Zn(Cap)·3H 2O and Mg(Cap)4.Herein,it is worthily mentioned that the FTIR spectroscopic technique was employed to recognized the nature of coordination between captopril ligand and copper,chromium,zinc and magnesium(Ⅱ)metal ions.In view of the infrared spectroscopic tool,the copper(Ⅱ)metal ion coordinated toward captopril drug ligand through sulfur atom of SH group dependent on the absent of stretching vibration band of—SH.Based on this result,the stretching motion ofνa(COO)shifts clearly indicates that Cu 2+,Cr 2+,Zn 2+and Mg 2+the carboxylic group is employed as coordinative site for all compounds as a metal-ligand coordinative bond.As a general behavior,it is verified that the coordination compound thermal stability(considering the release of captopril molecules,not the release of water molecules)is affected by the metal cation radius:minor radius is associated with higher thermal stability,probably due to a higher metal-captopril bond dissociation enthalpy.展开更多
The coordination compounds,{Cu[CH_3C_6H_4N(CH_2COO)_2]}.2H_2O and {Cu[CH_3OC_6H_4N(CH_2COO)_2]}.2H_2O,have been prepared and its crystal struc- tures determined.The final discrepancy factors are R=0.052,R_w=0.061 for ...The coordination compounds,{Cu[CH_3C_6H_4N(CH_2COO)_2]}.2H_2O and {Cu[CH_3OC_6H_4N(CH_2COO)_2]}.2H_2O,have been prepared and its crystal struc- tures determined.The final discrepancy factors are R=0.052,R_w=0.061 for (I)and R=0.052,R_w=0.039 for(Ⅱ).The geometry of the coordination poly- hedron with Cu(Ⅱ)is a distorted tetragonal pyramid for(Ⅰ)and an unsym- metrical and extended tetragonal bipyramid for(Ⅱ),respectively.The re- sults of EHMO calculations indicate that the ligand mainly provided the field with very few of its electrons being coordinated to the central atom.展开更多
[Cu_(0.84)Au_(0.16)(PPh_3)_2(SC(Ph)NHPh)Cl]·0.5CS_2=,Mr=895.79,monoclinic,space group P2_1/a,a=17.231(3),b=14.611(2),c=18.000(3) ,β=105.56(2)°,V=4365(1) ~3, Z=4,D_c=1.37g/cm^3.,λ(MoK_α)=0.71073 ,μ=12.15c...[Cu_(0.84)Au_(0.16)(PPh_3)_2(SC(Ph)NHPh)Cl]·0.5CS_2=,Mr=895.79,monoclinic,space group P2_1/a,a=17.231(3),b=14.611(2),c=18.000(3) ,β=105.56(2)°,V=4365(1) ~3, Z=4,D_c=1.37g/cm^3.,λ(MoK_α)=0.71073 ,μ=12.15cm^(-1),F(000)=1855,R=0.052, R_W=0.045 for 3930 observed reflections with Ⅰ>1.5σ(Ⅰ).The central metal atom has a dis. torted tetrahedral geometry with bond lengths Cu-S=2.384(2) (Au-S=2.389(4)), Cu-Cl=2.481(3)(Au-Cl=2.474(1))and Cu-P=2.269(2)-2.289(2)(Au-P=2.270(4)-2.279(4)) .展开更多
Two novel coordination compounds of Zn(Ⅱ) with Ph_3P+(CH_2)_2CO-_2(L), namely, [ZnL_4(H_2O)_2]·(ClO_4)_2·2H_2O(compound 1) and [Zn_2Cl_4(μ-L-O,O′)_2](compound 2), have been prepared. The single crystal X-...Two novel coordination compounds of Zn(Ⅱ) with Ph_3P+(CH_2)_2CO-_2(L), namely, [ZnL_4(H_2O)_2]·(ClO_4)_2·2H_2O(compound 1) and [Zn_2Cl_4(μ-L-O,O′)_2](compound 2), have been prepared. The single crystal X-ray structure analysis of these compounds indicates that in compound 1 the Zn(Ⅱ) atom is coordinated by four monodentate carboxylato groups on the equatorial plane and two aqua ligands occupy the axial coordination positions. The pendant oxygen atoms form strong hydrogen bonds with the aqua molecules which results in the stability of this structure. In compound 2, two Zn(Ⅱ) atoms are bridged by a pair of carboxylato groups, showing a skew-bridge mode, and thus enabling a long Zn(Ⅱ)…Zn(Ⅱ) separation. As we know, it is a dinuclear coordination compound with the longest Zn…Zn separation.展开更多
Six coordination compounds of Pt(Ⅱ)L_2 and Ir(Ⅲ)L_3 type(where L is PT^-, 3Me-PT^-or 4Me-PT^-)are reported here.Four coordination compounds of the latter two ligands have never been reported before,while PT^-'s ...Six coordination compounds of Pt(Ⅱ)L_2 and Ir(Ⅲ)L_3 type(where L is PT^-, 3Me-PT^-or 4Me-PT^-)are reported here.Four coordination compounds of the latter two ligands have never been reported before,while PT^-'s were synthesized with H_2PtCl_6 and(NH_4)_3IrCl_6 respectively,which were different from the methods of Davidson et al.~1 and Sterinbrech^2.They were characterized by elemental analysis, UV,IR,~1HNMR and molar conductance.Their structural formulas have been determined,and the mechanism of synthetic reaction has been discussed.展开更多
The stability of the coordination compounds of the first transition series metal ions(Mn(Ⅱ),Co(Ⅱ),Ni(Ⅱ),Cu(Ⅱ)and Zn(Ⅱ))with 2-mercaptopyridine-1- oxide is reported.A coordination compound CoL_2 is synthesized and...The stability of the coordination compounds of the first transition series metal ions(Mn(Ⅱ),Co(Ⅱ),Ni(Ⅱ),Cu(Ⅱ)and Zn(Ⅱ))with 2-mercaptopyridine-1- oxide is reported.A coordination compound CoL_2 is synthesized and characterized for the first time.展开更多
In this paper protonation constants of the title lisand and stability constants of its coordination compounds with rare earths have been determined by potentiometric titration at 25±0.1℃ and ionic strength of 0....In this paper protonation constants of the title lisand and stability constants of its coordination compounds with rare earths have been determined by potentiometric titration at 25±0.1℃ and ionic strength of 0.10mol.dm^(-3)NaClO_4. The coordination of rare earths with DL-alanyl-alanine has been discussed. The stability of the coordination compound shows 'tetrad effect'. The position for yttrium shifts from its usual Bo-Er region to the vicinity of Tb.展开更多
In this paper,we report the deductive formula used for the method of dual-wavelength corresponding solutions under condition of having ligand interference and the stability constants of three new coordination compound...In this paper,we report the deductive formula used for the method of dual-wavelength corresponding solutions under condition of having ligand interference and the stability constants of three new coordination compounds [AuL_2]^+determined with this method.The stability of the three compounds,the necessity of controlling pH in experimental systems and the advantage of this method are discussed in detail.展开更多
<span style="font-family:Verdana;">Coordination compounds of 2-amino-3-methylbutanoic acid were synthesized with chromium(III) and oxovanadium(IV) ions. M:L;1:2. Adducts of these complexes using 1,10-p...<span style="font-family:Verdana;">Coordination compounds of 2-amino-3-methylbutanoic acid were synthesized with chromium(III) and oxovanadium(IV) ions. M:L;1:2. Adducts of these complexes using 1,10-phenantroline and ethylenediamine were further synthesized, M:L, (1:2). These compounds were characterized using electronic, infra-red spectrophotometry, magnetic susceptibility measurement and percentage metal analyses. The zones of inhibition and minimum inhibitory concentrations of the compounds against eight microbes were studied. The results obtained indicated an octahedral geometry for the Cr(III) complexes, indicative of additional coordination of two water molecules. On the other hand a square pyramid geometry was obtained for the binary oxovanadium complex and its 1,10-phenantroline adduct. However</span><span style="font-family:Verdana;"><span style="font-family:Verdana;"><span style="font-family:Verdana;">,</span></span></span><span style="font-family:Verdana;"><span style="font-family:Verdana;"><span style="font-family:Verdana;"> for the oxovanadium ethylenediamine adduct a distorted octahedral geometry was proposed. The result for the antibacterial studies indicated that both mixed ligand complexes of 1,10-phenantroline exhibited good antibacterial activity, and in some cases better activity than the standard, streptomycin.</span></span></span>展开更多
<span style="font-family:Verdana;">Coordination compounds of 3-hydroxy-2-methyl-4</span><i><span style="font-family:Verdana;">H</span></i><span style="fo...<span style="font-family:Verdana;">Coordination compounds of 3-hydroxy-2-methyl-4</span><i><span style="font-family:Verdana;">H</span></i><span style="font-family:Verdana;">-pyran-4-one with </span><span style="font-family:Verdana;">iron(III), cobat(III) and chromium(III) were synthesized with M:L (1:2)</span><span style="font-family:Verdana;">. Mixed ligand coordination compounds of 3-hydroxy-2-methyl-4</span><i><span style="font-family:Verdana;">H</span></i><span style="font-family:Verdana;">-pyran-4-one and 1,2-diaminocyclohexane using the same metal ions were also synthesized </span><b><span style="font-family:Verdana;">M:L1</span></b><span style="font-family:Verdana;">:</span><b><span style="font-family:Verdana;">L2</span></b><span style="font-family:Verdana;"> (1:1:1) where </span><b><span style="font-family:Verdana;">L1</span></b><span style="font-family:Verdana;"> is 3-hydroxy-2-methyl-4</span><i><span style="font-family:Verdana;">H</span></i><span style="font-family:Verdana;">-pyran-4-one and </span><b><span style="font-family:Verdana;">L2</span></b><span style="font-family:Verdana;"> is 1,2-diaminocyclohexane. The coordination compounds obtained were characterized using electronic and infrared spectral analyses, magnetic susceptibility and percentage metal analysis. They were also evaluated for their cytotoxic and antioxidant activities. The result obtained suggested that octahedral geometry was obtained for all the compounds, as a result of additional two molecules of the solvent coordinated to the metal ions. Both the primary and secondary ligands coordinated in a bidentate fashion. The synthesized compounds exhibited moderate cytotoxicity, although none was as active as the standard. The cobalt(III) mixed ligand complex elicited the highest activity. The synthesized compounds all exhibited good to moderate antioxidant activity.</span>展开更多
Two novel energetic coordination compounds Zn2（DAT）5（H2O）3（TNR）2 and Co2（DAT）5（H2O）3（TNR）2 were synthesized and their structures were characterized by elemental analysis and FT-IR spectroscopy.The crystal ...Two novel energetic coordination compounds Zn2（DAT）5（H2O）3（TNR）2 and Co2（DAT）5（H2O）3（TNR）2 were synthesized and their structures were characterized by elemental analysis and FT-IR spectroscopy.The crystal structures were determined by single-crystal X-ray diffraction.The results reveal that the compounds have similar molecular structures and the crystals belong to the triclinic system,space group P with a = 11.491（3）,b = 13.564（3）,c = 15.496（3） ,V = 2180.4（8） 3,C17H28 Zn2N36O19,Mr = 1203.02 g·mol-1,Dc = 1.832 g·cm-3,μ（MoKα） = 1.221 mm-1,F（000） = 1223,Z = 2,R = 0.0596 and wR = 0.1514 for 11289 observed reflections（I 〉 2σ（I）） for Zn2（DAT）5（H2O）3（TNR）2 and a = 11.5291（13）,b = 13.4894（15）,c = 15.4852（17） ,V = 2164.8（4） 3,C17H28Co2N36O19,Mr = 1190.14 g·mol-1,Dc = 1.826 g·cm-3,μ（MoKα） = 0.888 mm-1,F（000） = 1211,Z = 2,R = 0.0576 and wR = 0.1431 for 11218 observed reflections（I 〉 2σ（I）） for Co2（DAT）5（H2O）3（TNR）2,respectively.The thermal decomposition characteristics of the com-pounds were investigated using differential scanning calorimetry and thermal gravimetry-diffediffer-rential thermal gravimetry.The results of thermal decomposition processes were similar for the two compounds.Both undergo four-step decomposition after the loss of coordinated H2O molecules.The final solid residues for the two DAT complexes were the corresponding metal oxides.The kinetic parameter of the first exothermic process of the compounds was studied by applying the Kissinger and Ozawa-Doyle methods.The thermodynamic parameters of the activation could be calculated.Sensitivity tests revealed that Co2（DAT）5（H2O）3（TNR）2 was more sensitive than Zn2（DAT）5（H2O）3（TNR）2.展开更多
Two coordination compounds, namely [Ce（3,5-Br2BC）3（3,5-HBrzBC）]n （1） and [Zn（3,5-Br2BC）2（phen）] （2, 3,5-HBr2BC = 3,5-dibromobenzoic acid, phen = 1,10-phenanthroline）, were assembled. Single-crystal X-ray d...Two coordination compounds, namely [Ce（3,5-Br2BC）3（3,5-HBrzBC）]n （1） and [Zn（3,5-Br2BC）2（phen）] （2, 3,5-HBr2BC = 3,5-dibromobenzoic acid, phen = 1,10-phenanthroline）, were assembled. Single-crystal X-ray diffraction studies show that compound 1 possesses a ID chain coordination network, which is further extended into a 3D supramolecular architecture via Br..＇Br and Br＇＂O halogen bonding. Compound 2 consists of a mononuclear molecule, which is assembled to a 3D supramolecular framework through C-H..-O hydrogen bond, π-π stacking interactions and Br..π halogen bonding. Luminescent and magnetic properties of both compounds have also been studied.展开更多
<span style='font-family:Verdana;font-size:12px;'>The medicinal uses and applications of metal complexes are of increasing clinical and commercial importance;this is as a result of some level of success ...<span style='font-family:Verdana;font-size:12px;'>The medicinal uses and applications of metal complexes are of increasing clinical and commercial importance;this is as a result of some level of success </span><span style='font-family:Verdana;font-size:12px;'>achieved so far. In this regard, novel enamine free-base ligands were synthesized</span><span style='font-family:Verdana;font-size:12px;'> by the condensation of terephthalaldehyde and 2-(methylamino)ethanol. This afforded a dinegative </span><i><span style='font-family:Verdana;font-size:12px;'>ONNO</span></i><span style='font-family:Verdana;font-size:12px;'> donor enamine, free base, characterized using </span><sup><span style='font-family:Verdana;font-size:12px;'>1</span></sup><span style='font-family:Verdana;font-size:12px;'>H and </span><sup><span style='font-family:Verdana;font-size:12px;'>13</span></sup><span style='font-family:Verdana;font-size:12px;'>C NMR, Fourier-transformed infrared and UV-vis spectroscopy. Coordination compounds of the enamine were also synthesized using Cu(II), Ni(II), Co(II) and VO(IV) ions. These complexes were characterized by electronic, IR spectrophotometry, mass spectrometry, magnetic susceptibility and </span><span style='font-family:Verdana;font-size:12px;'>E</span><span style='font-family:Verdana;font-size:12px;'>DX. The compounds were thereafter evaluated for their antimicrobial and cytotoxic activities. The data obtained w</span><span style='font-size:12px;font-family:Verdana;'>ere</span><span style='font-size:12px;font-family:Verdana;'> supportive of a</span><span style='font-size:12px;font-family:Verdana;'>n</span><span style='font-size:10.0pt;font-family:''><span style='font-family:Verdana;font-size:12px;'> octahedral geometry</span><span style='font-family:Verdana;font-size:12px;'> for the Cu(II) complex, a square-pyramidal geometry for the vanadium complex and a 4-coordinate square-planar geometry for both the cobalt and nickel complexes. The magnetic susceptibility data revealed that the complexes are magnetically dilute and mononuclear with exception of the cobalt complex. The ligands and the complexes did not exhibit significant antimicrobial and cytotoxic assays, indicative of the nontoxicity of the ligand and complexe</span><span style='font-family:Verdana;font-size:12px;'>s.</span></span>展开更多
<span style="font-family:Verdana;">Aminoethanoic acid undergoes condensation with 1,4-benzenedicarboxaldehyde</span><span><span><span style="font-family:""><sp...<span style="font-family:Verdana;">Aminoethanoic acid undergoes condensation with 1,4-benzenedicarboxaldehyde</span><span><span><span style="font-family:""><span style="font-family:Verdana;"> to form an O, N, N, O donor Schiff base, </span><i><span style="font-family:Verdana;">N,N'</span></i><span style="font-family:Verdana;">-di(carboxymethylene)</span></span></span></span><span><span><span style="font-family:""> </span></span></span><span><span><span style="font-family:""><span style="font-family:Verdana;">terephthalaldehyde, Ligand L. Coordination compounds of this Schiff base us</span><span><span style="font-family:Verdana;">ing Ni (II), Cu (II), </span><span style="font-family:Verdana;">VO</span><span style="font-family:Verdana;"> (IV) and Co (II) were then obtained </span><i><span style="font-family:Verdana;">in-situ</span></i><span style="font-family:Verdana;">. The</span></span><span style="font-family:Verdana;"> Schiff base and the complexes were evaluated for their antimicrobial and DNA binding abilities. Molecular docking studies of the ligand and synthesized compounds were also carried out. Evidence for the formation of the Schiff base coordination compounds and the coordinating atoms was obtained from </span><sup><span style="font-family:Verdana;">1</span></sup><span style="font-family:Verdana;">H NMR, infrared and ultraviolet spectral data, EDX, EDTA complexometric titration and magnetic susceptibility measurement. The results obtained are consistent with octahedral geometry for Ni (II) complex</span></span></span></span><span style="font-family:Verdana;"><span style="font-family:Verdana;"><span style="font-family:Verdana;">,</span></span></span><span style="font-family:Verdana;"><span style="font-family:Verdana;"><span style="font-family:Verdana;"> the metal ion coordinating to one molecule of Ligand L</span></span></span><span style="font-family:Verdana;"><span style="font-family:Verdana;"><span style="font-family:Verdana;"> and</span></span></span><span style="font-family:Verdana;"><span style="font-family:Verdana;"><span style="font-family:Verdana;"> with additional coordination with two oxygen atoms of two molecules of the solvent. A square-planar geometry was suggested for both Co (II), and Cu (II) complexes and a five-coordinate, square pyramidal geometry for the VO (IV) complex. The results further indicated that the carboxylic acid of Ligand L was not deprotonated both in the free base and also the complexes. In addition, the results showed that Compound 2 elicited the best antimicrobial activity potential. Generally, the compounds exhibited considerable good affinity to CT-DNA.</span></span></span>展开更多
Based on the ideas of coordination and design chemistry,we propose a new strategy to break through the limitation of the number of oxidizing acid radicals in energetic coordination compounds by preparing multi-functio...Based on the ideas of coordination and design chemistry,we propose a new strategy to break through the limitation of the number of oxidizing acid radicals in energetic coordination compounds by preparing multi-functional type energetic coordination compounds.Therefore,we creatively designed and prepared the ligand 5-amino-1-methyl-pyrazole-4-carbohydrazide(AMPZCA)and complex Cu(HAMPZCA)_(2)(ClO_(4))_(4)·2H_(2)O(ECCs-1).As expected,the structure of ECCs-1 was a double-type ionic-salt coordination compound,which was proved by IR,EA,and single-crystal XRD.Because of the special structural combination,ECCs-1 has more ClO_(4)^(−),higher OB value,and excellent detonation performance(D=7700 m s^(−1),P=27.9 GPa).In addition,ECCs-1 exhibits acceptable mechanical sensitivity due to the introduction of methyl groups in the ligand(IS=10 J,FS=40 N).Laser initiation and detonation initiation tests show that ECCs-1 has the potential to play a dual role as both primary and secondary explosives.展开更多
The development of novel coordination compounds as energetic materials still faces significant challenges,particularly in overcoming the proportion of negative ions,which is a challenging task.Here,we prepare the liga...The development of novel coordination compounds as energetic materials still faces significant challenges,particularly in overcoming the proportion of negative ions,which is a challenging task.Here,we prepare the ligand HDAPZCA(3,5-diamino-1H-pyrazole-4-carbohydrazide),whose skeletal ring and substituent play different roles.展开更多
Synthesis,characterization(HRMS,NMR,EPR,UV-Vis spectroscopy,and electrochemistry)and in vitro cytotoxic investigation of a series of new ferrocene-containing derivatives,based onω-ferrocene carboxylic acids and 2-alk...Synthesis,characterization(HRMS,NMR,EPR,UV-Vis spectroscopy,and electrochemistry)and in vitro cytotoxic investigation of a series of new ferrocene-containing derivatives,based onω-ferrocene carboxylic acids and 2-alkylthioimidazolin-4-ones as well as their copper coordination compounds,have been reported.A series of ferrocene–imidazolone conjugates with different lengths and donor properties of the linker fragments have been synthesized;all the obtained compounds were studied in complexation reactions with copper(Ⅰ)and copper(Ⅱ)perchlorates.It is shown that the synthesised conjugates rapidly and efficiently convert coordinating copper ions into the Cu(+1)oxidation state,but a change in the length of the linker in ferrocene–imidazolone ligands fundamentally changes the ratio of products formed as a result of iron oxidation/copper reduction and complexation by various mechanisms.After comparing the data on the qualitative and quantitative composition of the reaction mixtures and the kinetic characteristics of the processes occurring in the mixtures of ferrocene–imidazolones with copper(II)perchlorate,a scheme of the ongoing reactions was proposed which may fully explain all the observed processes and products.It has been shown that the obtained bimetallic Cu/Fe coordination compounds are more toxic than cisplatin and induce apoptosis in micromolar concentrations on Hek-293 and MCF-7 cell lines.展开更多
In this study we present a(re-)investigation into cyclodimethylsiloxanes in relation to silyl-ether bonding towards alkali metal ions.We demonstrate that all(non-radioactive)alkali metal ions can be incorporated into ...In this study we present a(re-)investigation into cyclodimethylsiloxanes in relation to silyl-ether bonding towards alkali metal ions.We demonstrate that all(non-radioactive)alkali metal ions can be incorporated into D_(n) cyclosiloxane frameworks(D=(SiMe_(2)O),n=5–8),employing appropriate cation–anion combinations.Starting with the Li^(+)cation we were able to observe the coordination of D_(5) with Li^(+)based on a suitable X-ray structure after reacting D_(5) with LiI and GaI_(3).Due to template effects,the dinuclear coordination compound[Li2(D_(5))(D_(6))(GaI_(4))_(2)](1)was obtained.The direct reaction of D_(6) with LiI and GaI_(3) yields[Li(D_(6))GaI_(4)](2)in quantitative yield.Na^(+)ions could be trapped in D_(6) and D_(7) ligand moieties after the conversion of NaI,GaI_(3),and the respective siloxane.The molecular structure of[Na(D_(6))GaI_(4)](3)reveals a six-fold coordinated Na^(+)ion,which is located on top of the siloxane D_(6).In the case of[Na(D_(7))(DCM)GaI_(4)](4),the larger ligand D_(7) provides 15-crown-5-like geometry in which the sodium ion is coordinated by the ligand in a coplanar fashion and further saturated by the solvent DCM(DCM=dichloromethane).The K^(+)ion was bound within the D_(7) ligand in a similar manner and[K(D_(7))(DCM)GaI_(4)](5)could be characterized.Due to the resemblance of NH_(4)^(+)to K^(+),this cation was also employed for complex formation.Counterintuitively,we were able to synthesize and characterize the first ever non-metal-cyclosiloxane coordination compound.After the conversion of D_(6) with NH_(4)I and GaI_(3),the compound[NH_(4)(D_(7))][Ga_(2)I_(7)](6)was obtained.The ammonium cation favors D_(7) coordination over D_(6),and the willing formation of hydrogen bonding in such a siloxane moiety was realized.As these compounds could be obtained,we also tested the limits of silyl-ether bonding.Therefore,we reacted D_(8) with in situ generated Rb[GaI_(4)]and Cs[GaI_(4)].In the case of Rb^(+),we could cumbersomely characterize[Rb(D_(8))(DCM)GaI_(4)](7)via an X-ray structure,as well as by means of mass spectrometry,but the compound starts decomposing readily in solution.The reaction with the Cs^(+)salt failed.To obtain meaningful spectroscopic data from a Rb^(+)compound and to somehow obtain a Cs^(+)complex,we employed the weakly coordinating anion[Al_(F)]^(−)(Al_(F)^(−)=[Al{OC(CF_(3))_(3)}_(4)]^(−)).The conversion of M[Al_(F)]then yielded 11[M(D_(8))AL_(F)](M=Rb:8;M=Cs^(+):9)in the solid state.Both compounds 8 and 9 were fully characterized.Finally,we aimed at synthesizing 2:1 complexes of such siloxanes.The reactions of excess D_(5) with K[Al_(F)]and D_(6) with Cs[Al_(F)]turned out to be expedient and,in the forms of[K(D_(5))_(2)][Al_(F)](10)and[Cs(D_(6))_(2)][Al_(F)](12),the first ever sandwich-type complexes observed bearing a cyclosiloxane ligand were characterized.展开更多
基金supported by the National Natural Science Foundation of China(22121005,92372203,92372001,52072186,and 52301278)the National Key Research and Development Program of China(2022YFB2402200)+3 种基金the Science and Technology Plans of Tianjin(23JCYBJC00170)the Fundamental Research Funds for the Central Universities,Nankai University(63241206 and 9242000710)Shanghai Jiao Tong University Shaoxing Research Institute of Renewable Energy and Molecular Engineering(JDSX2023003)the Natural Science Foundation of Jiangsu Province(BK20230937).
文摘Redox-active organic compounds have received much attention as high-capacity electrodes for rechargeable batteries.However,the high solubility in organic electrolytes during charge and discharge processes hinders the practical exploitation of organic compounds.This study presents a cobalt-based metal–organic coordination compound with bifunctional coordinated water(Co-MOC-H_(2)O)for sodium-ion storage.The coordinated water enhances interactions between sodium ions and nitrogen atoms in organic ligands through chelation,activating the inert sodium-ion storage sites(C=N).Moreover,the stable hydrogen bonded framework formed by the coordinated water molecules prevents the active organic compounds from dissolving into the electrolyte,thereby enhancing cycling stability.With the bifunctional coordinated water molecules,the Co-MOC-H_(2)O electrode delivers a high capacity of 403 mAh g^(-1)at 0.2 A g^(-1)over 600 cycles and exhibits a capacity retention of 77.9%at 2 A g^(-1)after 1100 cycles.This work highlights the crucial role of the coordinated water molecules in constructing high capacity and long-life sodium-ion storage materials.
文摘<span style="font-family:Verdana;">The present work describes the synthesis of a novel heterocyclic azo dye by </span><span style="font-family:Verdana;">general diazonization of 2-amino-4,5-dimethylthiazole followed by the di</span><span style="font-family:Verdana;">azo-</span><span><span><span style="font-family:;" "=""> </span></span></span><span><span><span style="font-family:;" "=""><span style="font-family:Verdana;">coupling of the resulting diazonium ion with 5-methyl-2-(propan-2-</span><span><span style="font-family:Verdana;">yl)phenol to obtain ligand </span><b><span style="font-family:Verdana;">L</span></b><span style="font-family:Verdana;">. This was characterized using Fouri</span></span><span style="font-family:Verdana;">er-transformed infrared and electronic spectrophotometry. Ligand </span><b><span style="font-family:Verdana;">L </span></b><span style="font-family:Verdana;">was further coordinated with five </span><span style="font-family:Verdana;">metal ions, M:L, 1:2 </span></span></span></span><span style="font-family:Verdana;"><span style="font-family:Verdana;"><span style="font-family:Verdana;">[</span></span></span><span style="font-family:Verdana;"><span style="font-family:Verdana;"><span style="font-family:Verdana;">M</span></span></span><span><span><span style="font-family:;" "=""> </span></span></span><span style="font-family:Verdana;"><span style="font-family:Verdana;"><span style="font-family:Verdana;">= Cu(II), Mn(II), Zn(II), Ni(II) and Co(II)</span></span></span><span style="font-family:Verdana;"><span style="font-family:Verdana;"><span style="font-family:Verdana;">]</span></span></span><span style="font-family:Verdana;"><span style="font-family:Verdana;"><span style="font-family:Verdana;">. The </span></span></span><span><span><span style="font-family:;" "=""><span style="font-family:Verdana;">coordination compounds obtained were characterized by electronic, IR spectrophotometry, magnetic susceptibility and percentage metal analyses. The results obtained suggested that a thiazoylazo dye was obtained as ligand </span><b><span style="font-family:Verdana;">L</span></b><span style="font-family:Verdana;">. It was proposed that two molecules of the solvent coordinated to the metal ion in addition with the ligands to give an octahedral geometry for copper(II), manganese(II) and nickel(II) complexes. On the other hand, square planar </span><span style="font-family:Verdana;">geometry was suggested for zinc(II) and cobalt(II) complexes. The an</span><span style="font-family:Verdana;">ti-infla</span></span></span></span><span style="font-family:Verdana;"><span style="font-family:Verdana;"><span style="font-family:Verdana;">- </span></span></span><span><span><span style="font-family:;" "=""><span style="font-family:Verdana;">mmatory activity of the ligand and coordination compounds was evaluated using four </span><i><span style="font-family:Verdana;">in</span></i> <i><span style="font-family:Verdana;">vitro</span></i><span style="font-family:Verdana;">-based assays viz: </span><span><span style="font-family:Verdana;">xanthine oxidase and lipoxygenase inhibition assay, membrane stability and protein denaturation assay. The synthesized compounds generally exhibited good anti-inflammatory activity in all </span><span style="font-family:Verdana;">the assays carried out. However, the reference standards, in this instance,</span><span style="font-family:Verdana;"> were more effective in the case of xanthine oxidase, lipoxygenase and protein denaturation inhibitory assays. For the membrane stability study, the </span><span><span style="font-family:Verdana;">coordination compounds and ligand </span><b><span style="font-family:Verdana;">L </span></b><span style="font-family:Verdana;">elicited more potent anti-inflammatory</span></span><span style="font-family:Verdana;"> activity than the standard drug.</span></span></span></span></span>
基金The Deanship of Scientific Research at Princess Nourah bint Abdulrahman University,through the Research Groups Program Grant no.(RGP-1440-0003)
文摘In this work,we have reported the synthesis and spectroscopic characterization of captopril(Cap)coordination compounds:Cu(Cap)·2H 2O,Cr(Cap)·H 2O,Zn(Cap)·3H 2O and Mg(Cap)4.Herein,it is worthily mentioned that the FTIR spectroscopic technique was employed to recognized the nature of coordination between captopril ligand and copper,chromium,zinc and magnesium(Ⅱ)metal ions.In view of the infrared spectroscopic tool,the copper(Ⅱ)metal ion coordinated toward captopril drug ligand through sulfur atom of SH group dependent on the absent of stretching vibration band of—SH.Based on this result,the stretching motion ofνa(COO)shifts clearly indicates that Cu 2+,Cr 2+,Zn 2+and Mg 2+the carboxylic group is employed as coordinative site for all compounds as a metal-ligand coordinative bond.As a general behavior,it is verified that the coordination compound thermal stability(considering the release of captopril molecules,not the release of water molecules)is affected by the metal cation radius:minor radius is associated with higher thermal stability,probably due to a higher metal-captopril bond dissociation enthalpy.
基金Subject supported by the Doctoral Foundation of National Education Commission of China
文摘The coordination compounds,{Cu[CH_3C_6H_4N(CH_2COO)_2]}.2H_2O and {Cu[CH_3OC_6H_4N(CH_2COO)_2]}.2H_2O,have been prepared and its crystal struc- tures determined.The final discrepancy factors are R=0.052,R_w=0.061 for (I)and R=0.052,R_w=0.039 for(Ⅱ).The geometry of the coordination poly- hedron with Cu(Ⅱ)is a distorted tetragonal pyramid for(Ⅰ)and an unsym- metrical and extended tetragonal bipyramid for(Ⅱ),respectively.The re- sults of EHMO calculations indicate that the ligand mainly provided the field with very few of its electrons being coordinated to the central atom.
基金Project supported by the National Natural Science Foundation of China
文摘[Cu_(0.84)Au_(0.16)(PPh_3)_2(SC(Ph)NHPh)Cl]·0.5CS_2=,Mr=895.79,monoclinic,space group P2_1/a,a=17.231(3),b=14.611(2),c=18.000(3) ,β=105.56(2)°,V=4365(1) ~3, Z=4,D_c=1.37g/cm^3.,λ(MoK_α)=0.71073 ,μ=12.15cm^(-1),F(000)=1855,R=0.052, R_W=0.045 for 3930 observed reflections with Ⅰ>1.5σ(Ⅰ).The central metal atom has a dis. torted tetrahedral geometry with bond lengths Cu-S=2.384(2) (Au-S=2.389(4)), Cu-Cl=2.481(3)(Au-Cl=2.474(1))and Cu-P=2.269(2)-2.289(2)(Au-P=2.270(4)-2.279(4)) .
文摘Two novel coordination compounds of Zn(Ⅱ) with Ph_3P+(CH_2)_2CO-_2(L), namely, [ZnL_4(H_2O)_2]·(ClO_4)_2·2H_2O(compound 1) and [Zn_2Cl_4(μ-L-O,O′)_2](compound 2), have been prepared. The single crystal X-ray structure analysis of these compounds indicates that in compound 1 the Zn(Ⅱ) atom is coordinated by four monodentate carboxylato groups on the equatorial plane and two aqua ligands occupy the axial coordination positions. The pendant oxygen atoms form strong hydrogen bonds with the aqua molecules which results in the stability of this structure. In compound 2, two Zn(Ⅱ) atoms are bridged by a pair of carboxylato groups, showing a skew-bridge mode, and thus enabling a long Zn(Ⅱ)…Zn(Ⅱ) separation. As we know, it is a dinuclear coordination compound with the longest Zn…Zn separation.
文摘Six coordination compounds of Pt(Ⅱ)L_2 and Ir(Ⅲ)L_3 type(where L is PT^-, 3Me-PT^-or 4Me-PT^-)are reported here.Four coordination compounds of the latter two ligands have never been reported before,while PT^-'s were synthesized with H_2PtCl_6 and(NH_4)_3IrCl_6 respectively,which were different from the methods of Davidson et al.~1 and Sterinbrech^2.They were characterized by elemental analysis, UV,IR,~1HNMR and molar conductance.Their structural formulas have been determined,and the mechanism of synthetic reaction has been discussed.
文摘The stability of the coordination compounds of the first transition series metal ions(Mn(Ⅱ),Co(Ⅱ),Ni(Ⅱ),Cu(Ⅱ)and Zn(Ⅱ))with 2-mercaptopyridine-1- oxide is reported.A coordination compound CoL_2 is synthesized and characterized for the first time.
文摘In this paper protonation constants of the title lisand and stability constants of its coordination compounds with rare earths have been determined by potentiometric titration at 25±0.1℃ and ionic strength of 0.10mol.dm^(-3)NaClO_4. The coordination of rare earths with DL-alanyl-alanine has been discussed. The stability of the coordination compound shows 'tetrad effect'. The position for yttrium shifts from its usual Bo-Er region to the vicinity of Tb.
文摘In this paper,we report the deductive formula used for the method of dual-wavelength corresponding solutions under condition of having ligand interference and the stability constants of three new coordination compounds [AuL_2]^+determined with this method.The stability of the three compounds,the necessity of controlling pH in experimental systems and the advantage of this method are discussed in detail.
文摘<span style="font-family:Verdana;">Coordination compounds of 2-amino-3-methylbutanoic acid were synthesized with chromium(III) and oxovanadium(IV) ions. M:L;1:2. Adducts of these complexes using 1,10-phenantroline and ethylenediamine were further synthesized, M:L, (1:2). These compounds were characterized using electronic, infra-red spectrophotometry, magnetic susceptibility measurement and percentage metal analyses. The zones of inhibition and minimum inhibitory concentrations of the compounds against eight microbes were studied. The results obtained indicated an octahedral geometry for the Cr(III) complexes, indicative of additional coordination of two water molecules. On the other hand a square pyramid geometry was obtained for the binary oxovanadium complex and its 1,10-phenantroline adduct. However</span><span style="font-family:Verdana;"><span style="font-family:Verdana;"><span style="font-family:Verdana;">,</span></span></span><span style="font-family:Verdana;"><span style="font-family:Verdana;"><span style="font-family:Verdana;"> for the oxovanadium ethylenediamine adduct a distorted octahedral geometry was proposed. The result for the antibacterial studies indicated that both mixed ligand complexes of 1,10-phenantroline exhibited good antibacterial activity, and in some cases better activity than the standard, streptomycin.</span></span></span>
文摘<span style="font-family:Verdana;">Coordination compounds of 3-hydroxy-2-methyl-4</span><i><span style="font-family:Verdana;">H</span></i><span style="font-family:Verdana;">-pyran-4-one with </span><span style="font-family:Verdana;">iron(III), cobat(III) and chromium(III) were synthesized with M:L (1:2)</span><span style="font-family:Verdana;">. Mixed ligand coordination compounds of 3-hydroxy-2-methyl-4</span><i><span style="font-family:Verdana;">H</span></i><span style="font-family:Verdana;">-pyran-4-one and 1,2-diaminocyclohexane using the same metal ions were also synthesized </span><b><span style="font-family:Verdana;">M:L1</span></b><span style="font-family:Verdana;">:</span><b><span style="font-family:Verdana;">L2</span></b><span style="font-family:Verdana;"> (1:1:1) where </span><b><span style="font-family:Verdana;">L1</span></b><span style="font-family:Verdana;"> is 3-hydroxy-2-methyl-4</span><i><span style="font-family:Verdana;">H</span></i><span style="font-family:Verdana;">-pyran-4-one and </span><b><span style="font-family:Verdana;">L2</span></b><span style="font-family:Verdana;"> is 1,2-diaminocyclohexane. The coordination compounds obtained were characterized using electronic and infrared spectral analyses, magnetic susceptibility and percentage metal analysis. They were also evaluated for their cytotoxic and antioxidant activities. The result obtained suggested that octahedral geometry was obtained for all the compounds, as a result of additional two molecules of the solvent coordinated to the metal ions. Both the primary and secondary ligands coordinated in a bidentate fashion. The synthesized compounds exhibited moderate cytotoxicity, although none was as active as the standard. The cobalt(III) mixed ligand complex elicited the highest activity. The synthesized compounds all exhibited good to moderate antioxidant activity.</span>
基金supported by the National Natural Science Foundation of China (NSAF: 10776002)the project of State Key Laboratory of Science and Technology (No. QNKT11-06, YBKY10-03)the Program for New Century Excellent Talents in University (NCET-09-0051)
文摘Two novel energetic coordination compounds Zn2（DAT）5（H2O）3（TNR）2 and Co2（DAT）5（H2O）3（TNR）2 were synthesized and their structures were characterized by elemental analysis and FT-IR spectroscopy.The crystal structures were determined by single-crystal X-ray diffraction.The results reveal that the compounds have similar molecular structures and the crystals belong to the triclinic system,space group P with a = 11.491（3）,b = 13.564（3）,c = 15.496（3） ,V = 2180.4（8） 3,C17H28 Zn2N36O19,Mr = 1203.02 g·mol-1,Dc = 1.832 g·cm-3,μ（MoKα） = 1.221 mm-1,F（000） = 1223,Z = 2,R = 0.0596 and wR = 0.1514 for 11289 observed reflections（I 〉 2σ（I）） for Zn2（DAT）5（H2O）3（TNR）2 and a = 11.5291（13）,b = 13.4894（15）,c = 15.4852（17） ,V = 2164.8（4） 3,C17H28Co2N36O19,Mr = 1190.14 g·mol-1,Dc = 1.826 g·cm-3,μ（MoKα） = 0.888 mm-1,F（000） = 1211,Z = 2,R = 0.0576 and wR = 0.1431 for 11218 observed reflections（I 〉 2σ（I）） for Co2（DAT）5（H2O）3（TNR）2,respectively.The thermal decomposition characteristics of the com-pounds were investigated using differential scanning calorimetry and thermal gravimetry-diffediffer-rential thermal gravimetry.The results of thermal decomposition processes were similar for the two compounds.Both undergo four-step decomposition after the loss of coordinated H2O molecules.The final solid residues for the two DAT complexes were the corresponding metal oxides.The kinetic parameter of the first exothermic process of the compounds was studied by applying the Kissinger and Ozawa-Doyle methods.The thermodynamic parameters of the activation could be calculated.Sensitivity tests revealed that Co2（DAT）5（H2O）3（TNR）2 was more sensitive than Zn2（DAT）5（H2O）3（TNR）2.
基金supported by the Natural Science Foundation of Shanxi Province(No.2013011011-6)the Subject Team of Taiyuan University of Science and Technology
文摘Two coordination compounds, namely [Ce（3,5-Br2BC）3（3,5-HBrzBC）]n （1） and [Zn（3,5-Br2BC）2（phen）] （2, 3,5-HBr2BC = 3,5-dibromobenzoic acid, phen = 1,10-phenanthroline）, were assembled. Single-crystal X-ray diffraction studies show that compound 1 possesses a ID chain coordination network, which is further extended into a 3D supramolecular architecture via Br..＇Br and Br＇＂O halogen bonding. Compound 2 consists of a mononuclear molecule, which is assembled to a 3D supramolecular framework through C-H..-O hydrogen bond, π-π stacking interactions and Br..π halogen bonding. Luminescent and magnetic properties of both compounds have also been studied.
文摘<span style='font-family:Verdana;font-size:12px;'>The medicinal uses and applications of metal complexes are of increasing clinical and commercial importance;this is as a result of some level of success </span><span style='font-family:Verdana;font-size:12px;'>achieved so far. In this regard, novel enamine free-base ligands were synthesized</span><span style='font-family:Verdana;font-size:12px;'> by the condensation of terephthalaldehyde and 2-(methylamino)ethanol. This afforded a dinegative </span><i><span style='font-family:Verdana;font-size:12px;'>ONNO</span></i><span style='font-family:Verdana;font-size:12px;'> donor enamine, free base, characterized using </span><sup><span style='font-family:Verdana;font-size:12px;'>1</span></sup><span style='font-family:Verdana;font-size:12px;'>H and </span><sup><span style='font-family:Verdana;font-size:12px;'>13</span></sup><span style='font-family:Verdana;font-size:12px;'>C NMR, Fourier-transformed infrared and UV-vis spectroscopy. Coordination compounds of the enamine were also synthesized using Cu(II), Ni(II), Co(II) and VO(IV) ions. These complexes were characterized by electronic, IR spectrophotometry, mass spectrometry, magnetic susceptibility and </span><span style='font-family:Verdana;font-size:12px;'>E</span><span style='font-family:Verdana;font-size:12px;'>DX. The compounds were thereafter evaluated for their antimicrobial and cytotoxic activities. The data obtained w</span><span style='font-size:12px;font-family:Verdana;'>ere</span><span style='font-size:12px;font-family:Verdana;'> supportive of a</span><span style='font-size:12px;font-family:Verdana;'>n</span><span style='font-size:10.0pt;font-family:''><span style='font-family:Verdana;font-size:12px;'> octahedral geometry</span><span style='font-family:Verdana;font-size:12px;'> for the Cu(II) complex, a square-pyramidal geometry for the vanadium complex and a 4-coordinate square-planar geometry for both the cobalt and nickel complexes. The magnetic susceptibility data revealed that the complexes are magnetically dilute and mononuclear with exception of the cobalt complex. The ligands and the complexes did not exhibit significant antimicrobial and cytotoxic assays, indicative of the nontoxicity of the ligand and complexe</span><span style='font-family:Verdana;font-size:12px;'>s.</span></span>
文摘<span style="font-family:Verdana;">Aminoethanoic acid undergoes condensation with 1,4-benzenedicarboxaldehyde</span><span><span><span style="font-family:""><span style="font-family:Verdana;"> to form an O, N, N, O donor Schiff base, </span><i><span style="font-family:Verdana;">N,N'</span></i><span style="font-family:Verdana;">-di(carboxymethylene)</span></span></span></span><span><span><span style="font-family:""> </span></span></span><span><span><span style="font-family:""><span style="font-family:Verdana;">terephthalaldehyde, Ligand L. Coordination compounds of this Schiff base us</span><span><span style="font-family:Verdana;">ing Ni (II), Cu (II), </span><span style="font-family:Verdana;">VO</span><span style="font-family:Verdana;"> (IV) and Co (II) were then obtained </span><i><span style="font-family:Verdana;">in-situ</span></i><span style="font-family:Verdana;">. The</span></span><span style="font-family:Verdana;"> Schiff base and the complexes were evaluated for their antimicrobial and DNA binding abilities. Molecular docking studies of the ligand and synthesized compounds were also carried out. Evidence for the formation of the Schiff base coordination compounds and the coordinating atoms was obtained from </span><sup><span style="font-family:Verdana;">1</span></sup><span style="font-family:Verdana;">H NMR, infrared and ultraviolet spectral data, EDX, EDTA complexometric titration and magnetic susceptibility measurement. The results obtained are consistent with octahedral geometry for Ni (II) complex</span></span></span></span><span style="font-family:Verdana;"><span style="font-family:Verdana;"><span style="font-family:Verdana;">,</span></span></span><span style="font-family:Verdana;"><span style="font-family:Verdana;"><span style="font-family:Verdana;"> the metal ion coordinating to one molecule of Ligand L</span></span></span><span style="font-family:Verdana;"><span style="font-family:Verdana;"><span style="font-family:Verdana;"> and</span></span></span><span style="font-family:Verdana;"><span style="font-family:Verdana;"><span style="font-family:Verdana;"> with additional coordination with two oxygen atoms of two molecules of the solvent. A square-planar geometry was suggested for both Co (II), and Cu (II) complexes and a five-coordinate, square pyramidal geometry for the VO (IV) complex. The results further indicated that the carboxylic acid of Ligand L was not deprotonated both in the free base and also the complexes. In addition, the results showed that Compound 2 elicited the best antimicrobial activity potential. Generally, the compounds exhibited considerable good affinity to CT-DNA.</span></span></span>
基金the projects of NSFC(22175025)for their generous financial support.
文摘Based on the ideas of coordination and design chemistry,we propose a new strategy to break through the limitation of the number of oxidizing acid radicals in energetic coordination compounds by preparing multi-functional type energetic coordination compounds.Therefore,we creatively designed and prepared the ligand 5-amino-1-methyl-pyrazole-4-carbohydrazide(AMPZCA)and complex Cu(HAMPZCA)_(2)(ClO_(4))_(4)·2H_(2)O(ECCs-1).As expected,the structure of ECCs-1 was a double-type ionic-salt coordination compound,which was proved by IR,EA,and single-crystal XRD.Because of the special structural combination,ECCs-1 has more ClO_(4)^(−),higher OB value,and excellent detonation performance(D=7700 m s^(−1),P=27.9 GPa).In addition,ECCs-1 exhibits acceptable mechanical sensitivity due to the introduction of methyl groups in the ligand(IS=10 J,FS=40 N).Laser initiation and detonation initiation tests show that ECCs-1 has the potential to play a dual role as both primary and secondary explosives.
基金the projects of NSFC(22175025)for their generous financial support.
文摘The development of novel coordination compounds as energetic materials still faces significant challenges,particularly in overcoming the proportion of negative ions,which is a challenging task.Here,we prepare the ligand HDAPZCA(3,5-diamino-1H-pyrazole-4-carbohydrazide),whose skeletal ring and substituent play different roles.
基金the Russian Foundation of Basic Research(Projects No.19-29-08007 and 19-33-90103)for the financial supportsupported by the M.V.Lomonosov Moscow State University Program of Developmentsupported by Russian Science Foundation grant(No.19-79-30062).
文摘Synthesis,characterization(HRMS,NMR,EPR,UV-Vis spectroscopy,and electrochemistry)and in vitro cytotoxic investigation of a series of new ferrocene-containing derivatives,based onω-ferrocene carboxylic acids and 2-alkylthioimidazolin-4-ones as well as their copper coordination compounds,have been reported.A series of ferrocene–imidazolone conjugates with different lengths and donor properties of the linker fragments have been synthesized;all the obtained compounds were studied in complexation reactions with copper(Ⅰ)and copper(Ⅱ)perchlorates.It is shown that the synthesised conjugates rapidly and efficiently convert coordinating copper ions into the Cu(+1)oxidation state,but a change in the length of the linker in ferrocene–imidazolone ligands fundamentally changes the ratio of products formed as a result of iron oxidation/copper reduction and complexation by various mechanisms.After comparing the data on the qualitative and quantitative composition of the reaction mixtures and the kinetic characteristics of the processes occurring in the mixtures of ferrocene–imidazolones with copper(II)perchlorate,a scheme of the ongoing reactions was proposed which may fully explain all the observed processes and products.It has been shown that the obtained bimetallic Cu/Fe coordination compounds are more toxic than cisplatin and induce apoptosis in micromolar concentrations on Hek-293 and MCF-7 cell lines.
基金financially supported by the Deutsche Forschungsgemeinschaft(DFG).
文摘In this study we present a(re-)investigation into cyclodimethylsiloxanes in relation to silyl-ether bonding towards alkali metal ions.We demonstrate that all(non-radioactive)alkali metal ions can be incorporated into D_(n) cyclosiloxane frameworks(D=(SiMe_(2)O),n=5–8),employing appropriate cation–anion combinations.Starting with the Li^(+)cation we were able to observe the coordination of D_(5) with Li^(+)based on a suitable X-ray structure after reacting D_(5) with LiI and GaI_(3).Due to template effects,the dinuclear coordination compound[Li2(D_(5))(D_(6))(GaI_(4))_(2)](1)was obtained.The direct reaction of D_(6) with LiI and GaI_(3) yields[Li(D_(6))GaI_(4)](2)in quantitative yield.Na^(+)ions could be trapped in D_(6) and D_(7) ligand moieties after the conversion of NaI,GaI_(3),and the respective siloxane.The molecular structure of[Na(D_(6))GaI_(4)](3)reveals a six-fold coordinated Na^(+)ion,which is located on top of the siloxane D_(6).In the case of[Na(D_(7))(DCM)GaI_(4)](4),the larger ligand D_(7) provides 15-crown-5-like geometry in which the sodium ion is coordinated by the ligand in a coplanar fashion and further saturated by the solvent DCM(DCM=dichloromethane).The K^(+)ion was bound within the D_(7) ligand in a similar manner and[K(D_(7))(DCM)GaI_(4)](5)could be characterized.Due to the resemblance of NH_(4)^(+)to K^(+),this cation was also employed for complex formation.Counterintuitively,we were able to synthesize and characterize the first ever non-metal-cyclosiloxane coordination compound.After the conversion of D_(6) with NH_(4)I and GaI_(3),the compound[NH_(4)(D_(7))][Ga_(2)I_(7)](6)was obtained.The ammonium cation favors D_(7) coordination over D_(6),and the willing formation of hydrogen bonding in such a siloxane moiety was realized.As these compounds could be obtained,we also tested the limits of silyl-ether bonding.Therefore,we reacted D_(8) with in situ generated Rb[GaI_(4)]and Cs[GaI_(4)].In the case of Rb^(+),we could cumbersomely characterize[Rb(D_(8))(DCM)GaI_(4)](7)via an X-ray structure,as well as by means of mass spectrometry,but the compound starts decomposing readily in solution.The reaction with the Cs^(+)salt failed.To obtain meaningful spectroscopic data from a Rb^(+)compound and to somehow obtain a Cs^(+)complex,we employed the weakly coordinating anion[Al_(F)]^(−)(Al_(F)^(−)=[Al{OC(CF_(3))_(3)}_(4)]^(−)).The conversion of M[Al_(F)]then yielded 11[M(D_(8))AL_(F)](M=Rb:8;M=Cs^(+):9)in the solid state.Both compounds 8 and 9 were fully characterized.Finally,we aimed at synthesizing 2:1 complexes of such siloxanes.The reactions of excess D_(5) with K[Al_(F)]and D_(6) with Cs[Al_(F)]turned out to be expedient and,in the forms of[K(D_(5))_(2)][Al_(F)](10)and[Cs(D_(6))_(2)][Al_(F)](12),the first ever sandwich-type complexes observed bearing a cyclosiloxane ligand were characterized.
