简介:ReactionsofCuSCNwithtetramethylthiuramdisulfideinCH3CNinthepresenceofstyreneandN,N,N',N',N'-pentamethyldiethylenetriaminegaverisetoanewcopper(Ⅰ)complexofN,N'-dimethyldithio-cabamate{[Cu(S2CNMe2)]2}n.ThetitlecompoundcrystallizedinthetriclinicP-1spacegroupwithlatticeparametersα=0.7610(4)nm,b=0.8911(4)nm,c=0.9268(5)nm,α=68.66(1)°,β=83.88(2)°,γ=79.31(2)°,V=0.5748(5)nm^3,Z=2.Thecompoundhasaunique1DchainstructurecomposedofCuSCSCuSCSeight-memberedringsandapairofCu-Sbonds,thestructureofwhichhasbeendeterminedbysingle-crystalX-raycrystallography.Theisolationofthiscompoundmayprovidesomehelpfulinformationforthecauseoftheinductionperiodsofthereverseatomtransferradicalpolymerization.
简介:ThepropertiesofPbn(n=2―30)clustersincludingbindingenergies,seconddifferencesinenergy,andHOMO-LUMOgaps,especiallyfragmentationenergiesandionizationpotentials,havebeenstudiedbyabinitiocalculation.ThemainfragmentationproductsofPbn+areshowntobePb+Pbn-1+forn≤14andtwosmallclusterfragmentsforlargeroneswithn>14.ThePb13+appearsfrequentlyastheproductsinthefragmentationsoflargeclusters.Also,thecalculatedionizationpotentialsoftheclustersareconsistentwiththeexperimentdata.
简介:Aseriesofaromaticimineswerereducedtocorrespondingaminesinexcellentyieldsby2-phenyl-N,N-dimethylbenzimidazoline(PDMBI)photochemicallyinthepresenceofmagnesiumperchloride(Mg(ClO4)2).AMg2+mediatedphotoinducedelectrontransfermechanismwasproposed.
简介:Thetwocompounds,2,2-dimethyl-4-S-(N,N-dimethyldithiocarbamato)-5-(1,2,4-triazol-l-yl)-propione(1)and2,2-dimethyl-4-S-(N,N-diethyldithiocarbamato)-5-(1,2,4-triazol-1-yl)-3-propione(2),werepreparedbyreactingN,N-dialkyldithiocarbamatesodiumwith2,2-dimethyl-4-bromo-5-(1,2,4-triazol-1-yl)-propione.Theirstructureswereidentifiedbyelementalanalysis,IRand^1HNMRspectroscopy.Thestructureof1hasbeendeterminedbyX-raysinglecrystalstructureanalysis.ItcrystallizesinmonoclinicsystemwithspacegroupP21/c,a=1.2315(3)nm,b=1.2057(2)nm,c=1.2532(3)nm,β=118.55(3)°,Z=4,V=1.6345(6)nm^3,Dc=1.221g/cm^3,μ=0.324mm^-1,F(000)=640,finalR1=0.0449.ThereisobviouspotentiallyweakC—H...Nintermolecularinteractioninthecrystal,whichstabilizesthecrystalstructure.Theresultofthebiologicaltestshowedthatthetwocompoundshavefungistasisandplantgrowthregulatingactivities.
简介:Aggregationofsomenitrogen-containingheterocycliccompoundshavebeeninvestigatedbymeansoffluorescencespec-troscopyinaqueousoraquiorganobinarymixturesofdifferentΦvaluesforthefirsttime.TheaggregatorsstudiedareN-butylcarbazole(CBZ-4),N-octylcarbazole(CBZ-8),N-do-decylcarbazole(CBZ-12),andN-hexadecylcarbazole(CBZ-16).Theiraggregatingtendencieshavebeenevaluatedbymeasuringtheircriticalaggregateconcentrationvalues(CAgC’s).OurresultsindicatethattheN-alkylcarbazoles,justliketheanthracenederivativeswithdifferentchain-lengths,canalsobeusedasfluorescenceprobesforevaluatingaggregatingtendenciesorCAgCvalues.
简介:采用HF/DFT的混合泛函PBE0和UPBE0优化了配合物[Os(PH3)2(CN)2(N^N)](其中N^N=2,2′-吡啶)的基态和激发态结构.在基态和激发态结构的基础上,利用含时密度泛函理论(TD-DFT)方法,结合极化连续介质(PCM)模型分别计算了它在二氯甲烷(1)、甲醇(2)、气态(3)和乙腈(4)溶液中的吸收和发射光谱.研究结果表明:优化得到的几何结构参数和相应的实验值符合得非常好.在极性较大的溶剂(2和4)中Os—P(1)和Os—C(1)键较长,Os—N(3)键较短,溶剂的极性会影响配合物的电子云分布.配合物在1-4溶剂中的最低能吸收和发射均来自分子轨道68→71的激发,该激发被指认为[d(Os)+π(CN)+π(N^N)→π*(N^N)]的跃迁具有混合的MLCT/LLCT特征.配合物在1-4溶剂中的最低能吸收和发射分别在471,410,488和445nm以及598,536,634和545nm,表明随着溶剂极性的逐渐增大(3〈1〈4〈2),最低能吸收和发射发生明显的蓝移.这显示出通过改变溶剂极性可以调节配合物的发光颜色.
简介:NineteenL-N-2-hydroxyethylaminoacidsandL-N,N-bis(2-hydroxyethyl)aminoacidswerepreparedfromthereactionofchlorohydrinwithL-alanine,L-valine,L-leucine,L-isoleucine,L-phenylalanine,L-serine,L-thrcunine,L-glutamicacid,L-asparticacidandglycine.L-N,N,N’,N’-tetra(2-hydroxyethyl)cystinewaspreparedbythereactionofL-cystinewithchlorohydrin.
简介:以乙酰丙酮和1R,2R-环己二胺进行缩合得到N,N'-双(乙酰丙酮)-1R,2R-环己二胺的Schiff碱配体L’,以乙酰丙酮和1S,2S-环己二胺进行缩合得到N,N'双(乙酰丙酮)-1S,2S-环己二胺的Schiff碱配体L^2,然后将L^1和L^2与AgClO4,AgBF4,AgSbF6进行配位反应,得到了3个配合物Ag2(L^1)(L^2)ClO4)2n(1),Ag2(L^1)(L^2)(BF4)2n(2)和Ag2(L^1)(L^2)(SbF6)2n(3),并用元素分析,FT—IR和X-射线单晶衍射进行了表征。结果表明,配合物1-3都属于单斜晶系,空间群P21/n,配合物1的中心Ag(I)离子采用扭曲四面体的配位构型,配合物2和3的中心Ag(I)离子都是近似平面三角形的配位构型。配合物1—3都通过配位作用向空间扩展形成2D网状结构。
简介:Thecrystalandmolecularstructureofcopper(Ⅱ)dimericcomplexofS-methyl-B-N-(pyridineN-oxide-2-ylmethylidene)dithiocarbazatewithacetonitrile,[CuL(CH3CN)]2(ClO4)2,wasdeterminedbyX-raydiffraction.ThecomplexcrystalizesinmonoclinicsystemwithspacegroupP21/n,a=7.685(2),6=20.160(6),c=10.847(5)A,B=107.89(3),Z=2,Dc=1.788g/cm3,F(000)=835.8,u=18.17cm-1(Moka,R=0.057.EachCu(Ⅱ)ioninthecomplexissurroundedbyadistortedsquarepyramidal.ThebasalplaneiscomprisedofS,NandOatomsofoneligandtogetherwithaNatomofthesolvent--acetonitrile,whiletheaxialpositionisoccupiedbytheSatomoftheotherligand.ThebondlengthofCu-S(bridging)is3.038A.andCu-Cudistanceis3.700A.
简介:合成了N,N′-亚水杨基皮考林酰肼(HL)及其铁配合物[FeL2](C26H20FeN6O4,Mr=536.33).X射线衍射实验结果表明,标题配合物晶体属于正交晶系,空间群为Pbcn,晶体学参数:a=1.4970(1)nm,b=1.51556(9)nm,c=2.0920(2)nm,V=4.7462(6)nm3,Z=8,Dc=1.501Mg·m-3,F(000)=2208,μ(MoKα)=0.682mm-1,R=0.0695,Rw=0.1502.在配合物[FeL2]中,铁(Ⅱ)原子具有扭曲的八面体配位构型,晶体通过分子间氢键作用形成缔合分子对.红外光谱表明,配体在形成配合物后,ν(CO)和ν(CN)红移.电子光谱表明存在π-π*和d-π*的跃迁;荧光光谱表明,配合物金属对配体n-π*激发引起的荧光发射峰有较大的影响.
简介:Theinteractionsofoxidativeradicals(Br2,HOetc.)withN-phosphoryldipeptidederivatives(NDM-TrpOMeandNDT-MetOMe)havebeeninvestigatedbyusingpulseradiolysisatdifferentpHvalues.IthasbeenfoundthatBr2andHOradicalsoxidizetheMet-siteandTrp-siteinthedipeptidederivativesviaformationofthethree-electron-bondedintermediateandindolylradicalsimultaneously.Thentheintramolecularelectrontransferalongthepeptidebackboneoccurs.Therateconstantsofelectrontransfer,k,havebeendeterminedandthereactionmechanismhasbeendeduced.