C6H5COCHCOCF3)3[(C6H5)3PO]2Eu,Mr=1354.01,triclinic P1,a=11.244(3),b=12.252(3),c=23.784(1),α=79.66(2),β=76.38(3),γ=71.44(3)°,V=2999.33,Z=2,Dc=1.499g/cm3,μ(MoKα)=11.79 cm-1,final R=0.066(Rw=0.069) for 7899 obs...C6H5COCHCOCF3)3[(C6H5)3PO]2Eu,Mr=1354.01,triclinic P1,a=11.244(3),b=12.252(3),c=23.784(1),α=79.66(2),β=76.38(3),γ=71.44(3)°,V=2999.33,Z=2,Dc=1.499g/cm3,μ(MoKα)=11.79 cm-1,final R=0.066(Rw=0.069) for 7899 observed reflections with I】3σ(Ⅰ),The europium ion(Ⅲ) is coordinated by eight oxygen atoms,of which six from C6H5COCHCOCF3 and the other two from (C6H5)3PO,to form a dodecahedral configuration with the average distance of Eu-O(C6H5COCHCOCF3) of 2.410 and that of Eu-O[(C6H5)3PO] of 2.385.The coordination of Eu(Ⅲ) with the ligands was characterized by IR and Raman spectroscopy.The molecular rigidity,which effects luminescence of the complexes,was discussed by fluorescence spectroscopy of the Eu(Ⅲ) complexes.展开更多
Bipyrimidines have been chosen as(N^N)(N^N) bridging ligands for connecting metal centers.IrⅢ-LnⅢ(Ln = Nd,Yb,Er) bimetallic complexes [Ir(dfppy)2(μ-bpm)Ln(TTA)3]Cl were synthesized by using Ir(dfppy)2(bpm)Cl as the...Bipyrimidines have been chosen as(N^N)(N^N) bridging ligands for connecting metal centers.IrⅢ-LnⅢ(Ln = Nd,Yb,Er) bimetallic complexes [Ir(dfppy)2(μ-bpm)Ln(TTA)3]Cl were synthesized by using Ir(dfppy)2(bpm)Cl as the ligand coordinating to lanthanide complexes Ln(TTA)3·2H2O.The stability constants between Ir(dfppy)2(bpm)Cl and lanthanide ions were measured by fluorescence titration.The obvious quenching of visible emission from IrⅢ complex in the IrⅢ-LnⅢ(Ln = Nd,Yb,Er) bimetallic complexes indicates that energy transfer occurred from IrⅢ center to lanthanides.NIR emissions from NdⅢ,YbⅢ,and ErⅢ were obtained under the excitation of visible light by selective excitation of the IrⅢ-based chromophore.It was proven that Ir(dfppy)2(bpm)Cl as the ligand could effectively sensitize NIR emission from NdⅢ,YbⅢ,and ErⅢ.展开更多
Trace Ir(Ⅲ)complex enhanced aggregation-induced electrochemiluminescence(AIECL)of poly-tetraphenylethene(p TPE)in aqueous media was investigated for the first time.The poly-TPE end-capped by Ir(Ⅲ)complex(Ir@p TPE)an...Trace Ir(Ⅲ)complex enhanced aggregation-induced electrochemiluminescence(AIECL)of poly-tetraphenylethene(p TPE)in aqueous media was investigated for the first time.The poly-TPE end-capped by Ir(Ⅲ)complex(Ir@p TPE)and its corresponding model polymer poly-TPE(Ph@pTPE)could be synthesized by Suzuki coupling polymerization reaction of 1,2-bis(4-bromophenyl)-1,2-diphenylethene(M-1)with 1,2-diphenyl-1,2-bis(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)ethene(M-2)and the continuous Suzuki coupling end-capped reaction of poly-TPE-pinacol boronate with(pq)2 Ir(pico)Br and bromobenzene,respectively.Subsequently,the corresponding Ir@p TPE Pdots and Ph@p TPE Pdots encapsulated with poly(styrene-co-maleicanhydride)(PSMA)could be obtained by nanoprecipitation method.Compared with Ph@p TPE Pdots,the Ir@p TPE Pdots with a trace amount of Ir(Ⅲ)complex(1.34‰of Ir(Ⅲ)content,wt)could exhibit 9.9-fold enhancement of the electrochemiluminescence(ECL)signal for visual emission.This work provided a novel strategy on designing highly efficient ECL materials based on trace Ir(Ⅲ)-end capping AIE-active polymer dots.展开更多
A simple and sensitive electrogenerated chemiluminescence(ECL)sensor array was developed for the discrimination of three biothiols,including homocysteine(Hcy),cysteine(Cys)and glutathione(GSH)using two bis-cyclometala...A simple and sensitive electrogenerated chemiluminescence(ECL)sensor array was developed for the discrimination of three biothiols,including homocysteine(Hcy),cysteine(Cys)and glutathione(GSH)using two bis-cyclometalated Ir(Ⅲ)complexes as ECL probes.Two aldehyde groups bearing bis-cyclometalated Ir(Ⅲ)complexes were selected as ECL probes,including[(bt)2Ir(phen-CHO)]PF_(6)(bt=2-phenylbenzothiazole,phen-CHO=1,10-phenanthroline-5-carboxaldehyde,probe 1)and[(ppy)_(2)Ir(phen-CHO)]PF_(6)(ppy=2-phenylpyridine,probe 2).A“signal on”ECL method was proposed for biothiols assay based on the increase in ECL intensity of two ECL probes by biothiols.Three biothiols can be detected with detection limits of 0.8,0.7 and 0.8μM by probe 1 and 0.3,0.4 and 0.5μM by probe 2 for Cys,Hcy and GSH,respectively.Two-element sensor array was assembled for the detection of three biothiols due to the different enhancement effects of biothiols on the ECL intensity of two ECL probes.The ECL sensor array combining with the principal component analysis was applied to discriminate three biothiols.This study demonstrates that the ECL sensor array using dual ECL reagents provides a promis-ing way for the discrimination of multiple biothiols with good sensitivity and simpleness.展开更多
文摘C6H5COCHCOCF3)3[(C6H5)3PO]2Eu,Mr=1354.01,triclinic P1,a=11.244(3),b=12.252(3),c=23.784(1),α=79.66(2),β=76.38(3),γ=71.44(3)°,V=2999.33,Z=2,Dc=1.499g/cm3,μ(MoKα)=11.79 cm-1,final R=0.066(Rw=0.069) for 7899 observed reflections with I】3σ(Ⅰ),The europium ion(Ⅲ) is coordinated by eight oxygen atoms,of which six from C6H5COCHCOCF3 and the other two from (C6H5)3PO,to form a dodecahedral configuration with the average distance of Eu-O(C6H5COCHCOCF3) of 2.410 and that of Eu-O[(C6H5)3PO] of 2.385.The coordination of Eu(Ⅲ) with the ligands was characterized by IR and Raman spectroscopy.The molecular rigidity,which effects luminescence of the complexes,was discussed by fluorescence spectroscopy of the Eu(Ⅲ) complexes.
基金Supported by the National Basic Research Program of China (Grant No. 2006CB601103)the National Natural Science Foundation of China (Grant Nos. 20221101, 50772003, 20671006, 20971006, and 90922004)
文摘Bipyrimidines have been chosen as(N^N)(N^N) bridging ligands for connecting metal centers.IrⅢ-LnⅢ(Ln = Nd,Yb,Er) bimetallic complexes [Ir(dfppy)2(μ-bpm)Ln(TTA)3]Cl were synthesized by using Ir(dfppy)2(bpm)Cl as the ligand coordinating to lanthanide complexes Ln(TTA)3·2H2O.The stability constants between Ir(dfppy)2(bpm)Cl and lanthanide ions were measured by fluorescence titration.The obvious quenching of visible emission from IrⅢ complex in the IrⅢ-LnⅢ(Ln = Nd,Yb,Er) bimetallic complexes indicates that energy transfer occurred from IrⅢ center to lanthanides.NIR emissions from NdⅢ,YbⅢ,and ErⅢ were obtained under the excitation of visible light by selective excitation of the IrⅢ-based chromophore.It was proven that Ir(dfppy)2(bpm)Cl as the ligand could effectively sensitize NIR emission from NdⅢ,YbⅢ,and ErⅢ.
基金supported by the National Natural Science Foundation of China(21674046,51673093,21535003)the National Key Reaearch and Development Program of China(2016YFA0201200)。
文摘Trace Ir(Ⅲ)complex enhanced aggregation-induced electrochemiluminescence(AIECL)of poly-tetraphenylethene(p TPE)in aqueous media was investigated for the first time.The poly-TPE end-capped by Ir(Ⅲ)complex(Ir@p TPE)and its corresponding model polymer poly-TPE(Ph@pTPE)could be synthesized by Suzuki coupling polymerization reaction of 1,2-bis(4-bromophenyl)-1,2-diphenylethene(M-1)with 1,2-diphenyl-1,2-bis(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)ethene(M-2)and the continuous Suzuki coupling end-capped reaction of poly-TPE-pinacol boronate with(pq)2 Ir(pico)Br and bromobenzene,respectively.Subsequently,the corresponding Ir@p TPE Pdots and Ph@p TPE Pdots encapsulated with poly(styrene-co-maleicanhydride)(PSMA)could be obtained by nanoprecipitation method.Compared with Ph@p TPE Pdots,the Ir@p TPE Pdots with a trace amount of Ir(Ⅲ)complex(1.34‰of Ir(Ⅲ)content,wt)could exhibit 9.9-fold enhancement of the electrochemiluminescence(ECL)signal for visual emission.This work provided a novel strategy on designing highly efficient ECL materials based on trace Ir(Ⅲ)-end capping AIE-active polymer dots.
基金the National Natural Science Foundation of China(Nos.21775097,21775098)the Fundamental Research Funds for the Central Universities(GK201801006)。
文摘A simple and sensitive electrogenerated chemiluminescence(ECL)sensor array was developed for the discrimination of three biothiols,including homocysteine(Hcy),cysteine(Cys)and glutathione(GSH)using two bis-cyclometalated Ir(Ⅲ)complexes as ECL probes.Two aldehyde groups bearing bis-cyclometalated Ir(Ⅲ)complexes were selected as ECL probes,including[(bt)2Ir(phen-CHO)]PF_(6)(bt=2-phenylbenzothiazole,phen-CHO=1,10-phenanthroline-5-carboxaldehyde,probe 1)and[(ppy)_(2)Ir(phen-CHO)]PF_(6)(ppy=2-phenylpyridine,probe 2).A“signal on”ECL method was proposed for biothiols assay based on the increase in ECL intensity of two ECL probes by biothiols.Three biothiols can be detected with detection limits of 0.8,0.7 and 0.8μM by probe 1 and 0.3,0.4 and 0.5μM by probe 2 for Cys,Hcy and GSH,respectively.Two-element sensor array was assembled for the detection of three biothiols due to the different enhancement effects of biothiols on the ECL intensity of two ECL probes.The ECL sensor array combining with the principal component analysis was applied to discriminate three biothiols.This study demonstrates that the ECL sensor array using dual ECL reagents provides a promis-ing way for the discrimination of multiple biothiols with good sensitivity and simpleness.
