The mesomorphie properties of title complexes are investigated by means of DSC and polarizing microscopy. The mesophase temperature ranges of complexes are wider than that of corresponding organic ligands. The bridgin...The mesomorphie properties of title complexes are investigated by means of DSC and polarizing microscopy. The mesophase temperature ranges of complexes are wider than that of corresponding organic ligands. The bridging groups of the complexes have profoand effects on the mesomorphic behavior, When the bridging groups are opticallhy active. the compleve show chiral smectic展开更多
In recent twenty years,aggregation-induced emission(AIE),due to its excellent application prospect,has aroused widespread interests.The development of novel and easy to make AIE luminogens(AIEgens)is an attractive sub...In recent twenty years,aggregation-induced emission(AIE),due to its excellent application prospect,has aroused widespread interests.The development of novel and easy to make AIE luminogens(AIEgens)is an attractive subject.For this purpose,it is very important to study the structure-property relationship of AIEgens.Because azine derivatives are easy to synthesis and some of them have nice AIE properties,herein,a series of azine derivatives(ADs)were employed as models to study the influence of different functional groups,electronic effects and structures on the AIE properties of azine derivatives.The AIE mechanism were studied by single crystal analysis,density functional theory(DFT)calculations and so on.The results indicated that the o-hydroxyl aryl substituted azine compounds could show good AIE properties.Meanwhile,the AIE properties of o-hydroxyl aryl substituted azine compounds were also influenced by the electronic effects of the aryl groups in the azine compounds.The o-hydroxyl groups could form intramolecular hydrogen bond with imine group,which play key role to restrict the intramolecular rotation of the aryl groups and act as base stone for the AIE process of this kind compounds.The HOMO-LUMO energy gaps of o-hydroxyl substituted azine are smaller than other homologous compounds,which is agree with the proposed AIE mechanism.Finally,thanks to the AIE properties,the o-hydroxy-substituted azines could be used as efficient Al^(3+)and Cu^(2+)fluorescent chemosensors in different conditions.In addition,test strips based on AD10 has been prepared,which can conveniently detect Cu^(2+)in industrial wastewater.This research supplied a way for the design of novel easy to make AIEgens through simple azine derivatives.展开更多
A series of symmetrical azine-type liquid crystals were synthesized. The characteristic of these liquid crystals is that they had high clearing point （～320℃） and broad thermal range of nematic phase （～154℃）. I...A series of symmetrical azine-type liquid crystals were synthesized. The characteristic of these liquid crystals is that they had high clearing point （～320℃） and broad thermal range of nematic phase （～154℃）. It was also found that the end groups of the liquid crystals had effect on the mesomorphic properties.展开更多
A new convenient and environmentally benign procedure for synthesis of azines from hydrazme sulfate with several aromatic aldehydes coupled with grinding is studied. This reaction is carried out under solvent-free con...A new convenient and environmentally benign procedure for synthesis of azines from hydrazme sulfate with several aromatic aldehydes coupled with grinding is studied. This reaction is carried out under solvent-free conditions and in absence of catalyst to afford high yields of relevant azines.展开更多
Crystals of the title compound C22H12N62HCl?H2O (DAA稨Cl) were obtained from a HCl aqueous solution of 4, 5-diazafluorene-9-one azine. The crystal belongs to monoclinic, space group P21/c with a = 5.203(3), b = 8.991(...Crystals of the title compound C22H12N62HCl?H2O (DAA稨Cl) were obtained from a HCl aqueous solution of 4, 5-diazafluorene-9-one azine. The crystal belongs to monoclinic, space group P21/c with a = 5.203(3), b = 8.991(3), c = 22.17(1) , b = 92.13(4), V = 1036.2(9) 3, Z = 2, C22H18N6O2Cl2, Mr = 468.1, Dc = 1.503 g/cm3, F(000) = 484, m(MoKa) = 0.344 mm-1, R = 0.052 and wR = 0.056 for 755 observed reflections. The Cl…N(2) distance of 2.999(6) ?and Cl…HN(2) angle of 160.8(8)o imply the existence of a stronger H-bond between Cl and DAA. And both the rather longer ClH distance of 1.814(2) ?and the unexpected shorter N(2)H distance of 1.236(6) ?suggest the protonation of DAA molecule and explain the weak coordination ability of DAA to a metal center in the acidic solution.展开更多
Deuteriodifluoromethyl(CF_(2)D)is a challenging and important functional group due to difficult deuterium incorporation and lack of effective precursor reagents.Herein,we report a bench-stable reagent,deuteriodifluoro...Deuteriodifluoromethyl(CF_(2)D)is a challenging and important functional group due to difficult deuterium incorporation and lack of effective precursor reagents.Herein,we report a bench-stable reagent,deuteriodifluoromethyl phosphine(DDFP)from cheap deuterium source for selectivity deuteriodifluoromethylation of azines with a high deuterium incorporation yield.The late-stage modification of complex molecules further confirmed the potential of this reagent for practical applications.We expect that our reagent to find applications in synthesis of isotope-labelled molecules of interests for drug-discovery and related ilucidation of mechanism of action.展开更多
Cp^*Co(Ⅲ)-catalyzed direct C—H amidation of azines has been developed.This co nversion could proceed smoothly in the absence of external oxidants,acids or bases,with excellent regioselectivity and broad functional g...Cp^*Co(Ⅲ)-catalyzed direct C—H amidation of azines has been developed.This co nversion could proceed smoothly in the absence of external oxidants,acids or bases,with excellent regioselectivity and broad functional group tolerance,CO2 was released as the sole byproduct,thus providing an environmentally benign amidation process.The products obtained are important intermediates in organic synthesis.展开更多
New functionalized fused heterocycles, such as, 1,3,6,9,11-pentasubstituted-pyrido[3,2-f:6,5-f']bis([1,2,4]triazolo[4,3-a]-pyrimidin-5(1H)-ones (6) and 1,3-disubstituted-7-[(E)-2-(thiophen-2-yl)ethenyl]-1,4,9,9a-t...New functionalized fused heterocycles, such as, 1,3,6,9,11-pentasubstituted-pyrido[3,2-f:6,5-f']bis([1,2,4]triazolo[4,3-a]-pyrimidin-5(1H)-ones (6) and 1,3-disubstituted-7-[(E)-2-(thiophen-2-yl)ethenyl]-1,4,9,9a-tetrahydro-6H-[1,2,4]triazino[4,3-b][1,2,4,5]-tetrazin-6-ones (16) were synthesized via reaction of the hydrazonoyl chlorides (1) with 1,3,6-triphenyl-9-thioxo-9,10-dihydro-pyrimido [4,5-b]pyrido[4,5-d][1,2,4]triazolo[4,3-a]pyrimidin-5,7(1H,8H)-di-one (5) and 4-amino-6-[(2-thiophen-2-yl)ethenyl]-3-thioxo-3,4-dihydro-[1,2,4]triazin-5(2H)-one (11), respectively. The mechanism and the regioselectivity of the studied reactions have been discussed. The biological activity of the products has been evaluated against some fungi and bacteria species. The tested compounds exhibited moderate activity against the bacteria species.展开更多
An AIE-active azine derivative(1)was facilely synthesized by aldehyde-amine condensation of 2-hydroxy-1-naphthaldehyde and 3-methyl-2-benzothiazolinone hydrazone.It crystallizes in the monoclinic space group P21/n wit...An AIE-active azine derivative(1)was facilely synthesized by aldehyde-amine condensation of 2-hydroxy-1-naphthaldehyde and 3-methyl-2-benzothiazolinone hydrazone.It crystallizes in the monoclinic space group P21/n with a=8.2176(5),b=13.1733(7),c=14.5731(8)Å,β=90.521(5)º,and Z=4.Compound 1 exhibits aggregation-induced emission characteristics.In dilute solution,it is non-emissive,while strong emission was observed in the aqueous medium as a result of the molecular aggregation in poor solvent.The powder and crystals of 1 also exhibit strong fluorescence.In its crystal lattice,the molecules stack in a face-to-face style,but there is noπ-πstacking interaction due to the long distance between adjacent molecules.It is the loose stacking mode that blocks the nonradiative decay channel resulting in its AIE effect.展开更多
Diaminoglyoxime was reacted in water at 150-400℃ and at 27.5 MPa pressure in metal Ti tubing reactor. Experimental results indicate that, diaminoglyoxime can be converted into NH-3 and CO-2, either through direct hyd...Diaminoglyoxime was reacted in water at 150-400℃ and at 27.5 MPa pressure in metal Ti tubing reactor. Experimental results indicate that, diaminoglyoxime can be converted into NH-3 and CO-2, either through direct hydrolysis or through pyrolysis and polymerization, and then further hydrolysis. The possible reaction mechanism is nucleophilic addition of water.展开更多
The cyanide anion(CN^(–))is known to be one of the most toxic anions.Therefore,there is an urgent need to develop a reliable,sensitive,selective,rapid and effective method for the detection of CN^(–).Here,a self-ass...The cyanide anion(CN^(–))is known to be one of the most toxic anions.Therefore,there is an urgent need to develop a reliable,sensitive,selective,rapid and effective method for the detection of CN^(–).Here,a self-assembly strategy based on pillar[5]arene P5 and azine derivative AZ was used to construct supramolecular sensors,and it was found that the detection effect of CN^(–)was significantly improved by the assembly strategy.The sensitivity of the assembled sensor P5-AZ to CN^(–)is more than 10 times higher than that of AZ.The detect mechanism was further investigated by theoretical calculations and 1H NMR.The results showed that AZ detects CN–by a deprotonation process with fluorescence enhancement,while P5-AZ improves the sensitivity of CN^(–)recognition through hydrogen bonding,anion-πand anion-dipole interactions,as well as the strong bonding ability of the assembly.Supramolecular assembly P5-AZ has the advantages of low toxicity,high sensitivity,and more importantly,it provides a method to detect CN^(–)sensitivity in the aqueous phase and organisms by host-vip assembly.展开更多
Exploring new linkage chemistry is of fundamental significance for covalent organic frameworks(COFs)to expand their structure and functional diversity.Herein,we report a strategy for converting azine linkage into urea...Exploring new linkage chemistry is of fundamental significance for covalent organic frameworks(COFs)to expand their structure and functional diversity.Herein,we report a strategy for converting azine linkage into urea-and thiourea-based fused-ring connections in COFs by criss-cross[3+2]dipolar cycloaddition of azine with HNCO or KSCN.The as-prepared COFs with cyclized linkages exhibited enhanced chemical and thermal stability by locking the dynamic C=N linkages in the progenitor.Moreover,functions could be introduced into the skeleton of COFs by this postsynthetic cyclization method,which enabled significant improvements in functionality,demonstrated by the studies on CO_(2)/N_(2) selective sorption,proton conduction,and Hg^(2+)adsorption.The use of this[3+2]cycloaddition strategy not only enriched the chemistry of linkage conversion for COFs but also offered a new way to fabricate fused-ring-linked COFs,thereby representing a high level of controllability on connectivity and functionality of COFs.展开更多
文摘The mesomorphie properties of title complexes are investigated by means of DSC and polarizing microscopy. The mesophase temperature ranges of complexes are wider than that of corresponding organic ligands. The bridging groups of the complexes have profoand effects on the mesomorphic behavior, When the bridging groups are opticallhy active. the compleve show chiral smectic
基金supported by the National Natural Science Foundation of China(NSFC,No.22065031)the Key R&D Program of Gansu Province(No.21YF5GA066)+4 种基金Gansu Province College Industry Support Plan Project(No.2022CYZC-18)Natural Science Foundation of Gansu Province(Nos.2020-0405-JCC-630,20JR10RA088)Fundamental Research Funds for the Central Universities(Nos.31920190041,31920200002,31920190018,31920190013)Young Doctor Foundation of Gansu Province(No.2021QB-148)The Science and Technology Project Funded by Social Capital in Longnan City of Gansu Province(No.2021-SZ-01)。
文摘In recent twenty years,aggregation-induced emission(AIE),due to its excellent application prospect,has aroused widespread interests.The development of novel and easy to make AIE luminogens(AIEgens)is an attractive subject.For this purpose,it is very important to study the structure-property relationship of AIEgens.Because azine derivatives are easy to synthesis and some of them have nice AIE properties,herein,a series of azine derivatives(ADs)were employed as models to study the influence of different functional groups,electronic effects and structures on the AIE properties of azine derivatives.The AIE mechanism were studied by single crystal analysis,density functional theory(DFT)calculations and so on.The results indicated that the o-hydroxyl aryl substituted azine compounds could show good AIE properties.Meanwhile,the AIE properties of o-hydroxyl aryl substituted azine compounds were also influenced by the electronic effects of the aryl groups in the azine compounds.The o-hydroxyl groups could form intramolecular hydrogen bond with imine group,which play key role to restrict the intramolecular rotation of the aryl groups and act as base stone for the AIE process of this kind compounds.The HOMO-LUMO energy gaps of o-hydroxyl substituted azine are smaller than other homologous compounds,which is agree with the proposed AIE mechanism.Finally,thanks to the AIE properties,the o-hydroxy-substituted azines could be used as efficient Al^(3+)and Cu^(2+)fluorescent chemosensors in different conditions.In addition,test strips based on AD10 has been prepared,which can conveniently detect Cu^(2+)in industrial wastewater.This research supplied a way for the design of novel easy to make AIEgens through simple azine derivatives.
文摘A series of symmetrical azine-type liquid crystals were synthesized. The characteristic of these liquid crystals is that they had high clearing point （～320℃） and broad thermal range of nematic phase （～154℃）. It was also found that the end groups of the liquid crystals had effect on the mesomorphic properties.
文摘A new convenient and environmentally benign procedure for synthesis of azines from hydrazme sulfate with several aromatic aldehydes coupled with grinding is studied. This reaction is carried out under solvent-free conditions and in absence of catalyst to afford high yields of relevant azines.
基金The project was supported by the National Natural Science Foundation (29973036) of China
文摘Crystals of the title compound C22H12N62HCl?H2O (DAA稨Cl) were obtained from a HCl aqueous solution of 4, 5-diazafluorene-9-one azine. The crystal belongs to monoclinic, space group P21/c with a = 5.203(3), b = 8.991(3), c = 22.17(1) , b = 92.13(4), V = 1036.2(9) 3, Z = 2, C22H18N6O2Cl2, Mr = 468.1, Dc = 1.503 g/cm3, F(000) = 484, m(MoKa) = 0.344 mm-1, R = 0.052 and wR = 0.056 for 755 observed reflections. The Cl…N(2) distance of 2.999(6) ?and Cl…HN(2) angle of 160.8(8)o imply the existence of a stronger H-bond between Cl and DAA. And both the rather longer ClH distance of 1.814(2) ?and the unexpected shorter N(2)H distance of 1.236(6) ?suggest the protonation of DAA molecule and explain the weak coordination ability of DAA to a metal center in the acidic solution.
基金financial supported by Innovation Program of Shanghai Municipal Education Commission(No.201701070002E00037)supported by National Key Research Program of China(No.2017YFD0200505)the Fundamental Research Funds for the Central Universities。
文摘Deuteriodifluoromethyl(CF_(2)D)is a challenging and important functional group due to difficult deuterium incorporation and lack of effective precursor reagents.Herein,we report a bench-stable reagent,deuteriodifluoromethyl phosphine(DDFP)from cheap deuterium source for selectivity deuteriodifluoromethylation of azines with a high deuterium incorporation yield.The late-stage modification of complex molecules further confirmed the potential of this reagent for practical applications.We expect that our reagent to find applications in synthesis of isotope-labelled molecules of interests for drug-discovery and related ilucidation of mechanism of action.
基金the Ministry of Science and Technology of China(No.2016YFE0132600)Henan Center for Outstanding Overseas Scientists(No.GZS2020001)。
文摘Cp^*Co(Ⅲ)-catalyzed direct C—H amidation of azines has been developed.This co nversion could proceed smoothly in the absence of external oxidants,acids or bases,with excellent regioselectivity and broad functional group tolerance,CO2 was released as the sole byproduct,thus providing an environmentally benign amidation process.The products obtained are important intermediates in organic synthesis.
文摘New functionalized fused heterocycles, such as, 1,3,6,9,11-pentasubstituted-pyrido[3,2-f:6,5-f']bis([1,2,4]triazolo[4,3-a]-pyrimidin-5(1H)-ones (6) and 1,3-disubstituted-7-[(E)-2-(thiophen-2-yl)ethenyl]-1,4,9,9a-tetrahydro-6H-[1,2,4]triazino[4,3-b][1,2,4,5]-tetrazin-6-ones (16) were synthesized via reaction of the hydrazonoyl chlorides (1) with 1,3,6-triphenyl-9-thioxo-9,10-dihydro-pyrimido [4,5-b]pyrido[4,5-d][1,2,4]triazolo[4,3-a]pyrimidin-5,7(1H,8H)-di-one (5) and 4-amino-6-[(2-thiophen-2-yl)ethenyl]-3-thioxo-3,4-dihydro-[1,2,4]triazin-5(2H)-one (11), respectively. The mechanism and the regioselectivity of the studied reactions have been discussed. The biological activity of the products has been evaluated against some fungi and bacteria species. The tested compounds exhibited moderate activity against the bacteria species.
基金supported by the Natural Science Foundation of Hainan Province(No.20162028)the Program for Innovative Research Team in University(IRT-16R19)。
文摘An AIE-active azine derivative(1)was facilely synthesized by aldehyde-amine condensation of 2-hydroxy-1-naphthaldehyde and 3-methyl-2-benzothiazolinone hydrazone.It crystallizes in the monoclinic space group P21/n with a=8.2176(5),b=13.1733(7),c=14.5731(8)Å,β=90.521(5)º,and Z=4.Compound 1 exhibits aggregation-induced emission characteristics.In dilute solution,it is non-emissive,while strong emission was observed in the aqueous medium as a result of the molecular aggregation in poor solvent.The powder and crystals of 1 also exhibit strong fluorescence.In its crystal lattice,the molecules stack in a face-to-face style,but there is noπ-πstacking interaction due to the long distance between adjacent molecules.It is the loose stacking mode that blocks the nonradiative decay channel resulting in its AIE effect.
文摘Diaminoglyoxime was reacted in water at 150-400℃ and at 27.5 MPa pressure in metal Ti tubing reactor. Experimental results indicate that, diaminoglyoxime can be converted into NH-3 and CO-2, either through direct hydrolysis or through pyrolysis and polymerization, and then further hydrolysis. The possible reaction mechanism is nucleophilic addition of water.
基金supported by the NSFC(Nos.22065031,22061039,22001214,22165027)the Fundamental Research Funds for the Central Universities(No.31920230145)+4 种基金the Top-Notch Talent Project in Gansu Province,the Key R&D Program of Gansu Province(No.21YF5GA066)Gansu Province College Industry Support Plan Project(No.2022CYZC-18)Natural Science Foundation of Gansu Province(Nos.2020-0405-JCC-630,20JR10RA088,21JR1RA220)Gansu Province Science Foundation for Youths(23JRRA690)Northwest Normal University Young Scholars Research Capacity Improvement Program(NWNU-LKQN2023-05).
文摘The cyanide anion(CN^(–))is known to be one of the most toxic anions.Therefore,there is an urgent need to develop a reliable,sensitive,selective,rapid and effective method for the detection of CN^(–).Here,a self-assembly strategy based on pillar[5]arene P5 and azine derivative AZ was used to construct supramolecular sensors,and it was found that the detection effect of CN^(–)was significantly improved by the assembly strategy.The sensitivity of the assembled sensor P5-AZ to CN^(–)is more than 10 times higher than that of AZ.The detect mechanism was further investigated by theoretical calculations and 1H NMR.The results showed that AZ detects CN–by a deprotonation process with fluorescence enhancement,while P5-AZ improves the sensitivity of CN^(–)recognition through hydrogen bonding,anion-πand anion-dipole interactions,as well as the strong bonding ability of the assembly.Supramolecular assembly P5-AZ has the advantages of low toxicity,high sensitivity,and more importantly,it provides a method to detect CN^(–)sensitivity in the aqueous phase and organisms by host-vip assembly.
基金supported by the National Science Fund for Distinguished Young Scholars of China(grant no.21725404)the Science and Technology Committee of Shanghai Municipality,China(grant no.20JC1415400).
文摘Exploring new linkage chemistry is of fundamental significance for covalent organic frameworks(COFs)to expand their structure and functional diversity.Herein,we report a strategy for converting azine linkage into urea-and thiourea-based fused-ring connections in COFs by criss-cross[3+2]dipolar cycloaddition of azine with HNCO or KSCN.The as-prepared COFs with cyclized linkages exhibited enhanced chemical and thermal stability by locking the dynamic C=N linkages in the progenitor.Moreover,functions could be introduced into the skeleton of COFs by this postsynthetic cyclization method,which enabled significant improvements in functionality,demonstrated by the studies on CO_(2)/N_(2) selective sorption,proton conduction,and Hg^(2+)adsorption.The use of this[3+2]cycloaddition strategy not only enriched the chemistry of linkage conversion for COFs but also offered a new way to fabricate fused-ring-linked COFs,thereby representing a high level of controllability on connectivity and functionality of COFs.
