Compounds with visible-light-induced photoluminescence are particularly attractive in acting as the emitting components of light-emitting diodes and fluorescent probes for biological applications. A new complex [Zn(NC...Compounds with visible-light-induced photoluminescence are particularly attractive in acting as the emitting components of light-emitting diodes and fluorescent probes for biological applications. A new complex [Zn(NCS)_3(MQ)](MQ^+ = N-methyl-4,4?-bipyridinium) with an isolated molecular structure has been hydrothermally synthesized and characterized by single-crystal X-ray diffraction, elemental analysis, IR spectroscopy and solid-state photoluminescent determination. Crystal data: C_(14)H_(11)N_5S_3Zn, M_r = 410.83, monoclinic, space group P2_1/c, a = 8.809(5), b = 13.138(7), c = 15.580(9) ?, b = 104.433(10)°, V = 1746.2(17) ?~3, Z = 4, D–c = 1.563 g×cm^3, μ = 1.769 mm^(–1), F(000) = 832, the final R = 0.0376 and wR = 0.1243 for 2850 observed reflections with I > 2s(I). In the crystal structure, the zinc atom is tetrahedrally coordinated by one MQ+ ligand and three NCS– groups to yield a tetrahedral configuration. The bond length of Zn–NMQ is clearly shorter than those found in reported Zn(Ⅱ) complexes of 4,4?-bipy. The isolated units are joined by C–H···S interactions to generate a 2D hydrogen-bonding network. This compound displays visible light-induced photoluminescence, which originates from both intraligand charge-transfer of the MQ+ ligand and NCS~–→MQ^+ charge-transfer according to a density of states(DOS) calculation. Moreover, its emission band shows a clear blue shift compared with those of halide compounds.展开更多
A series of novel N-（substituted benzyl）-3,5-bis（benzylidene）-4-piperidones 5a--50 were synthesized with substituted benzylamines as raw materials via a series of Michael addition, Dieckmann condensation, hydrolys...A series of novel N-（substituted benzyl）-3,5-bis（benzylidene）-4-piperidones 5a--50 were synthesized with substituted benzylamines as raw materials via a series of Michael addition, Dieckmann condensation, hydrolysis decarboxylation and aldol condensation. The structures were confirmed by 1↑H NMR, IR, MS techniques and elemental analysis. Assay-based antiproliferative activity study using leukemic cell lines K562 revealed that most of the title compounds have high effectiveness in inhibiting leukemia K562 cells proliferation, among which the compounds 5g （IC50=7.81 μg·mL^-1）, 5k （IC50=6.35μg·mL^-1）, 51 （IC50=7.20 μg·mL^-1）, and 50 （IC50=5.79 μg·mL^-1） have better inhibition activities than standard 5-fluorouracil （IC50=8.56 μg·mL^-1）.展开更多
Cross double Mannich reaction and tandem cyclization were achieved under iodine catalyzed conditions,yielding a series of highly substituted 4-piperidones.Among the possible diastereomers,only one diastereomer was iso...Cross double Mannich reaction and tandem cyclization were achieved under iodine catalyzed conditions,yielding a series of highly substituted 4-piperidones.Among the possible diastereomers,only one diastereomer was isolated,which could be ascribed to the chair-like transition state in six-membered ring,in which all of the hindered groups are located in the pseudoequatorial orientation.展开更多
A multicomponent double Mannich reaction of amines, aldehydes and ketones was efficiently catalyzed by molecular iodine, producing a series of 4-piperidones in a stereoselective way. A variety of amines, aldehydes and...A multicomponent double Mannich reaction of amines, aldehydes and ketones was efficiently catalyzed by molecular iodine, producing a series of 4-piperidones in a stereoselective way. A variety of amines, aldehydes and ketones were tolerated in this tandem process, including those with labile functinal groups. Further investigation of the reaction between alkyl-imines and ketones showed that imines from amines and ketones were formed in situ and isomerized to enamine in the presence of molecular iodine to accelerate the corresponding Mannich addition.展开更多
基金supported by the National Natural Science Foundation of China(21221001,and 21471149)Key Research Program of Frontier Science,CAS(QYZDJ-SSW-SLH028)
文摘Compounds with visible-light-induced photoluminescence are particularly attractive in acting as the emitting components of light-emitting diodes and fluorescent probes for biological applications. A new complex [Zn(NCS)_3(MQ)](MQ^+ = N-methyl-4,4?-bipyridinium) with an isolated molecular structure has been hydrothermally synthesized and characterized by single-crystal X-ray diffraction, elemental analysis, IR spectroscopy and solid-state photoluminescent determination. Crystal data: C_(14)H_(11)N_5S_3Zn, M_r = 410.83, monoclinic, space group P2_1/c, a = 8.809(5), b = 13.138(7), c = 15.580(9) ?, b = 104.433(10)°, V = 1746.2(17) ?~3, Z = 4, D–c = 1.563 g×cm^3, μ = 1.769 mm^(–1), F(000) = 832, the final R = 0.0376 and wR = 0.1243 for 2850 observed reflections with I > 2s(I). In the crystal structure, the zinc atom is tetrahedrally coordinated by one MQ+ ligand and three NCS– groups to yield a tetrahedral configuration. The bond length of Zn–NMQ is clearly shorter than those found in reported Zn(Ⅱ) complexes of 4,4?-bipy. The isolated units are joined by C–H···S interactions to generate a 2D hydrogen-bonding network. This compound displays visible light-induced photoluminescence, which originates from both intraligand charge-transfer of the MQ+ ligand and NCS~–→MQ^+ charge-transfer according to a density of states(DOS) calculation. Moreover, its emission band shows a clear blue shift compared with those of halide compounds.
文摘A series of novel N-（substituted benzyl）-3,5-bis（benzylidene）-4-piperidones 5a--50 were synthesized with substituted benzylamines as raw materials via a series of Michael addition, Dieckmann condensation, hydrolysis decarboxylation and aldol condensation. The structures were confirmed by 1↑H NMR, IR, MS techniques and elemental analysis. Assay-based antiproliferative activity study using leukemic cell lines K562 revealed that most of the title compounds have high effectiveness in inhibiting leukemia K562 cells proliferation, among which the compounds 5g （IC50=7.81 μg·mL^-1）, 5k （IC50=6.35μg·mL^-1）, 51 （IC50=7.20 μg·mL^-1）, and 50 （IC50=5.79 μg·mL^-1） have better inhibition activities than standard 5-fluorouracil （IC50=8.56 μg·mL^-1）.
基金NSFC(No21002079)and Project(No20096203120002)supported by the Ministry of Education of the People's Republic of ChinaTechnological Innovation Project(NosNWNU-KJCXGC-03-75 and NWNU-KJCXGC-03-64) of Northwest Normal University for supporting our research
文摘Cross double Mannich reaction and tandem cyclization were achieved under iodine catalyzed conditions,yielding a series of highly substituted 4-piperidones.Among the possible diastereomers,only one diastereomer was isolated,which could be ascribed to the chair-like transition state in six-membered ring,in which all of the hindered groups are located in the pseudoequatorial orientation.
文摘A multicomponent double Mannich reaction of amines, aldehydes and ketones was efficiently catalyzed by molecular iodine, producing a series of 4-piperidones in a stereoselective way. A variety of amines, aldehydes and ketones were tolerated in this tandem process, including those with labile functinal groups. Further investigation of the reaction between alkyl-imines and ketones showed that imines from amines and ketones were formed in situ and isomerized to enamine in the presence of molecular iodine to accelerate the corresponding Mannich addition.
