Two naphthalene（NP） and bipyridinium（BIPY^2＋） alternately incorporated polymers P1 and P2 have been prepared through the formation of dynamic hydrazone bonds. The polymers formed NP–BIPY^2＋donor–acceptor inter...Two naphthalene（NP） and bipyridinium（BIPY^2＋） alternately incorporated polymers P1 and P2 have been prepared through the formation of dynamic hydrazone bonds. The polymers formed NP–BIPY^2＋donor–acceptor interaction-induced pleated secondary structure. Upon reducing the BIPY^2＋units to radical cation BIPY＋, intramolecular dimerization of the BIPY＋units induced the backbones to afford another pleated secondary structure. Adding electron-rich macrocyclic polyether bis-1,5-dinaphtho[38]crown-10 or electron-deficient cyclobis（paraquat-p-phenylene） cyclophane did not break the first foldamer by complexing the BIPY^2＋or NP units of the polymers, whereas the di（radical cationic）ring of the second cyclophane could break the second foldamer by forming threading complexes with the BIPY＋units of the polymers.展开更多
A novel redox-active bipyridinium ligand N-（3-carboxyphenyl）-4,4＇-bipyridinium chloride （HCPBPyC1） and its coordination polymer {[Cd2（CPBPy）2（BDC）（H2O）2Cl2]·6H2O}n 1 （H2BDC = benzene-1,4-dicarboxylic ...A novel redox-active bipyridinium ligand N-（3-carboxyphenyl）-4,4＇-bipyridinium chloride （HCPBPyC1） and its coordination polymer {[Cd2（CPBPy）2（BDC）（H2O）2Cl2]·6H2O}n 1 （H2BDC = benzene-1,4-dicarboxylic acid） were synthesized and characterized. Crystallographic data for 1： C42H44Cd2Cl2N4O16, Mr = 1156.51, monoclinic, space group C2/c, a = 21.046（3）, b = 11.0036（15）, c = 20.012（3）A, β = 98.694（8）°, Z = 4, V = 4581.1（11）A3, Dc = 1.677 g/cm^3, F（000） = 2280 and μ = 1.120 mm^-1. Complex 1 possesses a thick and undulated two-dimensional layer with （6,3） topology, which interpenetrates with two others （above and below） to extend into a three-dimensional supramolecular framework.展开更多
A three-dimensional flexible organic framework FOF-1 has been synthesized from the condensation of a tetratopic acylhydrazine and a rigid 4,4-diphenyl-4,4-bipyridinium dialdehyde in water through the quantitative form...A three-dimensional flexible organic framework FOF-1 has been synthesized from the condensation of a tetratopic acylhydrazine and a rigid 4,4-diphenyl-4,4-bipyridinium dialdehyde in water through the quantitative formation of hydrazone bond. FOF-1 is further applied to construct a polycatenane framework FOF-pc-1 through the quantitative cucurbit[7]uril encapsulation for the diphenylbipyridinium subunits of the framework by making use of the dynamic nature of the hydrazone bond in water. The bipyridinium subunits in both frameworks can be reduced their radical cation counterparts to produce conjugated radical cation-linked dynamic organic frameworks rc-FOF-1 or rc-FOF-pc-1. Polycatenation is revealed to enhance the stability of the dynamic frameworks in water, whereas depolycatenation can be reached for both FOF-pc-1 and rc-FOF-pc-1 by using a ferrocene guest to form a more stable complex with CB[7].展开更多
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
基金supported by The Ministry of Science and Technology of China (No. 2013CB834501)The Science and Technology Commission of Shanghai Municipality (No. 13M1400200)+1 种基金The Ministry of Education of China research fund for the doctoral programthe National Natural Science Foundation of China (Nos. 21432004 and 21472023)
文摘Two naphthalene（NP） and bipyridinium（BIPY^2＋） alternately incorporated polymers P1 and P2 have been prepared through the formation of dynamic hydrazone bonds. The polymers formed NP–BIPY^2＋donor–acceptor interaction-induced pleated secondary structure. Upon reducing the BIPY^2＋units to radical cation BIPY＋, intramolecular dimerization of the BIPY＋units induced the backbones to afford another pleated secondary structure. Adding electron-rich macrocyclic polyether bis-1,5-dinaphtho[38]crown-10 or electron-deficient cyclobis（paraquat-p-phenylene） cyclophane did not break the first foldamer by complexing the BIPY^2＋or NP units of the polymers, whereas the di（radical cationic）ring of the second cyclophane could break the second foldamer by forming threading complexes with the BIPY＋units of the polymers.
基金the National Natural Science Foundation of China (No. 20671090/5037206)the Key Project from CAS (No. KJCX2. YW.H01)
文摘A novel redox-active bipyridinium ligand N-（3-carboxyphenyl）-4,4＇-bipyridinium chloride （HCPBPyC1） and its coordination polymer {[Cd2（CPBPy）2（BDC）（H2O）2Cl2]·6H2O}n 1 （H2BDC = benzene-1,4-dicarboxylic acid） were synthesized and characterized. Crystallographic data for 1： C42H44Cd2Cl2N4O16, Mr = 1156.51, monoclinic, space group C2/c, a = 21.046（3）, b = 11.0036（15）, c = 20.012（3）A, β = 98.694（8）°, Z = 4, V = 4581.1（11）A3, Dc = 1.677 g/cm^3, F（000） = 2280 and μ = 1.120 mm^-1. Complex 1 possesses a thick and undulated two-dimensional layer with （6,3） topology, which interpenetrates with two others （above and below） to extend into a three-dimensional supramolecular framework.
基金financially supported by the National Natural Science Foundation of China (Nos. 21890732, 21890730 and21921003)。
文摘A three-dimensional flexible organic framework FOF-1 has been synthesized from the condensation of a tetratopic acylhydrazine and a rigid 4,4-diphenyl-4,4-bipyridinium dialdehyde in water through the quantitative formation of hydrazone bond. FOF-1 is further applied to construct a polycatenane framework FOF-pc-1 through the quantitative cucurbit[7]uril encapsulation for the diphenylbipyridinium subunits of the framework by making use of the dynamic nature of the hydrazone bond in water. The bipyridinium subunits in both frameworks can be reduced their radical cation counterparts to produce conjugated radical cation-linked dynamic organic frameworks rc-FOF-1 or rc-FOF-pc-1. Polycatenation is revealed to enhance the stability of the dynamic frameworks in water, whereas depolycatenation can be reached for both FOF-pc-1 and rc-FOF-pc-1 by using a ferrocene guest to form a more stable complex with CB[7].
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.
