The donor-acceptor complex derived from 2-amino-1,3-benzothiazole （ABT） and ethyl 5,6-benzocoumarin-3-carboxylate （EBCC） has been synthesized and its crystal structure was determined by single-crystal X-ray diffra...The donor-acceptor complex derived from 2-amino-1,3-benzothiazole （ABT） and ethyl 5,6-benzocoumarin-3-carboxylate （EBCC） has been synthesized and its crystal structure was determined by single-crystal X-ray diffraction. The crystal belongs to the monoclinic system, space group P21/c, with a = 8.6485（3）, b = 7.7743（3）, c = 29.1963（10） A, β = 92.0460（10）°, Z = 4, Mr = 418.45, V= 1961.79（12） A^3, Dc = 1.417 g/cm^3,μ = 0.199 mm^-1, F（000） = 872, the final R = 0.0350 and wR = 0.1226. The complex is an A…D…D＇…A＇ H-bonded tetramer. The intermolecular N-H…O and N-H…N hydrogen bonds, together with π-π stacking interactions, stabilize the crystal structure by forming a supramolecular architecture. It is found that, in solid state, the fluorescence emission of the complex is quenched significantly while the UV-vis spectrum exhibits a broad band at 346 nm with shoulder, which can be attributed to the donor-acceptor complex formed.展开更多
Despite the significance of hydrogen bonding in deep eutectic solvents（DESs） for desulfurization processes, little is understood about the relationship between the DES composition, hydrogen-bonding strength, and oxi...Despite the significance of hydrogen bonding in deep eutectic solvents（DESs） for desulfurization processes, little is understood about the relationship between the DES composition, hydrogen-bonding strength, and oxidative desulfurization activity. In this study, a new family of caprolactam-based acidic DESs was prepared with different molar ratios of caprolactam and oxalic acid. The prepared DESs were characterized by differential scanning calorimetry, Fourier transform infrared spectroscopy, 1 H nuclear magnetic resonance, and thermogravimetric analyses. These DESs were employed for oxidative desulfurization reactions and the desulfurization efficiency was found to vary regularly with the DES composition. The factors influencing the removal of dibenzothiophene were systematically investigated and the desulfurization efficiency of the caprolactam-based acidic DESs reached as high as 98% under optimal conditions. The removal of different sulfur compounds followed the order： dibenzothiophene 4,6-dimethyldibenzothiophene benzothiophene. The combined experimental data and characterization results revealed that the oxidative desulfurization efficiency of the system was influenced by the hydrogen bonding interactions with the DES, which can be optimized by adjusting the DES composition. These findings regarding hydrogen bonding in DESs provide new insight for better understanding of the mechanism of diesel deep desulfurization processes.展开更多
Two new binary cocrystals formulated as POM·NBA 1 and POM·DNSA 2 （POM = 3-methyl-4-nitro-pyridine-N-oxide, NBA = o-nitrobenzoic acid, DNSA = 3,5-dinitrosalicylic acid） have been successfully synthesized an...Two new binary cocrystals formulated as POM·NBA 1 and POM·DNSA 2 （POM = 3-methyl-4-nitro-pyridine-N-oxide, NBA = o-nitrobenzoic acid, DNSA = 3,5-dinitrosalicylic acid） have been successfully synthesized and characterized by elemental analysis, IR and X-ray single- crystal diffraction analysis. The crystal of 1 crystallizes in triclinic, space group P1, with a = 7.621（4）, b = 7.816（4）, c = 11.702（5） , α = 87.957（10）, β = 83.642（10）, γ = 81.535（10）o, C13H11N3O7, Z = 2, Mr = 321.25, V = 685.1（6） 3, Dc = 1.557 g/cm3, F（000） = 332, μ = 0.129 mm-1, the final R = 0.0632 and wR = 0.0831. The crystal of 2 crystallizes in monoclinic, space group P21/c with a = 14.910（9）, b = 5.904（3）, c =19.321（12） , β = 110.583（10）o, C13H10N4O10, Z = 4, Mr = 382.25, V = 1592.1（16） 3, Dc = 1.595 g/cm3, F（000） = 784, μ = 0.140 mm-1, the final R = 0.0598 and wR = 0.1589. Further structure analysis reveals that the POM with NBA and DNSA molecules in 1 and 2 are linked into 3D structures by the combination of strong O-H…O and weak C-H…O hydrogen bonds, π…π stackings and diverse short contacts, in which different C-H…O weak hydrogen bonds may play a key role in constructing the network structures.展开更多
The use of redox-active organic electrode materials in energy storage is restricted due to their inferior solvent resistance,abysmal conductivity,and the resultant low practical capacity.To address these issues,a clas...The use of redox-active organic electrode materials in energy storage is restricted due to their inferior solvent resistance,abysmal conductivity,and the resultant low practical capacity.To address these issues,a class of bipolar p-phenylenediimidazole-based small-molecule compounds are designed and fabricated.Theπ-conjugated backbone of these small molecules allows for electron delocalization on a big conjugation plane,endowing them with good conductivity and reaction reversibility.Furthermore,when the para-positions of phenylene are occupied by hydroxyl groups,as-formed intramolecular hydrogen bonds(N-H...O)between phenolic hydroxyl groups and the–NH groups of imidazole rings further enhance the structural planarity,resulting in higherπ-conjugation degree and better conductivity,and thus higher utilization of active sites and electrode capacity,proved by both experimental results and theoretical calculations.The optimized composite electrode DBNQ@rGO-45 shows a high specific capacity(∼308 mA h g^(−1)at 100 mA g^(−1))and a long cycling stability(112.9 mA h g^(−1)after 6000 cycles at 2000 mA g^(−1)).The significantly better electrochemical properties for hydroxyl group-containing compounds than those without hydroxyl groups attributed to intramolecular hydrogen bond-induced conjugation enhancement will inspire the structure design of organic electrodes for better energy storage.展开更多
The reaction of 2,4,6-tris（2-pyridyl）-1,3,5-triazine （tptz） and K2PdCl4 in THF/H2O （10：1） results in the hydrolysis of tptz to bis（2-pyridylcarbonyl）amide anion （bpca）, and affords complex Pd（bpca）Cl 1, w...The reaction of 2,4,6-tris（2-pyridyl）-1,3,5-triazine （tptz） and K2PdCl4 in THF/H2O （10：1） results in the hydrolysis of tptz to bis（2-pyridylcarbonyl）amide anion （bpca）, and affords complex Pd（bpca）Cl 1, which is the first example of Pd（Ⅱ）-promoted hydrolysis of ligands. Crystal data for 1： orthorhombic, space group Pbcn, a = 12.0136（17）, b = 14.180（2）, c = 6.9747（11）A, V= 1188.2（3） A3, Z = 4, Mr = 368.06, Dc = 2.058 g/cm3, F（000） = 720,μ = 1.786 mm^-1, λ（MoKα） = 0.71073 A, T= 293（2） K, 2θmax = 54.9°, GOOF = 1.085, the final R= 0.0647 and wR = 0.1051 for 1234 observed reflections with I 〉 2σ（I） （refinement on F2）. Complex 1 is connected through hydrogen bonding to give a 2D network. And weak Pd...Pd interactions are also found between adjacent molecules with the distance of 3.6074（5） A, so the complex is further extended into a 3D supramolecular structure. Thermal gravity analysis （TGA） shows that 1 exhibits high thermal stability below 310℃. X-ray powder diffraction （XRD） and UV/Vis spectrum of 1 are also discussed.展开更多
The soft nature has endowed conjugated polymers with promising applications in a wide range of field-effect transistor(FET)based flexible electronics.With unremitting efforts on revealing the molecular structure-prope...The soft nature has endowed conjugated polymers with promising applications in a wide range of field-effect transistor(FET)based flexible electronics.With unremitting efforts on revealing the molecular structure-property relationships,numerous novel conjugated polymers with high mobility and excellent mechanical property have been developed in the past decades.Incorporating hydrogen-bonding(H-bonding)units into semiconducting polymers is one of the most successful strategies for designing high-performance semiconducting materials.In this review,we aim to highlight the roles of H-bonding units in the performances of polymeric FETs from three aspects.These include(i)charge mobility enhancement for semiconducting polymers after incorporation of H-bonding units into the side chains,(ii)the effects of H-bonding units on the stretchability of conjugated polymers,and(iii)the improvement of self-healing properties of conjugated polymers containing dynamic hydrogen bonds due to the H-bonding units in the side chains or conjugated backbones.展开更多
A novel zinc(II)-based 3D metal organic framework(MOF)[Zn_(3)(L)_(3)(H_(2)L)·2DMF·H_(2)O]with dual hydrogenbond donor(HBD)groups of a free carboxyl and amine,was synthesized solvothermally via 2-aminoterepht...A novel zinc(II)-based 3D metal organic framework(MOF)[Zn_(3)(L)_(3)(H_(2)L)·2DMF·H_(2)O]with dual hydrogenbond donor(HBD)groups of a free carboxyl and amine,was synthesized solvothermally via 2-aminoterephthalic acid(H_(2)L)and 3,5-pyridinedicarboxylic acid ligands.The carboxyl and amine in the prepared Zn_(3)(L)_(3)(H_(2)L)acting as HBD groups can promote the CO_(2) cycloaddition reaction with epoxides.Besides this,the contained sufficient amino groups showing Lewis base properties also facilitated Zn_(3)(L)_(3)(H_(2)L)to activate CO_(2) by forming a carbamate intermediate,while Zn(II)centers acted as Lewis-acid sites accomplishing the epoxide activation.Therefore,Zn_(3)(L)_(3)(H_(2)L)with Lewis acid–base properties and dual HBD groups exhibited an efficient heterogeneous catalysis for the coupling of epoxides and CO_(2).The yield of the propylene carbonate(PC)achieved 99% under 80℃,1.0 MPa CO_(2) and solvent-free conditions.Corresponding carbonate yields of various epoxides could be over 95%even at room temperature by prolonging the reaction time.Moreover,Zn_(3)(L)_(3)(H_(2)L)showed extraordinary versatility to various epoxides and excellent recycling without any obvious loss in activity.Furthermore,a plausible mechanism was proposed for the CO_(2) cycloaddition to epoxides based on the structural evidence and catalytic effects.展开更多
It is a widely held view that the continuous hydrogen bonding network plays a crucial role in proton transport.Herein,we report the cyclic single-crystal-to-single-crystal transformation of three hydrogenbonded organi...It is a widely held view that the continuous hydrogen bonding network plays a crucial role in proton transport.Herein,we report the cyclic single-crystal-to-single-crystal transformation of three hydrogenbonded organic frameworks(HOFs),BPPA,BPPA-azo,and BPPA-gua,induced by the change of auxiliary ligands,which explicitly demonstrates that the hydrophilic interlayers of BPPA possess good self-adaptability to vip molecules.Their proton conducting performance was studied under different humidities at varying temperatures,indicating that the proton conductivity of BPPA with continuous hydrogen bonding networks formed by water molecules reaches 5.14×10^(−2)S cm^(−1) under 80℃ and 95% relative humidity(RH),which is four orders of magnitude higher than those of BPPA-azo and BPPA-gua with their continuous hydrogen bonding networks formed by 1,2,4-triazole and guanidine molecules,respectively,under the same conditions.The evidence from this study suggests that the rotational degrees of freedom of hydrogen bonding donors and acceptors play the most important role in the construction of efficient proton conduction pathways.展开更多
基金supported by the Jiangsu Planned Projects for Postdoctoral Research Funds (No. 0701001B)
文摘The donor-acceptor complex derived from 2-amino-1,3-benzothiazole （ABT） and ethyl 5,6-benzocoumarin-3-carboxylate （EBCC） has been synthesized and its crystal structure was determined by single-crystal X-ray diffraction. The crystal belongs to the monoclinic system, space group P21/c, with a = 8.6485（3）, b = 7.7743（3）, c = 29.1963（10） A, β = 92.0460（10）°, Z = 4, Mr = 418.45, V= 1961.79（12） A^3, Dc = 1.417 g/cm^3,μ = 0.199 mm^-1, F（000） = 872, the final R = 0.0350 and wR = 0.1226. The complex is an A…D…D＇…A＇ H-bonded tetramer. The intermolecular N-H…O and N-H…N hydrogen bonds, together with π-π stacking interactions, stabilize the crystal structure by forming a supramolecular architecture. It is found that, in solid state, the fluorescence emission of the complex is quenched significantly while the UV-vis spectrum exhibits a broad band at 346 nm with shoulder, which can be attributed to the donor-acceptor complex formed.
基金the National Natural Science Foundation of China (20001007 20131020)Natural Science Foundation of the Chinese Academy of Sciences (KJCX2-H3) and Fujian province (2000F006)
基金supported by the National Natural Science Foundation of China(21676230,21373177)~~
文摘Despite the significance of hydrogen bonding in deep eutectic solvents（DESs） for desulfurization processes, little is understood about the relationship between the DES composition, hydrogen-bonding strength, and oxidative desulfurization activity. In this study, a new family of caprolactam-based acidic DESs was prepared with different molar ratios of caprolactam and oxalic acid. The prepared DESs were characterized by differential scanning calorimetry, Fourier transform infrared spectroscopy, 1 H nuclear magnetic resonance, and thermogravimetric analyses. These DESs were employed for oxidative desulfurization reactions and the desulfurization efficiency was found to vary regularly with the DES composition. The factors influencing the removal of dibenzothiophene were systematically investigated and the desulfurization efficiency of the caprolactam-based acidic DESs reached as high as 98% under optimal conditions. The removal of different sulfur compounds followed the order： dibenzothiophene 4,6-dimethyldibenzothiophene benzothiophene. The combined experimental data and characterization results revealed that the oxidative desulfurization efficiency of the system was influenced by the hydrogen bonding interactions with the DES, which can be optimized by adjusting the DES composition. These findings regarding hydrogen bonding in DESs provide new insight for better understanding of the mechanism of diesel deep desulfurization processes.
基金supported by the National Natural Science Foundation of China (No. 50872057)
文摘Two new binary cocrystals formulated as POM·NBA 1 and POM·DNSA 2 （POM = 3-methyl-4-nitro-pyridine-N-oxide, NBA = o-nitrobenzoic acid, DNSA = 3,5-dinitrosalicylic acid） have been successfully synthesized and characterized by elemental analysis, IR and X-ray single- crystal diffraction analysis. The crystal of 1 crystallizes in triclinic, space group P1, with a = 7.621（4）, b = 7.816（4）, c = 11.702（5） , α = 87.957（10）, β = 83.642（10）, γ = 81.535（10）o, C13H11N3O7, Z = 2, Mr = 321.25, V = 685.1（6） 3, Dc = 1.557 g/cm3, F（000） = 332, μ = 0.129 mm-1, the final R = 0.0632 and wR = 0.0831. The crystal of 2 crystallizes in monoclinic, space group P21/c with a = 14.910（9）, b = 5.904（3）, c =19.321（12） , β = 110.583（10）o, C13H10N4O10, Z = 4, Mr = 382.25, V = 1592.1（16） 3, Dc = 1.595 g/cm3, F（000） = 784, μ = 0.140 mm-1, the final R = 0.0598 and wR = 0.1589. Further structure analysis reveals that the POM with NBA and DNSA molecules in 1 and 2 are linked into 3D structures by the combination of strong O-H…O and weak C-H…O hydrogen bonds, π…π stackings and diverse short contacts, in which different C-H…O weak hydrogen bonds may play a key role in constructing the network structures.
基金the financial support by the National Natural Science Foundation of China (22371010, 21771017, and 51702009)the "Hundred Talents Program" of the Chinese Academy of Sciences, the Fundamental Research Funds for the Central Universities+1 种基金the Shenzhen Science and Technology Program (JCYJ20210324115412035, JCYJ2021-0324123202008, JCYJ20210 324122803009 and ZDSYS20210813095534001)the Guangdong Basic and Applied Basic Research Foundation (2021A1515110880)
文摘The use of redox-active organic electrode materials in energy storage is restricted due to their inferior solvent resistance,abysmal conductivity,and the resultant low practical capacity.To address these issues,a class of bipolar p-phenylenediimidazole-based small-molecule compounds are designed and fabricated.Theπ-conjugated backbone of these small molecules allows for electron delocalization on a big conjugation plane,endowing them with good conductivity and reaction reversibility.Furthermore,when the para-positions of phenylene are occupied by hydroxyl groups,as-formed intramolecular hydrogen bonds(N-H...O)between phenolic hydroxyl groups and the–NH groups of imidazole rings further enhance the structural planarity,resulting in higherπ-conjugation degree and better conductivity,and thus higher utilization of active sites and electrode capacity,proved by both experimental results and theoretical calculations.The optimized composite electrode DBNQ@rGO-45 shows a high specific capacity(∼308 mA h g^(−1)at 100 mA g^(−1))and a long cycling stability(112.9 mA h g^(−1)after 6000 cycles at 2000 mA g^(−1)).The significantly better electrochemical properties for hydroxyl group-containing compounds than those without hydroxyl groups attributed to intramolecular hydrogen bond-induced conjugation enhancement will inspire the structure design of organic electrodes for better energy storage.
基金supported by 973 Program (2006CB932900)the National Natural Science Foundation of China (20571074)
文摘The reaction of 2,4,6-tris（2-pyridyl）-1,3,5-triazine （tptz） and K2PdCl4 in THF/H2O （10：1） results in the hydrolysis of tptz to bis（2-pyridylcarbonyl）amide anion （bpca）, and affords complex Pd（bpca）Cl 1, which is the first example of Pd（Ⅱ）-promoted hydrolysis of ligands. Crystal data for 1： orthorhombic, space group Pbcn, a = 12.0136（17）, b = 14.180（2）, c = 6.9747（11）A, V= 1188.2（3） A3, Z = 4, Mr = 368.06, Dc = 2.058 g/cm3, F（000） = 720,μ = 1.786 mm^-1, λ（MoKα） = 0.71073 A, T= 293（2） K, 2θmax = 54.9°, GOOF = 1.085, the final R= 0.0647 and wR = 0.1051 for 1234 observed reflections with I 〉 2σ（I） （refinement on F2）. Complex 1 is connected through hydrogen bonding to give a 2D network. And weak Pd...Pd interactions are also found between adjacent molecules with the distance of 3.6074（5） A, so the complex is further extended into a 3D supramolecular structure. Thermal gravity analysis （TGA） shows that 1 exhibits high thermal stability below 310℃. X-ray powder diffraction （XRD） and UV/Vis spectrum of 1 are also discussed.
基金supported by the National Key R&D Program of China(2018YFE0200700)NSFC(21790363,21871271,22090021,22075293,22021002,22071254).
文摘The soft nature has endowed conjugated polymers with promising applications in a wide range of field-effect transistor(FET)based flexible electronics.With unremitting efforts on revealing the molecular structure-property relationships,numerous novel conjugated polymers with high mobility and excellent mechanical property have been developed in the past decades.Incorporating hydrogen-bonding(H-bonding)units into semiconducting polymers is one of the most successful strategies for designing high-performance semiconducting materials.In this review,we aim to highlight the roles of H-bonding units in the performances of polymeric FETs from three aspects.These include(i)charge mobility enhancement for semiconducting polymers after incorporation of H-bonding units into the side chains,(ii)the effects of H-bonding units on the stretchability of conjugated polymers,and(iii)the improvement of self-healing properties of conjugated polymers containing dynamic hydrogen bonds due to the H-bonding units in the side chains or conjugated backbones.
基金financial support from the National Natural Science Foundation of China(21972034,21673060)the State Key Lab of Urban Water Resource and the Environment of Harbin Institute of Technology(HIT2019DX12).
文摘A novel zinc(II)-based 3D metal organic framework(MOF)[Zn_(3)(L)_(3)(H_(2)L)·2DMF·H_(2)O]with dual hydrogenbond donor(HBD)groups of a free carboxyl and amine,was synthesized solvothermally via 2-aminoterephthalic acid(H_(2)L)and 3,5-pyridinedicarboxylic acid ligands.The carboxyl and amine in the prepared Zn_(3)(L)_(3)(H_(2)L)acting as HBD groups can promote the CO_(2) cycloaddition reaction with epoxides.Besides this,the contained sufficient amino groups showing Lewis base properties also facilitated Zn_(3)(L)_(3)(H_(2)L)to activate CO_(2) by forming a carbamate intermediate,while Zn(II)centers acted as Lewis-acid sites accomplishing the epoxide activation.Therefore,Zn_(3)(L)_(3)(H_(2)L)with Lewis acid–base properties and dual HBD groups exhibited an efficient heterogeneous catalysis for the coupling of epoxides and CO_(2).The yield of the propylene carbonate(PC)achieved 99% under 80℃,1.0 MPa CO_(2) and solvent-free conditions.Corresponding carbonate yields of various epoxides could be over 95%even at room temperature by prolonging the reaction time.Moreover,Zn_(3)(L)_(3)(H_(2)L)showed extraordinary versatility to various epoxides and excellent recycling without any obvious loss in activity.Furthermore,a plausible mechanism was proposed for the CO_(2) cycloaddition to epoxides based on the structural evidence and catalytic effects.
基金supported by the National Natural Science Foundation of China(NSFC,Grant No.21771193,22275210,and 22201305)the Fundamental Research Funds for the Central Universities(22CX06024A)the Outstanding Youth Science Fund Projects of Shandong Province(2022HWYQ-070).
文摘It is a widely held view that the continuous hydrogen bonding network plays a crucial role in proton transport.Herein,we report the cyclic single-crystal-to-single-crystal transformation of three hydrogenbonded organic frameworks(HOFs),BPPA,BPPA-azo,and BPPA-gua,induced by the change of auxiliary ligands,which explicitly demonstrates that the hydrophilic interlayers of BPPA possess good self-adaptability to vip molecules.Their proton conducting performance was studied under different humidities at varying temperatures,indicating that the proton conductivity of BPPA with continuous hydrogen bonding networks formed by water molecules reaches 5.14×10^(−2)S cm^(−1) under 80℃ and 95% relative humidity(RH),which is four orders of magnitude higher than those of BPPA-azo and BPPA-gua with their continuous hydrogen bonding networks formed by 1,2,4-triazole and guanidine molecules,respectively,under the same conditions.The evidence from this study suggests that the rotational degrees of freedom of hydrogen bonding donors and acceptors play the most important role in the construction of efficient proton conduction pathways.
