Anion receptors including pyrimidine subunit were designed and synthesized and their binding abilities with various anions were investigated by fluorescence and ~1H NMR titration experiments.DFT calculations provided ...Anion receptors including pyrimidine subunit were designed and synthesized and their binding abilities with various anions were investigated by fluorescence and ~1H NMR titration experiments.DFT calculations provided some information for anion recognition.It is confirmed that both of two new pyrimidine anion receptors have the selectivity for Cl-.展开更多
Two types of palladiu m(Ⅱ)-based metallacalixarenes[ML]^(2+)and[ML_(2)]^(2+)have been synthesized through coordination-driven self-assembly from a series of flexible pyridine-bridged diimidazole ligands[2,6-bis((1 H-...Two types of palladiu m(Ⅱ)-based metallacalixarenes[ML]^(2+)and[ML_(2)]^(2+)have been synthesized through coordination-driven self-assembly from a series of flexible pyridine-bridged diimidazole ligands[2,6-bis((1 H-imidazol-1-yl)methyl)pyridine(L^(1)),2,6-bis((1 H-benzo[d]imidazol-1-yl)methyl)pyridine(L^(2)),2,6-bis((1 H-naphtho[2,3-d]imidazol-1-yl)methyl)pyridine(L^(3))],with palladium(II)-based building blocks[Pd(BF_(4))_(2)(M^(1)-BF_4)and(tmeda)Pd(NO_(3))_(2)(M^(2)-NO_(3))(tmeda=N,N,N',N'-tetramethyl-ethylenediamine)].All complexes were characterized by NMR spectroscopy(^(1)H NMR and^(13)C NMR),mass spectrometry(CSIMS,ESI-HRMS)and elemental analysis.The single crystal X-ray diffraction analysis of[M^(1)L^(2)_2](NO_(3))_(2),[M^(1)L^(3)_2](NO_(3))_(2),[M^(1)L^(3)_2](PF_6)_2 and[M~2 L^(3)](NO_(3))_(2)further confirmed the uniquely single bowl-shape and double bowl-shape structures.The anion binding properties within the metallacalixarenes as receptors were also investigated by NMR titration experiments in DMSO.展开更多
A new colorimetric recognition receptor 1 based on the dual capability containing NH binding sites of selectively sensing anionic guest species has been synthesized. Compared with other halide anions, its UV/Vis absor...A new colorimetric recognition receptor 1 based on the dual capability containing NH binding sites of selectively sensing anionic guest species has been synthesized. Compared with other halide anions, its UV/Vis absorption spectrum in dimethyl sulfoxide showed the response toward the presence of fluoride anion with high selectivity, and also displayed dramatic color changes from colorless to yellow in the presence of TBAF （5 × 10^-5 mol/L）. The similar UV/Vis absorption spectrum change also occurred when 1 was treated with AcO^- while a little change with H2PO^-4 and OH^-. Receptor 1 has almost not affinity abilities to Cl^-, Br^- and I^-. The binding ability of receptor 1 to fluoride with high selectivity over other halides contributes to the anion size and the ability of forming hydrogen bonding. While the different ability of binding with geometrically triangular （AcO^-）, tetrahedral （H2PO^-4 ） and linear （OH^-） anions maybe result from their geometry configuration.展开更多
A novel anion receptor2 bearing anthracene flurophore and thiourea was synthesized and identified by1H NMR, MS, IR and elemental analysis. The interaction between receptor2 and various α, ω-dicarboxylate anions was ...A novel anion receptor2 bearing anthracene flurophore and thiourea was synthesized and identified by1H NMR, MS, IR and elemental analysis. The interaction between receptor2 and various α, ω-dicarboxylate anions was studied by fluorescence spectrum. The obtained fluorescence data indicate that 1∶1 stoichiometry complex is formed between receptor2 with diferent dicarboxylate anions through a hydrogen-bonging interaction. The selectivity of2 for recognition of different dicarboxylates deponds on chain length of the anionic species. Key words anion receptor - fluorescence - synthesis - anion recognition CLC number O 626 Foundation item: Supported by the National Science Foundation of china (20372054)Biography: WANG Fa-jun (1976-), male, Master Candidate, research direction: supramolecular chemistry.展开更多
The intimate host-anion interactions will regulate thermodynamics and kinetics in the self-assembly of cationic cages mimicking biological counterparts.Herein,we report construction and transformation of three Pd(Ⅱ)-...The intimate host-anion interactions will regulate thermodynamics and kinetics in the self-assembly of cationic cages mimicking biological counterparts.Herein,we report construction and transformation of three Pd(Ⅱ)-based metal-organic cages(MOCs)depending on different anions.Stoichiometric conversions of the lantern-shaped MOC-34 into either octahedral MOC-35 or tricapped trigonal prism MOC-36 are induced by BF_(4)^(–)or NO_(3)^(–),respectively.MOC-36 is kinetically favored and can undergo quantitative conversion to the thermodynamically preferred MOC-35 upon heating,accelerated by excess BF_(4)^(–)to motivate dissociative dynamics of Pd-vertices and lower activation barrier of cage transformation.The guest encapsulation behaviors of MOC-35 and MOC-36 have also been tested.These results manifest a significance of host-anion dynamics beyond complementary anion template,shedding light on the understanding of intricate anion recognition in nature.展开更多
基金Project (21302232) supported by the National Natural Science Foundation of China
文摘Anion receptors including pyrimidine subunit were designed and synthesized and their binding abilities with various anions were investigated by fluorescence and ~1H NMR titration experiments.DFT calculations provided some information for anion recognition.It is confirmed that both of two new pyrimidine anion receptors have the selectivity for Cl-.
基金supported by the National Natural Science Foundation of China(No.21906002)Beijing Municipal Science and Technology Project(No.KM202010005010)+2 种基金Beijing Municipal Natural Science Fund Project of Beijing Education Committee science and technology project key project(No.KZ201710005001)Beijing municipal high level innovative team building program(No.IDHT20180504)Beijing Outstanding Young Scientist Program(No.BJJWZYJH01201910005017)。
文摘Two types of palladiu m(Ⅱ)-based metallacalixarenes[ML]^(2+)and[ML_(2)]^(2+)have been synthesized through coordination-driven self-assembly from a series of flexible pyridine-bridged diimidazole ligands[2,6-bis((1 H-imidazol-1-yl)methyl)pyridine(L^(1)),2,6-bis((1 H-benzo[d]imidazol-1-yl)methyl)pyridine(L^(2)),2,6-bis((1 H-naphtho[2,3-d]imidazol-1-yl)methyl)pyridine(L^(3))],with palladium(II)-based building blocks[Pd(BF_(4))_(2)(M^(1)-BF_4)and(tmeda)Pd(NO_(3))_(2)(M^(2)-NO_(3))(tmeda=N,N,N',N'-tetramethyl-ethylenediamine)].All complexes were characterized by NMR spectroscopy(^(1)H NMR and^(13)C NMR),mass spectrometry(CSIMS,ESI-HRMS)and elemental analysis.The single crystal X-ray diffraction analysis of[M^(1)L^(2)_2](NO_(3))_(2),[M^(1)L^(3)_2](NO_(3))_(2),[M^(1)L^(3)_2](PF_6)_2 and[M~2 L^(3)](NO_(3))_(2)further confirmed the uniquely single bowl-shape and double bowl-shape structures.The anion binding properties within the metallacalixarenes as receptors were also investigated by NMR titration experiments in DMSO.
文摘A new colorimetric recognition receptor 1 based on the dual capability containing NH binding sites of selectively sensing anionic guest species has been synthesized. Compared with other halide anions, its UV/Vis absorption spectrum in dimethyl sulfoxide showed the response toward the presence of fluoride anion with high selectivity, and also displayed dramatic color changes from colorless to yellow in the presence of TBAF （5 × 10^-5 mol/L）. The similar UV/Vis absorption spectrum change also occurred when 1 was treated with AcO^- while a little change with H2PO^-4 and OH^-. Receptor 1 has almost not affinity abilities to Cl^-, Br^- and I^-. The binding ability of receptor 1 to fluoride with high selectivity over other halides contributes to the anion size and the ability of forming hydrogen bonding. While the different ability of binding with geometrically triangular （AcO^-）, tetrahedral （H2PO^-4 ） and linear （OH^-） anions maybe result from their geometry configuration.
文摘A novel anion receptor2 bearing anthracene flurophore and thiourea was synthesized and identified by1H NMR, MS, IR and elemental analysis. The interaction between receptor2 and various α, ω-dicarboxylate anions was studied by fluorescence spectrum. The obtained fluorescence data indicate that 1∶1 stoichiometry complex is formed between receptor2 with diferent dicarboxylate anions through a hydrogen-bonging interaction. The selectivity of2 for recognition of different dicarboxylates deponds on chain length of the anionic species. Key words anion receptor - fluorescence - synthesis - anion recognition CLC number O 626 Foundation item: Supported by the National Science Foundation of china (20372054)Biography: WANG Fa-jun (1976-), male, Master Candidate, research direction: supramolecular chemistry.
基金supported by the NKRD Program of China(No.2021YFA1500401)the National Natural Science Foundation of China(Nos.21821003,21890380)the LIRTP of Guangdong Pearl River Talents Program(No.2017BT01C161)。
文摘The intimate host-anion interactions will regulate thermodynamics and kinetics in the self-assembly of cationic cages mimicking biological counterparts.Herein,we report construction and transformation of three Pd(Ⅱ)-based metal-organic cages(MOCs)depending on different anions.Stoichiometric conversions of the lantern-shaped MOC-34 into either octahedral MOC-35 or tricapped trigonal prism MOC-36 are induced by BF_(4)^(–)or NO_(3)^(–),respectively.MOC-36 is kinetically favored and can undergo quantitative conversion to the thermodynamically preferred MOC-35 upon heating,accelerated by excess BF_(4)^(–)to motivate dissociative dynamics of Pd-vertices and lower activation barrier of cage transformation.The guest encapsulation behaviors of MOC-35 and MOC-36 have also been tested.These results manifest a significance of host-anion dynamics beyond complementary anion template,shedding light on the understanding of intricate anion recognition in nature.
