The title compound BBBT-Dry (C17H12Br2S5, Mr=536.42) has been synthesized and its structure feature has been described. BBBT-DTT is characterized by one dimensional chains formed by S…S (head to head) and Br…Br (tai...The title compound BBBT-Dry (C17H12Br2S5, Mr=536.42) has been synthesized and its structure feature has been described. BBBT-DTT is characterized by one dimensional chains formed by S…S (head to head) and Br…Br (tail to tail) intermolecular interactions.展开更多
Dielectric properties of dithiol self-assemble monolayers (SAMs) under ac electric field were presented, Using a Hg-SAM/SAM-Ⅱg junction, the ac impedances of dithiol SAMs were measured using a sinusoidal perturbati...Dielectric properties of dithiol self-assemble monolayers (SAMs) under ac electric field were presented, Using a Hg-SAM/SAM-Ⅱg junction, the ac impedances of dithiol SAMs were measured using a sinusoidal perturbation of 30 mV (peak to-peak) with the frequency ranging from 1 Hz to 1 MHz at zero bias. The contributions from dithiol SAMs and solvent interlayers were separated due to their different behaviors at ac impedance. The peak position in the loss spectra (the plot; of tgδ vs. frequency) moves to low frequcney with the incrcase of chain length of dithiols. Using a correlation of peak position with the chain length, the active energies of 23-39 meV for dithiol SAMs of C6-C10 under an ac electric field were derived,展开更多
The magnetic susceptibility of (Bu4N)(NI(MEDT)2) and (Bu4N)(Ni(PHDT)2)(MEDT:5-methyl-6-hydro-1, 4-dithiin-2, 3-dithiolate, PHDT: 5-phenyl-6-hydro-1.4-dithiin- 2,3-dithiolate) was measured in the temperature range of 7...The magnetic susceptibility of (Bu4N)(NI(MEDT)2) and (Bu4N)(Ni(PHDT)2)(MEDT:5-methyl-6-hydro-1, 4-dithiin-2, 3-dithiolate, PHDT: 5-phenyl-6-hydro-1.4-dithiin- 2,3-dithiolate) was measured in the temperature range of 75-300K. The magnitudeof magnctic moments is consistent,with a doublet state arising from Ni(Ⅲ).Antiferromagnetic properties were discussed in consideration of molecularstructure.展开更多
The crystal of complex [Li(THF)4][Fe(S2C2B10H10)2(THF)] 3 belongs to monoclinic, space group P21 with a = 11.964(2), b = 16.527(3), c = 12.554(3) ? = 108.70(3)? V = 2351.3(8) 3, Z = 2, Mr = 835.95, Dc = 1.181 g/cm3, ...The crystal of complex [Li(THF)4][Fe(S2C2B10H10)2(THF)] 3 belongs to monoclinic, space group P21 with a = 11.964(2), b = 16.527(3), c = 12.554(3) ? = 108.70(3)? V = 2351.3(8) 3, Z = 2, Mr = 835.95, Dc = 1.181 g/cm3, (MoK? = 5.30 cm1, F(000) = 874, R = 0.0622 and Rw = 0.1538 for 1641 observed reflections with I > 2(I). The ionic complex of 3 contains the square pyramidal anion of [Fe(S2C2B10H10)2(THF)] and the tetrahedral cation of [Li(THF)4]+. The iron is 5-coordinated and located in the square pyramidal configuration. The iron atom and the four sulfur atoms are almost coplanar. The Lithium atom is coordinated with four oxygen atoms of four THF molecules and located in a tetrahedral configuration.展开更多
The synthesis and the crystal structure of the title compound (Bu4N)(2)Hg(S2C=C(CN)(2))(2) 1 is reported herein. The crystal is attributed to trielinic system and space group P-1, fw=965.88. The crystal lattice parame...The synthesis and the crystal structure of the title compound (Bu4N)(2)Hg(S2C=C(CN)(2))(2) 1 is reported herein. The crystal is attributed to trielinic system and space group P-1, fw=965.88. The crystal lattice parameters are a=9.45(1), b=15.827(2), c=17.619(2)Angstrom, alpha =108.12(2), beta =99.54(2), gamma =97.60(2)degrees, V=2421.9(8)Angstrom, mu (MoKalpha)=3.390mm(-1), Z=2, D-c=1.324g.cm(-3), F(000)=996, R=0.054, wR=0.058.展开更多
The reaction of the 16e half-sandwich complex Cp*Co(S2C2B10H10) (1) (Cp* = pentamethylcyclopentadienyl) with excess methyl acetylene monocarboxylate, HC≡C-CO2Me, affords the 18e complexes 2-6. Compound 2 bears a B-CH...The reaction of the 16e half-sandwich complex Cp*Co(S2C2B10H10) (1) (Cp* = pentamethylcyclopentadienyl) with excess methyl acetylene monocarboxylate, HC≡C-CO2Me, affords the 18e complexes 2-6. Compound 2 bears a B-CH2 unit in which B-substitution occurs in the B(3)/B(6) position of the ortho-carborane cage. Complexes 3-6 are geometrical isomers, in which the alkyne is twofold inserted into one of the Co-S bonds in all the four possible ways. Treatment of 1 with excess 3-butyn-2-one or phenyl ethynyl ketone, HC≡C-C(O)R (R = Me, Ph), at ambient temperature leads to the 18e complexes 7-10, respectively, with two alkynes inserted into one of the Co-S bonds. All the new complexes were fully characterized by spectroscopic techniques and elemental analysis. The solid-state structures of 2, 3, 5, 7, 8, 9 and 10 were further characterized by X-ray structural analysis.展开更多
The vicinal dithiol motif is widely present in proteins, and is critical for proteins’ structures and functions.In recent years, a variety of fluorescent probes with high specificity and outstanding optical propertie...The vicinal dithiol motif is widely present in proteins, and is critical for proteins’ structures and functions.In recent years, a variety of fluorescent probes with high specificity and outstanding optical properties for sensing protein vicinal dithiols have been developed. In this review, we summarized the fluorescent probes of protein vicinal dithiols in literature. These probes are classified into four types based on their acceptor sites, i.e., biarsenical probes, monoarsenical probes, dimaleimide probes and diacrylate probes.Through analyzing the properties of different probes, we expect that this review would help readers further understand the structural factors of these probes and provide the design strategy for novel fluorescent probes with improved properties.展开更多
A new cluster-cracking method to synthesize dithiolate metal complexes was reported and four unsymmetric complexes with formula (Me4N)(2)[M(Ln)(SPh)(2)] (M = Cd and Zn, L1 = dmit = 1, 3-dithiole-2-thione-4, 5-dithiola...A new cluster-cracking method to synthesize dithiolate metal complexes was reported and four unsymmetric complexes with formula (Me4N)(2)[M(Ln)(SPh)(2)] (M = Cd and Zn, L1 = dmit = 1, 3-dithiole-2-thione-4, 5-dithiolate, L2 = dmid = 1, 3-dithiole-2-one-4, 5-dithiolate, SPh = thiophenolate) (1-4) were characterized by, elemental analysis, ER, UV NMR spectra and so on. The advantages of this method am summarized in two aspects: (1) the preparation is very convenient; (2) the reaction usually completed giving the product with high,purity. The crystal structure of 1 showed that the bond distances of Cd(II) to the sulfur of the thiophenolate group are shorter than those of Cd(II) to the sulfur of dmit, so that the thiophenolate group does not be replaced in the reaction and the mixed ligand complexes are the dominant products. The dmit complexes showed well third-order NLO properties, but not of the dmid complexes, although druid is an analogue to dmit.展开更多
Currently,intensive research efforts focus on the fabrication of meso-structures of assembled colloidal quantum dots(QDs)with original optical and electronic properties.Such collective features originate from the QDs ...Currently,intensive research efforts focus on the fabrication of meso-structures of assembled colloidal quantum dots(QDs)with original optical and electronic properties.Such collective features originate from the QDs coupling,depending on the number of connected units and their distance.However,the development of general methodologies to assemble colloidal QD with precise stoichiometry and particle-particle spacing remains a key challenge.Here,we demonstrate that dimers of CdSe QDs,stable in solution,can be obtained by engineering QD surface chemistry,reducing the surface steric hindrance and favoring the link between two QDs.The connection is made by using alkyl dithiols as bifunctional linkers and different chain lengths are used to tune the interparticle distance from few nm down to 0.5 nm.The spectroscopic investigation highlights that coupling phenomena between the QDs in dimers are strongly dependent on the interparticle distance and QD size,ultimately affecting the exciton dissociation efficiency.展开更多
Three novel compounds [Ni(en)3](ndt)·H2O (1), [Co(en)3](ndt)·H2O (2) and [Mn(en)3](ndt)·H2O (3) (en= ethylenediamine, ndt= 1,5-naphthalenedithiolate) have been synthesized under hydr...Three novel compounds [Ni(en)3](ndt)·H2O (1), [Co(en)3](ndt)·H2O (2) and [Mn(en)3](ndt)·H2O (3) (en= ethylenediamine, ndt= 1,5-naphthalenedithiolate) have been synthesized under hydrothermal conditions, The structures were characterized by single crystal X-ray diffraction and all belong to monoclinic space group Cc. The [M(en)3]^2+ cations (M=Ni^Ⅱ, Co^Ⅱ, Mn^Ⅱ), ndt anions and crystallized water molecules assemble an iso-structural three-dimensional network through H-bonding interactions. Optical absorption properties and band gaps of such three compouds were determined with UV/Vis/NIR diffuse reflectance spectra.展开更多
文摘The title compound BBBT-Dry (C17H12Br2S5, Mr=536.42) has been synthesized and its structure feature has been described. BBBT-DTT is characterized by one dimensional chains formed by S…S (head to head) and Br…Br (tail to tail) intermolecular interactions.
文摘Dielectric properties of dithiol self-assemble monolayers (SAMs) under ac electric field were presented, Using a Hg-SAM/SAM-Ⅱg junction, the ac impedances of dithiol SAMs were measured using a sinusoidal perturbation of 30 mV (peak to-peak) with the frequency ranging from 1 Hz to 1 MHz at zero bias. The contributions from dithiol SAMs and solvent interlayers were separated due to their different behaviors at ac impedance. The peak position in the loss spectra (the plot; of tgδ vs. frequency) moves to low frequcney with the incrcase of chain length of dithiols. Using a correlation of peak position with the chain length, the active energies of 23-39 meV for dithiol SAMs of C6-C10 under an ac electric field were derived,
文摘The magnetic susceptibility of (Bu4N)(NI(MEDT)2) and (Bu4N)(Ni(PHDT)2)(MEDT:5-methyl-6-hydro-1, 4-dithiin-2, 3-dithiolate, PHDT: 5-phenyl-6-hydro-1.4-dithiin- 2,3-dithiolate) was measured in the temperature range of 75-300K. The magnitudeof magnctic moments is consistent,with a doublet state arising from Ni(Ⅲ).Antiferromagnetic properties were discussed in consideration of molecularstructure.
基金Financially Supported by the National Natural Science Foundation of China (29974029, 29925101) and Special Funds for Major State Basic Research Projects of China (G1999064800)
文摘The crystal of complex [Li(THF)4][Fe(S2C2B10H10)2(THF)] 3 belongs to monoclinic, space group P21 with a = 11.964(2), b = 16.527(3), c = 12.554(3) ? = 108.70(3)? V = 2351.3(8) 3, Z = 2, Mr = 835.95, Dc = 1.181 g/cm3, (MoK? = 5.30 cm1, F(000) = 874, R = 0.0622 and Rw = 0.1538 for 1641 observed reflections with I > 2(I). The ionic complex of 3 contains the square pyramidal anion of [Fe(S2C2B10H10)2(THF)] and the tetrahedral cation of [Li(THF)4]+. The iron is 5-coordinated and located in the square pyramidal configuration. The iron atom and the four sulfur atoms are almost coplanar. The Lithium atom is coordinated with four oxygen atoms of four THF molecules and located in a tetrahedral configuration.
基金the National Natural Science Foundation of China (No.29631040) and Committee of Sci. & Tech. of Beijing Foundation (No.95287180
文摘The synthesis and the crystal structure of the title compound (Bu4N)(2)Hg(S2C=C(CN)(2))(2) 1 is reported herein. The crystal is attributed to trielinic system and space group P-1, fw=965.88. The crystal lattice parameters are a=9.45(1), b=15.827(2), c=17.619(2)Angstrom, alpha =108.12(2), beta =99.54(2), gamma =97.60(2)degrees, V=2421.9(8)Angstrom, mu (MoKalpha)=3.390mm(-1), Z=2, D-c=1.324g.cm(-3), F(000)=996, R=0.054, wR=0.058.
基金the National Natural Science Foundation of China (20925104,90713023,20771055,20721002)the Major State Basic Research Development Program of China (2006CB806104)the National Basic Research Program of China (2007CB925101,2010CB923303)
文摘The reaction of the 16e half-sandwich complex Cp*Co(S2C2B10H10) (1) (Cp* = pentamethylcyclopentadienyl) with excess methyl acetylene monocarboxylate, HC≡C-CO2Me, affords the 18e complexes 2-6. Compound 2 bears a B-CH2 unit in which B-substitution occurs in the B(3)/B(6) position of the ortho-carborane cage. Complexes 3-6 are geometrical isomers, in which the alkyne is twofold inserted into one of the Co-S bonds in all the four possible ways. Treatment of 1 with excess 3-butyn-2-one or phenyl ethynyl ketone, HC≡C-C(O)R (R = Me, Ph), at ambient temperature leads to the 18e complexes 7-10, respectively, with two alkynes inserted into one of the Co-S bonds. All the new complexes were fully characterized by spectroscopic techniques and elemental analysis. The solid-state structures of 2, 3, 5, 7, 8, 9 and 10 were further characterized by X-ray structural analysis.
基金financial supports from the National Natural Science Foundation of China (Nos. 21572093 & 21778028)the 111 Project
文摘The vicinal dithiol motif is widely present in proteins, and is critical for proteins’ structures and functions.In recent years, a variety of fluorescent probes with high specificity and outstanding optical properties for sensing protein vicinal dithiols have been developed. In this review, we summarized the fluorescent probes of protein vicinal dithiols in literature. These probes are classified into four types based on their acceptor sites, i.e., biarsenical probes, monoarsenical probes, dimaleimide probes and diacrylate probes.Through analyzing the properties of different probes, we expect that this review would help readers further understand the structural factors of these probes and provide the design strategy for novel fluorescent probes with improved properties.
基金ProjectsupportedbytheNationalNaturalScienceFoundationofChina (No .2 0 0 710 2 4) theEducationCommitteeofJiangsuProvince (No .0 0KJB15 0 0 0 1) .
文摘A new cluster-cracking method to synthesize dithiolate metal complexes was reported and four unsymmetric complexes with formula (Me4N)(2)[M(Ln)(SPh)(2)] (M = Cd and Zn, L1 = dmit = 1, 3-dithiole-2-thione-4, 5-dithiolate, L2 = dmid = 1, 3-dithiole-2-one-4, 5-dithiolate, SPh = thiophenolate) (1-4) were characterized by, elemental analysis, ER, UV NMR spectra and so on. The advantages of this method am summarized in two aspects: (1) the preparation is very convenient; (2) the reaction usually completed giving the product with high,purity. The crystal structure of 1 showed that the bond distances of Cd(II) to the sulfur of the thiophenolate group are shorter than those of Cd(II) to the sulfur of dmit, so that the thiophenolate group does not be replaced in the reaction and the mixed ligand complexes are the dominant products. The dmit complexes showed well third-order NLO properties, but not of the dmid complexes, although druid is an analogue to dmit.
基金This work is financially supported by the H2020 FET project COPAC(Contract agreement n.766563)。
文摘Currently,intensive research efforts focus on the fabrication of meso-structures of assembled colloidal quantum dots(QDs)with original optical and electronic properties.Such collective features originate from the QDs coupling,depending on the number of connected units and their distance.However,the development of general methodologies to assemble colloidal QD with precise stoichiometry and particle-particle spacing remains a key challenge.Here,we demonstrate that dimers of CdSe QDs,stable in solution,can be obtained by engineering QD surface chemistry,reducing the surface steric hindrance and favoring the link between two QDs.The connection is made by using alkyl dithiols as bifunctional linkers and different chain lengths are used to tune the interparticle distance from few nm down to 0.5 nm.The spectroscopic investigation highlights that coupling phenomena between the QDs in dimers are strongly dependent on the interparticle distance and QD size,ultimately affecting the exciton dissociation efficiency.
文摘Three novel compounds [Ni(en)3](ndt)·H2O (1), [Co(en)3](ndt)·H2O (2) and [Mn(en)3](ndt)·H2O (3) (en= ethylenediamine, ndt= 1,5-naphthalenedithiolate) have been synthesized under hydrothermal conditions, The structures were characterized by single crystal X-ray diffraction and all belong to monoclinic space group Cc. The [M(en)3]^2+ cations (M=Ni^Ⅱ, Co^Ⅱ, Mn^Ⅱ), ndt anions and crystallized water molecules assemble an iso-structural three-dimensional network through H-bonding interactions. Optical absorption properties and band gaps of such three compouds were determined with UV/Vis/NIR diffuse reflectance spectra.