A 3-D supramolecular framework, [Er（pybz）2（Hnds）（H2O）2]·H2O （1, Hpybz = 4- pyridin-4-yl-benzoic acid, H2nds = naphthalene-1,5-disulfonic acid）, based on lanthanide ions and mixed ligands has been hydrothe...A 3-D supramolecular framework, [Er（pybz）2（Hnds）（H2O）2]·H2O （1, Hpybz = 4- pyridin-4-yl-benzoic acid, H2nds = naphthalene-1,5-disulfonic acid）, based on lanthanide ions and mixed ligands has been hydrothermally synthesized. The structure was determined by single-crystal X-ray diffraction and further characterized by IR, elemental analysis and thermogravimetric analysis. Compound 1 crystallizes in the monoclinic system, space group P21/n with a = 9.849（2）, b = 22.526（5）, c = 17.167（4） A, β =105.461（4）° and V = 3670.9（2） A^3. In 1, two seven-coordinated Er^3＋ ions are bridged by two pybz^- ligands to form a dimeric [Er2（COO）2] unit, which is further orderly linked by carboxyl of pybz^-ligand to obtain a 1-D chain running along the a axis. Interestingly, significant H-bonding and π-π stacking interactions link the neighboring parallel chains leading to a 3-D supramolecular network structure which displays 1-D rhombus open channels （17.2A× 22.5A）.展开更多
The complex [Cu2（H2dhbd）2（tpy）2]·CH3OH·4H2O 1 （H4dhbd =2,3-dihydroxybutanedioic acid, tpy = 2,2＇：6＇,2＇＇-terpyridine） has been hydrothermally synthesized and characterized by single-crystal X-ray d...The complex [Cu2（H2dhbd）2（tpy）2]·CH3OH·4H2O 1 （H4dhbd =2,3-dihydroxybutanedioic acid, tpy = 2,2＇：6＇,2＇＇-terpyridine） has been hydrothermally synthesized and characterized by single-crystal X-ray diffraction analysis. The crystal is of triclinic, space groups Pi with a= 8.6859（17）, b = 11.223（2）, c = 12.275（2）A, α = 112.454（3）, β= 98.435（3）, γ = 105.593（3）°, V= 1022.5（3） A^3, Z = 1, C38H42Cu2N6O18, Mr = 997.86, Dc = 1.621 g/cm^3, μ= 1.127 mm^-1, F（000） = 514, T = 293（2） K, the final R = 0.0539 and wR = 0.1394 for 3550 observed reflections with I 〉 2σ（I）. In the dinuclear unit, two Cun atoms are bridged by two H2dhbd chelate anions, forming a 14-membered ring, in which the distance of Cu…Cu atoms is 7.0526（12）A. Adjacent dinuclear units are constituted through π-π interactions and C-H…O hydrogen-bonding interactions, fashioning the final 3-D supramolecular framework with 1-D open channels. Variable-temperature magnetic susceptibility measurement indicates the presence of weak antiferromagnetic exchange interactions between Cu^II ions.展开更多
A neoteric organic-inorganic hybrid Co-substituted phosphotungstate H6{[Co(en)2(OAc)2]2[Co4(H2 O)2(PW9 O34)2]}?2 H2 en?36 H2 O(1, en = enthylenediamine) has been made under hydrothermal conditions and characterized by...A neoteric organic-inorganic hybrid Co-substituted phosphotungstate H6{[Co(en)2(OAc)2]2[Co4(H2 O)2(PW9 O34)2]}?2 H2 en?36 H2 O(1, en = enthylenediamine) has been made under hydrothermal conditions and characterized by IR spectrum, thermogravimetric analysis, diffuse-reflectance spectroscopy, powder X-ray diffraction, single-crystal X-ray diffraction and cyclic voltammetry, respectively. Crystal data for 1: monoclinic, P21/c, a = 18.2234(12), b = 15.3696(9), c = 20.1706(17) ?, β = 106.563(8)°, V = 5415.1(7) ?3, Z = 2, Mr = 6072.30, Dc = 3.724 g/cm3, μ = 20.087 mm-1, F(000) = 5540, R = 0.0585, w R = 0.1543 and S = 1.024. Single-crystal X-ray structure analysis reveals that compound 1 exhibits a 3-D supramolecular framework via H-bonding interactions, in which the discrete Co-complex is modified by two types of organic ligands, en and acetate. In addition, the adsorption experiments demonstrate compound 1 possesses a remarkable capability for scavenging of methylene blue.展开更多
Porous supramolecular frameworks based on metal-organic cages(MOCs)usually have poor structural stability after activation.This issue narrows the scope of their potential applications,particularly for the inclusion of...Porous supramolecular frameworks based on metal-organic cages(MOCs)usually have poor structural stability after activation.This issue narrows the scope of their potential applications,particularly for the inclusion of guest molecules that demand high porosity.Herein,the authors have reported the stabilization of a mesoporous zirconium MOC-based supramolecular framework with an in situ catalytic polymerization strategy.Due to the passivation effect imparted by this strategy,the introduced polymer is primarily distributed on the surface of the crystals,which results in the hybrid material retaining its crystallinity and permanent porosity.A preliminary application of this type of stabilized mesoporous supramolecular framework shows that among MOC-based supramolecular frameworks,it has the highest high-pressure methane uptake.Such a facile strategy may provide a general way to stabilize fragile porous materials and facilitate exploration of their potential applications.展开更多
A microporous supramolecular framework with high water and thermal stability can selectively absorb water molecules over methanol or ethanol due to the suitable channels.The model separation test on columns shows that...A microporous supramolecular framework with high water and thermal stability can selectively absorb water molecules over methanol or ethanol due to the suitable channels.The model separation test on columns shows that an ultra-pure ethanol(99.9%)can be obtained from the mixture of ethanol/water(95:5).Additionally,after refluxing the desolvated sample in 95%ethanol at 60℃for 5 h,the purity of ethanol rises up to 97.43%,which is obviously higher than 96.56%for 4 A molecular sieves.展开更多
Two new alkaline metal borates containing 1D{B5}/{B6}oxoboron helical chains,namely Na0.5[B5O8(OH)2]0.5[B5O6(OH)2]0.5·0.5H3O(1)and NaKCs[B6O9(OH)3](2)were synthesized under solvothermal conditions.Compound 1 cont...Two new alkaline metal borates containing 1D{B5}/{B6}oxoboron helical chains,namely Na0.5[B5O8(OH)2]0.5[B5O6(OH)2]0.5·0.5H3O(1)and NaKCs[B6O9(OH)3](2)were synthesized under solvothermal conditions.Compound 1 contains the interesting alternative left-and right-handed helical{[B5O8(OH)2][B5O6(OH)2]}2-({B5}-1 and{B5}-2)1D chains and compound 2 possesses the similar[B6O11(OH)3]7-({B6})chains.Their 1D chains are further assembled into 2D layers and 3D supramolecular frameworks through O-H…O hydrogen bonds.In addition,the UV cutoff edge of compounds 1 and 2 is both below 190 nm.展开更多
Accompanied by solid-state structural phase transitions,the switchable molecular dynamics(MD)and order-disorder transformation of(i-PrNHMe2)^(+)cation embedded in a deformable{[Ni(NCS)_(6)]^(4-)}_(∞)supramolecular fr...Accompanied by solid-state structural phase transitions,the switchable molecular dynamics(MD)and order-disorder transformation of(i-PrNHMe2)^(+)cation embedded in a deformable{[Ni(NCS)_(6)]^(4-)}_(∞)supramolecular framework are in-depth investigated by variable-temperature tests of single-crystal X-ray diffraction,dielectric measurement,and MD simulation.Interestingly,it is found that the confined swinging or flipping of the(i-PrNHMe_(2))^(+)cation as a whole is assisted by a synergistic change of its torsion angle.This research provides a helpful insight into the solid-state MD of moderate-sized quasi-spherical molecules/ions that feature a flexible inner core.展开更多
Based on the crystal structures of two cucurbit[6]uril/calix[n]arene-based supramolecular frameworks reported by Long and co-workers,we further investigated the interactions of cucurbit[6]uril with 4-sulfocalix[4]aren...Based on the crystal structures of two cucurbit[6]uril/calix[n]arene-based supramolecular frameworks reported by Long and co-workers,we further investigated the interactions of cucurbit[6]uril with 4-sulfocalix[4]arene and 4-sulfocalix[6]arene using ^(1)H NMR spectroscopy and isothermal titration calorimetry(ITC),respectively.Moreover,solid fluorescent materials were prepared via the adsorption of fluorescent dyes by these porous supramolecular frameworks,which exhibit a selective response to certain volatile organic compounds.展开更多
Curcurbit[n]uril(Q[n])-based supramolecular frameworks(QSFs) constructed from the outer surface interaction of Q[n]s(OSIQ) have the characteristic of simplicity,diversity and modulability.Their simplicity is reflected...Curcurbit[n]uril(Q[n])-based supramolecular frameworks(QSFs) constructed from the outer surface interaction of Q[n]s(OSIQ) have the characteristic of simplicity,diversity and modulability.Their simplicity is reflected in their simple composition and preparation methods used for QSFs.The diversity of supramolecular organic frameworks(SOFs) is reflected in the synthesis methods and structural characteristics of the as-obtained QSFs,as well as the variety of structural directing agents and basic building blocks used to prepare QSFs.The modulability is reflected by the controllable channel size in the QSFs,which can be adjusted using different sizes of Q[n]s.In this work,the first re ported cucurbituril Q[6]was selected as the basic building block and three Q[6]-based su p ramolecular frameworks were obtained from aqueous HCl solutions in the presence of [CdCl_(4)]^(2-)respectively.The OSIQs are the main driving forces for the formation of these frameworks.This study shows the diversity of the QSFs.展开更多
A series of Cd(Ⅱ) coordination complexes with an elongated 2,4-dipyridyl-type building block trans-1-(2-pyridyl)-2-(4-pyridyl)ethylene (bpe) and different dicarboxylate ligands have been presented. Generally, bpe sho...A series of Cd(Ⅱ) coordination complexes with an elongated 2,4-dipyridyl-type building block trans-1-(2-pyridyl)-2-(4-pyridyl)ethylene (bpe) and different dicarboxylate ligands have been presented. Generally, bpe shows the unidentate coordination mode and serves as the terminal pendant, whereas the dicarboxylate ligands display various binding fashions to interlink the metal centers to form 1-D comb-like chain, ribbon, and fishbone arrays, as well as 2-D 44 and 4.82 layered networks. Notably, the bpe building block is also involved in secondary interactions such as hydrogen bonding and aromatic stacking to construct the resulting supramolecular architectures. Thermal stability of these complexes has been studied by TG-DTA technique.展开更多
Azo-based pillar[6]arene supramolecular organic frameworks are reported for CO_(2) and N_(2) adsorption and separation by density functional theory and grand canonical Monte–Carlo simulation.Azo-based pillar[6]arene ...Azo-based pillar[6]arene supramolecular organic frameworks are reported for CO_(2) and N_(2) adsorption and separation by density functional theory and grand canonical Monte–Carlo simulation.Azo-based pillar[6]arene provides suitable environment for CO_(2) adsorption and selectivity.The adsorption and selectivity results show that introducing azo groups can effectively improve CO_(2) adsorption and selectivity over N_(2),and both CO_(2) adsorption and CO_(2) selectivity over N_(2) follow the sequence pillar[6]arene N_(4)>pillar[6]arene N2>pillar[6]arene.Pillar[6]arene N_(4) exhibits CO_(2) adsorption capacity of1.36 mmol/g,and superior selectivity of CO_(2) over N_(2) of116.75 with equal molar fraction at 1 bar(1 bar=105 Pa)and 298 K.Interaction analysis confirms that both the Coulomb and van derWaals interactions between CO_(2) with pillar[6]arene frameworks are greater than that of N_(2).The stronger affinity of CO_(2) with pillar[6]arene N_(4) than other structures and the larger isosteric heat differences between CO_(2) and N2 rendered pillar[6]arene N4 to present the high CO_(2) adsorption capacity and high CO_(2) selectivity over N_(2).Our results highlight the potential of azo-functionalization as an excellent means to improve pillar[6]arene for CO_(2) capture and separation.展开更多
A new complex, [Cd（Himc）2（H2O）2] 1, obtained from imidazole-4-carboxylatic acid （H2imc） and Cd（ClO4）2·6H2O, has been synthesized. The crystal structure was determined by X-ray diffraction. The title compo...A new complex, [Cd（Himc）2（H2O）2] 1, obtained from imidazole-4-carboxylatic acid （H2imc） and Cd（ClO4）2·6H2O, has been synthesized. The crystal structure was determined by X-ray diffraction. The title compound crystallizes in the orthorhombic system, space group Pccn, with a = 7.4886（11）, b = 11.9667（18）, c = 13.550（2） A, V= 1214.3（3） A3, Z = 4, Mr= 370.60, Dc = 2.027 mg/m3, F（000） = 728,μ （MoKa） = 1.829 mm^-1, the final R = 0.0243 and wR = 0.0591 for 1150 unique reflections with I 〉 2σ（I）. The cadmium（II） center in the title complex is coordinated with two oxygen and two nitrogen atoms from two bidentate chelated imidazole-4-carboxlate ligands together with two water molecules, giving a distorted octahedral coordination geometry. A one-dimensional hydrogen bonding chain is formed via intermolecular O-H...O hydrogen bonds, and such adjacent chains are further stacked through intermolecular π-π and hydrogen bonding interactions to form a 3D supramolecular framework. Complex 1 exhibits a fluorescent emission band at 290 nm （λex = 236 nm） in the solid state.展开更多
A Ni（Ⅱ） supramolecular complex,[Ni 2 （btec）（3py） 2 （H 2 O） 8 ]（H 2 O） 4 （1）,has been synthesized by Ni（ClO 4） 2 ·6H 2 O,benzene-1,2,4,5-tetracarboxylic acid （H 4 btec） and terminal ligand 3-hydro...A Ni（Ⅱ） supramolecular complex,[Ni 2 （btec）（3py） 2 （H 2 O） 8 ]（H 2 O） 4 （1）,has been synthesized by Ni（ClO 4） 2 ·6H 2 O,benzene-1,2,4,5-tetracarboxylic acid （H 4 btec） and terminal ligand 3-hydroxypyridine （3py） in aqueous solution.The title compound crystallizes in triclinic system,space group P1,with a=8.5637（12）,b=9.4138（13）,c=10.3611（14）,α=67.9540（10）,β=85.1740（10）,γ=76.9890（10）°,V=754.33（18） 3,Z=2,M r=386.96,D c=1.704 Mg/m 3,μ=1.345 mm-1,F（000）=402,the final R=0.0222 and wR=0.0563 for 2675 observed reflections with I 2σ（Ⅰ）.The adjacent discrete molecules are further self-assembled by intermolecular π-π and O-H···O hydrogen bonding interactions to construct a 3D supramolecular framework.Magnetic measurement shows weak ferromagnetic interaction in the range of 2～300 K.展开更多
In recent years, considerable attention has been paid to supramolecular networks based on metal organic building blocks because of their potential applications in diverse fields, such as, catalysis, optics, sensors, m...In recent years, considerable attention has been paid to supramolecular networks based on metal organic building blocks because of their potential applications in diverse fields, such as, catalysis, optics, sensors, magnetism, and molecular recognition^[1-3]. On the ba- sis of the principles of crystal engineering and special synthesis strategies, several novel supramolecular frameworks have been assembled from various organic, inorganic and metal-organic moieties, which largely en- riches the structure chemistry of solid state materi-als^[4-9].展开更多
Dimension-controllable supramolecular organic frameworks(SOFs)with aggregation-enhanced fluorescence are hierarchically fabricated through the host-guest interactions of cucurbit[8]uril(CB[8])and coumarin-modified tet...Dimension-controllable supramolecular organic frameworks(SOFs)with aggregation-enhanced fluorescence are hierarchically fabricated through the host-guest interactions of cucurbit[8]uril(CB[8])and coumarin-modified tetraphenylethylene derivatives(TPEC).The three-dimensional layered SOFs could be constructed from the further stacking of two-dimensional mono-layered structures via simply regulating the self-assembly conditions including the culturing time and concentration.Upon light irradiation under the wavelength of 365 nm,the photodimerization of coumarin moieties occurred,which resulted in the transformation of the resultant TPECn/CB[8]4n two-dimensional SOFs into robust covalently-connected 2D polymers with molecular thickness.Interestingly,the supramolecular system of TPEC/CB[8]exhibited intriguing multicolor fluorescence emission from yellow to blue in the time range of 0-24 h at 365 nm irradiation,possessing potential applicability for photochromic fluorescence ink.展开更多
基金supported by the National Natural Science Fund for Distinguished Young Scholars of China (No. 20725101)the 973 Program (No. 2006CB932904)+2 种基金the NSF of Fujian Province (Nos. E0510030 and 2008F3120)the Knowledge Innovation Program of CAS (No. KJCX2.YW.H01)NNSFC (No. 20521101)
文摘A 3-D supramolecular framework, [Er（pybz）2（Hnds）（H2O）2]·H2O （1, Hpybz = 4- pyridin-4-yl-benzoic acid, H2nds = naphthalene-1,5-disulfonic acid）, based on lanthanide ions and mixed ligands has been hydrothermally synthesized. The structure was determined by single-crystal X-ray diffraction and further characterized by IR, elemental analysis and thermogravimetric analysis. Compound 1 crystallizes in the monoclinic system, space group P21/n with a = 9.849（2）, b = 22.526（5）, c = 17.167（4） A, β =105.461（4）° and V = 3670.9（2） A^3. In 1, two seven-coordinated Er^3＋ ions are bridged by two pybz^- ligands to form a dimeric [Er2（COO）2] unit, which is further orderly linked by carboxyl of pybz^-ligand to obtain a 1-D chain running along the a axis. Interestingly, significant H-bonding and π-π stacking interactions link the neighboring parallel chains leading to a 3-D supramolecular network structure which displays 1-D rhombus open channels （17.2A× 22.5A）.
基金supported by the National Natural Science Foundation of China (20773104)the Program for New Century Excellent Talents in University (NCET-06-0891)+2 种基金the Key Project of Key Laboratory of Shaanxi Province (08JZ81)the Natural Science Foundation of Hubei Province (2009CBD030)the Important Project of Hubei Provincial Education Office (09HB33)
文摘The complex [Cu2（H2dhbd）2（tpy）2]·CH3OH·4H2O 1 （H4dhbd =2,3-dihydroxybutanedioic acid, tpy = 2,2＇：6＇,2＇＇-terpyridine） has been hydrothermally synthesized and characterized by single-crystal X-ray diffraction analysis. The crystal is of triclinic, space groups Pi with a= 8.6859（17）, b = 11.223（2）, c = 12.275（2）A, α = 112.454（3）, β= 98.435（3）, γ = 105.593（3）°, V= 1022.5（3） A^3, Z = 1, C38H42Cu2N6O18, Mr = 997.86, Dc = 1.621 g/cm^3, μ= 1.127 mm^-1, F（000） = 514, T = 293（2） K, the final R = 0.0539 and wR = 0.1394 for 3550 observed reflections with I 〉 2σ（I）. In the dinuclear unit, two Cun atoms are bridged by two H2dhbd chelate anions, forming a 14-membered ring, in which the distance of Cu…Cu atoms is 7.0526（12）A. Adjacent dinuclear units are constituted through π-π interactions and C-H…O hydrogen-bonding interactions, fashioning the final 3-D supramolecular framework with 1-D open channels. Variable-temperature magnetic susceptibility measurement indicates the presence of weak antiferromagnetic exchange interactions between Cu^II ions.
基金supported by the NSFC(Nos.21571016,21831001 and 91122028)the NSFC for Distinguished Young Scholars(No.20725101)
文摘A neoteric organic-inorganic hybrid Co-substituted phosphotungstate H6{[Co(en)2(OAc)2]2[Co4(H2 O)2(PW9 O34)2]}?2 H2 en?36 H2 O(1, en = enthylenediamine) has been made under hydrothermal conditions and characterized by IR spectrum, thermogravimetric analysis, diffuse-reflectance spectroscopy, powder X-ray diffraction, single-crystal X-ray diffraction and cyclic voltammetry, respectively. Crystal data for 1: monoclinic, P21/c, a = 18.2234(12), b = 15.3696(9), c = 20.1706(17) ?, β = 106.563(8)°, V = 5415.1(7) ?3, Z = 2, Mr = 6072.30, Dc = 3.724 g/cm3, μ = 20.087 mm-1, F(000) = 5540, R = 0.0585, w R = 0.1543 and S = 1.024. Single-crystal X-ray structure analysis reveals that compound 1 exhibits a 3-D supramolecular framework via H-bonding interactions, in which the discrete Co-complex is modified by two types of organic ligands, en and acetate. In addition, the adsorption experiments demonstrate compound 1 possesses a remarkable capability for scavenging of methylene blue.
基金This study was financially supported by the National Nature Science Foundation of China(nos.21771177 and 51603206)the Strategic Priority Research Program of CAS(no.XDB20000000)the Key Research Program of Frontier Sciences,CAS(no.QYZDB-SSW-SLH019).
文摘Porous supramolecular frameworks based on metal-organic cages(MOCs)usually have poor structural stability after activation.This issue narrows the scope of their potential applications,particularly for the inclusion of guest molecules that demand high porosity.Herein,the authors have reported the stabilization of a mesoporous zirconium MOC-based supramolecular framework with an in situ catalytic polymerization strategy.Due to the passivation effect imparted by this strategy,the introduced polymer is primarily distributed on the surface of the crystals,which results in the hybrid material retaining its crystallinity and permanent porosity.A preliminary application of this type of stabilized mesoporous supramolecular framework shows that among MOC-based supramolecular frameworks,it has the highest high-pressure methane uptake.Such a facile strategy may provide a general way to stabilize fragile porous materials and facilitate exploration of their potential applications.
基金support from the National Key Research and Development Program of China(No.2017YFA0700102)the National Natural Science Foundation of China(Nos.21871266 and 21731006)+1 种基金the Key Research Program of Frontier Science CAS(No.QYZDY-SSW-SLH025)Youth Innovation Promotion Association CAS.
文摘A microporous supramolecular framework with high water and thermal stability can selectively absorb water molecules over methanol or ethanol due to the suitable channels.The model separation test on columns shows that an ultra-pure ethanol(99.9%)can be obtained from the mixture of ethanol/water(95:5).Additionally,after refluxing the desolvated sample in 95%ethanol at 60℃for 5 h,the purity of ethanol rises up to 97.43%,which is obviously higher than 96.56%for 4 A molecular sieves.
基金Supported by the National Natural Science Foundation of China(Nos.21571016,21831001 and 91122028)the National Natural Science Foundation of China for Distinguished Young Scholars(No.20725101).
文摘Two new alkaline metal borates containing 1D{B5}/{B6}oxoboron helical chains,namely Na0.5[B5O8(OH)2]0.5[B5O6(OH)2]0.5·0.5H3O(1)and NaKCs[B6O9(OH)3](2)were synthesized under solvothermal conditions.Compound 1 contains the interesting alternative left-and right-handed helical{[B5O8(OH)2][B5O6(OH)2]}2-({B5}-1 and{B5}-2)1D chains and compound 2 possesses the similar[B6O11(OH)3]7-({B6})chains.Their 1D chains are further assembled into 2D layers and 3D supramolecular frameworks through O-H…O hydrogen bonds.In addition,the UV cutoff edge of compounds 1 and 2 is both below 190 nm.
基金supported by the National Natural Science Foundation of China(Nos.21971091,21901089 and 22161021)the Natural Science Foundation of Jiangxi Province(No.20212BAB203021)
文摘Accompanied by solid-state structural phase transitions,the switchable molecular dynamics(MD)and order-disorder transformation of(i-PrNHMe2)^(+)cation embedded in a deformable{[Ni(NCS)_(6)]^(4-)}_(∞)supramolecular framework are in-depth investigated by variable-temperature tests of single-crystal X-ray diffraction,dielectric measurement,and MD simulation.Interestingly,it is found that the confined swinging or flipping of the(i-PrNHMe_(2))^(+)cation as a whole is assisted by a synergistic change of its torsion angle.This research provides a helpful insight into the solid-state MD of moderate-sized quasi-spherical molecules/ions that feature a flexible inner core.
基金the financial support of National Natural Science Foundation of China(Nos.51663005,21761007 and21871064)Science and Technology Plan Project of Guizhou Province(Nos.20175788 and 20185781)+2 种基金the Creative Research Groups of Guizhou Provincial Education Department(No.2017028)the Innovation Program for High-level Talents of Guizhou Province(No.20165657)“Chun-Hui” Fund of Chinese Ministry of Education(No.Z2017005)。
文摘Based on the crystal structures of two cucurbit[6]uril/calix[n]arene-based supramolecular frameworks reported by Long and co-workers,we further investigated the interactions of cucurbit[6]uril with 4-sulfocalix[4]arene and 4-sulfocalix[6]arene using ^(1)H NMR spectroscopy and isothermal titration calorimetry(ITC),respectively.Moreover,solid fluorescent materials were prepared via the adsorption of fluorescent dyes by these porous supramolecular frameworks,which exhibit a selective response to certain volatile organic compounds.
基金the financial support of the National Natural Science Foundation of China(Nos.21761007,51663005 and 21871064)Science and Technology Plan Project of Guizhou Province(Nos.20175788 and 20185781)。
文摘Curcurbit[n]uril(Q[n])-based supramolecular frameworks(QSFs) constructed from the outer surface interaction of Q[n]s(OSIQ) have the characteristic of simplicity,diversity and modulability.Their simplicity is reflected in their simple composition and preparation methods used for QSFs.The diversity of supramolecular organic frameworks(SOFs) is reflected in the synthesis methods and structural characteristics of the as-obtained QSFs,as well as the variety of structural directing agents and basic building blocks used to prepare QSFs.The modulability is reflected by the controllable channel size in the QSFs,which can be adjusted using different sizes of Q[n]s.In this work,the first re ported cucurbituril Q[6]was selected as the basic building block and three Q[6]-based su p ramolecular frameworks were obtained from aqueous HCl solutions in the presence of [CdCl_(4)]^(2-)respectively.The OSIQs are the main driving forces for the formation of these frameworks.This study shows the diversity of the QSFs.
基金Supported by the National Natural Science Foundation of China (Grant No. 20671071)Program for New Century Excellent Talents in University (Grant No. NCET-07-0613), and Tianjin Normal University
文摘A series of Cd(Ⅱ) coordination complexes with an elongated 2,4-dipyridyl-type building block trans-1-(2-pyridyl)-2-(4-pyridyl)ethylene (bpe) and different dicarboxylate ligands have been presented. Generally, bpe shows the unidentate coordination mode and serves as the terminal pendant, whereas the dicarboxylate ligands display various binding fashions to interlink the metal centers to form 1-D comb-like chain, ribbon, and fishbone arrays, as well as 2-D 44 and 4.82 layered networks. Notably, the bpe building block is also involved in secondary interactions such as hydrogen bonding and aromatic stacking to construct the resulting supramolecular architectures. Thermal stability of these complexes has been studied by TG-DTA technique.
基金Project supported by Shandong Province Higher Education Science and Technology Program,China(Grant No.J17KA016)State Key Laboratory of Bio-Fibers and Eco-Textiles(Grant No.K2019-12)the Cultivation Fund of Henan Normal University,China(Grant No.2020PL15).
文摘Azo-based pillar[6]arene supramolecular organic frameworks are reported for CO_(2) and N_(2) adsorption and separation by density functional theory and grand canonical Monte–Carlo simulation.Azo-based pillar[6]arene provides suitable environment for CO_(2) adsorption and selectivity.The adsorption and selectivity results show that introducing azo groups can effectively improve CO_(2) adsorption and selectivity over N_(2),and both CO_(2) adsorption and CO_(2) selectivity over N_(2) follow the sequence pillar[6]arene N_(4)>pillar[6]arene N2>pillar[6]arene.Pillar[6]arene N_(4) exhibits CO_(2) adsorption capacity of1.36 mmol/g,and superior selectivity of CO_(2) over N_(2) of116.75 with equal molar fraction at 1 bar(1 bar=105 Pa)and 298 K.Interaction analysis confirms that both the Coulomb and van derWaals interactions between CO_(2) with pillar[6]arene frameworks are greater than that of N_(2).The stronger affinity of CO_(2) with pillar[6]arene N_(4) than other structures and the larger isosteric heat differences between CO_(2) and N2 rendered pillar[6]arene N4 to present the high CO_(2) adsorption capacity and high CO_(2) selectivity over N_(2).Our results highlight the potential of azo-functionalization as an excellent means to improve pillar[6]arene for CO_(2) capture and separation.
基金supported by the Natural Science Foundation of Henan Province (No.0511022600)the Department of Education of Henan Province (No.200510482006)
文摘A new complex, [Cd（Himc）2（H2O）2] 1, obtained from imidazole-4-carboxylatic acid （H2imc） and Cd（ClO4）2·6H2O, has been synthesized. The crystal structure was determined by X-ray diffraction. The title compound crystallizes in the orthorhombic system, space group Pccn, with a = 7.4886（11）, b = 11.9667（18）, c = 13.550（2） A, V= 1214.3（3） A3, Z = 4, Mr= 370.60, Dc = 2.027 mg/m3, F（000） = 728,μ （MoKa） = 1.829 mm^-1, the final R = 0.0243 and wR = 0.0591 for 1150 unique reflections with I 〉 2σ（I）. The cadmium（II） center in the title complex is coordinated with two oxygen and two nitrogen atoms from two bidentate chelated imidazole-4-carboxlate ligands together with two water molecules, giving a distorted octahedral coordination geometry. A one-dimensional hydrogen bonding chain is formed via intermolecular O-H...O hydrogen bonds, and such adjacent chains are further stacked through intermolecular π-π and hydrogen bonding interactions to form a 3D supramolecular framework. Complex 1 exhibits a fluorescent emission band at 290 nm （λex = 236 nm） in the solid state.
基金supported by the Natural Science Foundation of Henan Province (Nos. 092102310075 and 0511022600)
文摘A Ni（Ⅱ） supramolecular complex,[Ni 2 （btec）（3py） 2 （H 2 O） 8 ]（H 2 O） 4 （1）,has been synthesized by Ni（ClO 4） 2 ·6H 2 O,benzene-1,2,4,5-tetracarboxylic acid （H 4 btec） and terminal ligand 3-hydroxypyridine （3py） in aqueous solution.The title compound crystallizes in triclinic system,space group P1,with a=8.5637（12）,b=9.4138（13）,c=10.3611（14）,α=67.9540（10）,β=85.1740（10）,γ=76.9890（10）°,V=754.33（18） 3,Z=2,M r=386.96,D c=1.704 Mg/m 3,μ=1.345 mm-1,F（000）=402,the final R=0.0222 and wR=0.0563 for 2675 observed reflections with I 2σ（Ⅰ）.The adjacent discrete molecules are further self-assembled by intermolecular π-π and O-H···O hydrogen bonding interactions to construct a 3D supramolecular framework.Magnetic measurement shows weak ferromagnetic interaction in the range of 2～300 K.
基金Supported by the National Natural Science Foundation of China(Nos.20371007,20476011).
文摘In recent years, considerable attention has been paid to supramolecular networks based on metal organic building blocks because of their potential applications in diverse fields, such as, catalysis, optics, sensors, magnetism, and molecular recognition^[1-3]. On the ba- sis of the principles of crystal engineering and special synthesis strategies, several novel supramolecular frameworks have been assembled from various organic, inorganic and metal-organic moieties, which largely en- riches the structure chemistry of solid state materi-als^[4-9].
基金supported by Anhui Province Natural Science Funds(2008085QE209)K2020-03 from the State Key Laboratory of Molecular Engineering of Polymers(Fudan University)。
文摘Dimension-controllable supramolecular organic frameworks(SOFs)with aggregation-enhanced fluorescence are hierarchically fabricated through the host-guest interactions of cucurbit[8]uril(CB[8])and coumarin-modified tetraphenylethylene derivatives(TPEC).The three-dimensional layered SOFs could be constructed from the further stacking of two-dimensional mono-layered structures via simply regulating the self-assembly conditions including the culturing time and concentration.Upon light irradiation under the wavelength of 365 nm,the photodimerization of coumarin moieties occurred,which resulted in the transformation of the resultant TPECn/CB[8]4n two-dimensional SOFs into robust covalently-connected 2D polymers with molecular thickness.Interestingly,the supramolecular system of TPEC/CB[8]exhibited intriguing multicolor fluorescence emission from yellow to blue in the time range of 0-24 h at 365 nm irradiation,possessing potential applicability for photochromic fluorescence ink.
