The structure of a new macrocyclic compound, clemochinenoside A obtained from Clematis chinensis was identified by NMR, FAB-MS, NOE and chemical hydrolysis.
Novel pyridine-containing macrocyclic compounds, such as 6,12,19,25-tetramethyl-7,11,20,24-dinitrilo-dibenzo [b,m]1,4,12,15-tetra-azacyclodoc osine (TMCD), were synthesized and used as electron transport layer in or...Novel pyridine-containing macrocyclic compounds, such as 6,12,19,25-tetramethyl-7,11,20,24-dinitrilo-dibenzo [b,m]1,4,12,15-tetra-azacyclodoc osine (TMCD), were synthesized and used as electron transport layer in organic electroluminescent devices. Devices with a structure of glass/indium-tin oxide/arylamine derivative/ tris(quinolinolato)aluminum(Ⅲ) (Alq)/TMCD/LiF/Al exhibited green emission from the Alq layer with external quantum efficiency of 0.84% and luminous efficiency of 1.3 lm/W. The derivatives of TMCD were synthesized and characterized as well. These compounds were also found to be useful as the electron-transporting materials in organic electroluminescent devices.展开更多
The structure of a new macrocyclic compound,clemochinenoside B, isolated from the root of Clematis chinensis was elucidated by means of NMR,FAB-MS,NOE and chemical hydrolysis.
Tetra-Schiff base macrocyclic compound containing benzo-12-crown-4 was synthesized via condensation of 2, 6-diformyl-4-methyl-phenol with 4, 5- diaminobenzo-12C- 4 promoted by proton. The compound was characterized b...Tetra-Schiff base macrocyclic compound containing benzo-12-crown-4 was synthesized via condensation of 2, 6-diformyl-4-methyl-phenol with 4, 5- diaminobenzo-12C- 4 promoted by proton. The compound was characterized by MS, IR 1HNMR spectroscopy and elemental analysis.展开更多
The title compound 1,4,23,26,29,48-hexaaza-6,9:16,19:31,34:41,44-tetrabenzo-12, 15,37,40-tetraoxa-cyclodotetracontane-4,5,18,19,25,26,39,40-octaene 1 (C40H46N6O4) was synthe- sized by [2+2] condensation of diethylenet...The title compound 1,4,23,26,29,48-hexaaza-6,9:16,19:31,34:41,44-tetrabenzo-12, 15,37,40-tetraoxa-cyclodotetracontane-4,5,18,19,25,26,39,40-octaene 1 (C40H46N6O4) was synthe- sized by [2+2] condensation of diethylenetriamine with 4,4?diformyl-diphenoxyethane (dialdehyde) in a mixed solvent of ethanol and tetrahydrofuran. The crystal data are: Mr = 674.83, triclinic, P, a = 5.8249(1), b = 9.4114(8), c = 17.649(2) ? a = 79.310(7), b = 85.397(4), g = 78.970(8), V = 932.1(1) ?, Z = 1, Dc = 1.202 g/cm3, F(000) = 360, m(MoKa) = 0.079 mm-1, R = 0.0486 and wR = 0.1439. The title molecule has a crystallographic center symmetry. The distance between the two secondary amine nitrogen atoms is 18.890(3) ?展开更多
Two new macrocyclic compounds, [Cu2(L)2](ClO4)4·2CH3OH (1) and [Cu(L)](ClO4)2·2H2O (2) (L = 1,3,10,12,15,18-hexaazatetracyclodocosane) were synthesized by condensation reactions involving amine...Two new macrocyclic compounds, [Cu2(L)2](ClO4)4·2CH3OH (1) and [Cu(L)](ClO4)2·2H2O (2) (L = 1,3,10,12,15,18-hexaazatetracyclodocosane) were synthesized by condensation reactions involving amines and formaldehyde in the presence of copper anion. Compound 1 crystallizes in triclinic, space group Pí with a = 10.442(2), b = 14.197(3), c = 17.388(4), α = 91.218(4), β = 90.69(3), γ = 93.756(4)o, V = 2520.4(9)3, Z = 2, F(000) = 1260, Dc = 1.589 Mg/m3, Mr = 1205.92, μ = 1.137 mm-1, λ = 0.71073, the final R = 0.0668 and wR = 0.1573 for 9703 observed reflections with I 2σ(I). Compound 2 crystallizes in monoclinic, space group C2/c with a = 16.911(2), b = 11.4172(15), c = 27.059(4), β = 107.787(2)o, V = 4974.7(12)3, Z = 8, F(000) = 2504, Dc = 1.610 Mg/m3, Mr = 602.92, μ = 1.155 mm-1, λ = 0.71073, the final R = 0.0419 and wR = 0.1131 for 4374 observed reflections with I 2σ(I).展开更多
The crystal structure of copper(Ⅱ) complex with a new 14-membered tetraazamacrocyclic ligand 5,5,7,12,12,14-hexamethy1-1,4,8,11-tetraazacyclotetradecane-N'N'-diacetic acid,[CuC16N4H34(CH2COO)(CH2COOH)]·C...The crystal structure of copper(Ⅱ) complex with a new 14-membered tetraazamacrocyclic ligand 5,5,7,12,12,14-hexamethy1-1,4,8,11-tetraazacyclotetradecane-N'N'-diacetic acid,[CuC16N4H34(CH2COO)(CH2COOH)]·ClO4·0. 5HCIO4·1. 5H2O was determined. Crystallographic data: Mr = 639.22,orthorhombic, space group Pcnb with a=11.743(4),b=16.446(2),c=29.611 (4) A,Z=8,V=5726(3) A3, Dc=1.482 g·cm-3, F(000)=1344,μ=9. 64 cm-1,R=0.063,and Rw=0.067 for 2386 reflections with I≥3σ(I). The structure shows an unusual configuration in which two carboxyl groups were bonded to two neighboring nitrogen atoms of the macrocycle, N1 and N4, and six methyl substituents occur on one side of the macrocycle, while two carboxyl groups on the other side, and central copper(Ⅱ) ion forms a five-coordinated geometry.展开更多
A novel [1+1] Schiff-base macrocyclic compound 3 has been synthesized from precursor 1, 1,3-bis(2'- formylphenoxy)-2-propanol, and precursor 2, resorcinol-bis(4-aminophenyl)ether, via condensation and cyclizacti...A novel [1+1] Schiff-base macrocyclic compound 3 has been synthesized from precursor 1, 1,3-bis(2'- formylphenoxy)-2-propanol, and precursor 2, resorcinol-bis(4-aminophenyl)ether, via condensation and cyclizaction using Ba2+ as template. The macrocycle 3 was further reduced giving saturated macrocycle 4. The structures of 3 and 4 were characterized by elemental analysis, ~H NMR, IR, and MS spectra, and their structures were determined via single crystal X-ray diffraction studies. X-ray diffraction analysis revealed that the macrocyclic compound 3 has a folded conformation, and the corresponding reduced product 4 adopts a twisted and folded conformation due to its flexible nature. ~ 2013 Bi-Xue Zhu. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.展开更多
A mixed-valence dinuclear manganese complex, [Mn ⅡMn ⅢL](ClO 4)·1/2MeOH, where L is a macrocyclic ligand derived from the cyclocondensation of sodium 2,6-diformyl-4-methylphenolate with N,N-bis(2-aminoethyl)...A mixed-valence dinuclear manganese complex, [Mn ⅡMn ⅢL](ClO 4)·1/2MeOH, where L is a macrocyclic ligand derived from the cyclocondensation of sodium 2,6-diformyl-4-methylphenolate with N,N-bis(2-aminoethyl)-2-hydroxybenzyl amine, was obtained and its structure was determined by X-ray diffraction. The orange crystal is a monoclinic system with space group P2 1/c and lattice parameters a=1.1617(4), b=1.4005(3), c=1.4641(3) nm, β=113.03(2)°, and Z=2. The crystal structure shows that each pendant-arm is bonded in a bidentate fashion to the adjacent metal atom and that both the arms are on the same side of the macrocycle. The two Mn atoms are bridged by two μ 2-phenoxy oxygen atoms of the tetra-imine macrocycle, and each Mn atom, locating in a trigonal prismatic coordination environment(N 3O 3), is six-coordinated by the two imine nitrogen atoms, one tertiary nitrogen atom and a pendant phenol moiety apart from the two oxygen atoms.展开更多
The synthesis of eight new arsamacrocyclic Polyethers was described. The structures of these compounds were characterized by elemental analysis, IR, H-1-NMR and MS.
The first reported X-ray crystal structure of a new (2:2) macrocyclic thiocarbohydrazone, effectively derived from thiocarbohydrazide and di(2-formylphenoxy)ethylene is shown.
The title compound, (C 34 H 54 N 2O 10 )[Eu(NO 3) 5](C 34 H 52 N 2O 10 =1,2 bis(2,3 benzo 10 aza 15 crown 5 N ethyleneoxy)ethane), was synthesized in acetonitrile solution and its ...The title compound, (C 34 H 54 N 2O 10 )[Eu(NO 3) 5](C 34 H 52 N 2O 10 =1,2 bis(2,3 benzo 10 aza 15 crown 5 N ethyleneoxy)ethane), was synthesized in acetonitrile solution and its crystal structure was determined by X ray analysis. The crystal crystallizes in monoclinic, space group P21/c with cell parameters a =1 1801(2) nm, b =2 3560(5) nm, c =1 7025(3) nm, β =99 67(3)°, V =4 6662(16) nm 3, Z =4, D c=1 581 g/cm 3. The europium ion is coordinated with ten oxygen atoms from five nitrato groups, and neither O atoms nor N atoms of the macrocyclic compound are bonded to the europium ion.展开更多
Several novel Schiff base macrocyclic compounds containing thiophene were synthesized from d/ethyl 3,4-dialkoxythiophene-2,5-dicarboxylate, cyanuric chloride, diethylarnine and p-nitrophenol by reduction, oxidation, s...Several novel Schiff base macrocyclic compounds containing thiophene were synthesized from d/ethyl 3,4-dialkoxythiophene-2,5-dicarboxylate, cyanuric chloride, diethylarnine and p-nitrophenol by reduction, oxidation, substitution and cyclization, and their structures were characterized by IR, NMR and electrospray ionization-rnass spectrorneter(ESI-MS). The studies on their UV-Vis absorption spectra show that Schiff base rnacrocycles 6-10 have selective recognition for Fe^3+.展开更多
Two macrocyclic polyoxazoles with different sizes and numbers of side chains were designed and synthesized from the linear-type precursors obtained by the iterative application of oxazole formation reaction via effect...Two macrocyclic polyoxazoles with different sizes and numbers of side chains were designed and synthesized from the linear-type precursors obtained by the iterative application of oxazole formation reaction via effective trimerization or dimerization respectively under highly diluted conditions in one pot.展开更多
Supramolecular polymers, which combined of the supramolecular chemistry and polymer science, are constructed from monomers together by reversible noncovalent interactions. Supramolecular polymers in aqueous solution a...Supramolecular polymers, which combined of the supramolecular chemistry and polymer science, are constructed from monomers together by reversible noncovalent interactions. Supramolecular polymers in aqueous solution are especially important due to their superior biocompatibility and environmental adaptation, which determined they have wide applications in various areas, such as drug delivery, selfhealing, shape memory. Macrocyclic compounds, such as cyclodextrins, calixarenes, cucurbiturils and pillar[n]arenes, are the most used building blocks in the preparation of supramolecular polymers.Macrocycle-based supramolecular polymers, which introduce the host-guest interaction in the system,endow these polymers with interesting and smart physical-chemical properties. In this review, we summarized recent studies about supramolecular polymers in aqueous solution based on macrocyclic compounds.展开更多
We present the design and synthesis of polyoxazole-based macrocycles containing a phosphonate group.A reliable route was established that allows for convenient and versatile incorporation of various phosphonate functi...We present the design and synthesis of polyoxazole-based macrocycles containing a phosphonate group.A reliable route was established that allows for convenient and versatile incorporation of various phosphonate functionalities such as phosphonate ester,acid,and salt at the macrocyclic ring periphery.Such unprecedented macrocyclic compounds are anticipated to be appealing candidates as telomerase inhibitors.展开更多
General and straightforward synthetic strategy towards the iron(Ⅱ)clathrochelates with functionalizing substituents in their apical capping and one of the three chelate ribbed fragments was developed.Their hexachloro...General and straightforward synthetic strategy towards the iron(Ⅱ)clathrochelates with functionalizing substituents in their apical capping and one of the three chelate ribbed fragments was developed.Their hexachloroclathrochelate precursors were prepared by the direct template condensation of dichloroglyoxime with a suitable boronic acid on the Fe^(2+) ion as a matrix and underwent a stepwise nucleophilic substitution with S_(2)-,N_(2)- or O_(2)-bis-nucleophiles,forming the alicyclic or aromatic N_(2)-,S_(2)-or O_(2)-six-membered fragments.Depending on the reaction conditions and precursor-to-dinucleophile molar ratios,iron(Ⅱ)clathrochelates with one(S,O and N),two(S,O and N)or three(S and O)X_(2)-six-membered ribbed substituent(s)were obtained.Their reactivity substantially decreases in a row:Cl_(6)-Cage>Cl_(4)X_(2)-Cage(where X=S,O or,especially,N)>Cl_(2)X_(4)-Cage(where X=S or O).The reactive monoribbed-functionalized clathrochelates underwent further chemical transformations giving the target macrobicyclic complexes with terminal vector groups.As follows from the single crystal XRD data,their FeN_(6)-coordination polyhedra possess the geometry intermediate between a trigonal prism and a trigonal antiprism(φ=21.3°—25.20°).Fe-N distances vary from 1.887(6)to 1.933(8)Å.Their 3D-molecules,the hydrophobic–hydrophilic balance in which can be tuned using a ribbed functionalization,form in the crystals the intermolecular specific halogen bonds and/or hydrophobic interactions.展开更多
Pillar[n]arenes,which were first reported by our groupin2008,arepromisingmacrocycliccompounds in supramolecular chemistry.The simple,tubular,and highly symmetrical shape of pillar[n]arenes has allowed various supramol...Pillar[n]arenes,which were first reported by our groupin2008,arepromisingmacrocycliccompounds in supramolecular chemistry.The simple,tubular,and highly symmetrical shape of pillar[n]arenes has allowed various supramolecular assemblies with well-defined structures to be constructed.展开更多
文摘The structure of a new macrocyclic compound, clemochinenoside A obtained from Clematis chinensis was identified by NMR, FAB-MS, NOE and chemical hydrolysis.
基金the Scientific Research Foundation for the Returned Overseas Chinese Scholars,State Education Ministry(No.2005383).
文摘Novel pyridine-containing macrocyclic compounds, such as 6,12,19,25-tetramethyl-7,11,20,24-dinitrilo-dibenzo [b,m]1,4,12,15-tetra-azacyclodoc osine (TMCD), were synthesized and used as electron transport layer in organic electroluminescent devices. Devices with a structure of glass/indium-tin oxide/arylamine derivative/ tris(quinolinolato)aluminum(Ⅲ) (Alq)/TMCD/LiF/Al exhibited green emission from the Alq layer with external quantum efficiency of 0.84% and luminous efficiency of 1.3 lm/W. The derivatives of TMCD were synthesized and characterized as well. These compounds were also found to be useful as the electron-transporting materials in organic electroluminescent devices.
文摘The structure of a new macrocyclic compound,clemochinenoside B, isolated from the root of Clematis chinensis was elucidated by means of NMR,FAB-MS,NOE and chemical hydrolysis.
文摘Tetra-Schiff base macrocyclic compound containing benzo-12-crown-4 was synthesized via condensation of 2, 6-diformyl-4-methyl-phenol with 4, 5- diaminobenzo-12C- 4 promoted by proton. The compound was characterized by MS, IR 1HNMR spectroscopy and elemental analysis.
基金The project was financially supported from the National Natural Science Foundation of China (No. 20171012)+5 种基金 and the Natural Science Foundation of Fujian province (No.E0110010)
文摘The title compound 1,4,23,26,29,48-hexaaza-6,9:16,19:31,34:41,44-tetrabenzo-12, 15,37,40-tetraoxa-cyclodotetracontane-4,5,18,19,25,26,39,40-octaene 1 (C40H46N6O4) was synthe- sized by [2+2] condensation of diethylenetriamine with 4,4?diformyl-diphenoxyethane (dialdehyde) in a mixed solvent of ethanol and tetrahydrofuran. The crystal data are: Mr = 674.83, triclinic, P, a = 5.8249(1), b = 9.4114(8), c = 17.649(2) ? a = 79.310(7), b = 85.397(4), g = 78.970(8), V = 932.1(1) ?, Z = 1, Dc = 1.202 g/cm3, F(000) = 360, m(MoKa) = 0.079 mm-1, R = 0.0486 and wR = 0.1439. The title molecule has a crystallographic center symmetry. The distance between the two secondary amine nitrogen atoms is 18.890(3) ?
文摘Two new macrocyclic compounds, [Cu2(L)2](ClO4)4·2CH3OH (1) and [Cu(L)](ClO4)2·2H2O (2) (L = 1,3,10,12,15,18-hexaazatetracyclodocosane) were synthesized by condensation reactions involving amines and formaldehyde in the presence of copper anion. Compound 1 crystallizes in triclinic, space group Pí with a = 10.442(2), b = 14.197(3), c = 17.388(4), α = 91.218(4), β = 90.69(3), γ = 93.756(4)o, V = 2520.4(9)3, Z = 2, F(000) = 1260, Dc = 1.589 Mg/m3, Mr = 1205.92, μ = 1.137 mm-1, λ = 0.71073, the final R = 0.0668 and wR = 0.1573 for 9703 observed reflections with I 2σ(I). Compound 2 crystallizes in monoclinic, space group C2/c with a = 16.911(2), b = 11.4172(15), c = 27.059(4), β = 107.787(2)o, V = 4974.7(12)3, Z = 8, F(000) = 2504, Dc = 1.610 Mg/m3, Mr = 602.92, μ = 1.155 mm-1, λ = 0.71073, the final R = 0.0419 and wR = 0.1131 for 4374 observed reflections with I 2σ(I).
文摘The crystal structure of copper(Ⅱ) complex with a new 14-membered tetraazamacrocyclic ligand 5,5,7,12,12,14-hexamethy1-1,4,8,11-tetraazacyclotetradecane-N'N'-diacetic acid,[CuC16N4H34(CH2COO)(CH2COOH)]·ClO4·0. 5HCIO4·1. 5H2O was determined. Crystallographic data: Mr = 639.22,orthorhombic, space group Pcnb with a=11.743(4),b=16.446(2),c=29.611 (4) A,Z=8,V=5726(3) A3, Dc=1.482 g·cm-3, F(000)=1344,μ=9. 64 cm-1,R=0.063,and Rw=0.067 for 2386 reflections with I≥3σ(I). The structure shows an unusual configuration in which two carboxyl groups were bonded to two neighboring nitrogen atoms of the macrocycle, N1 and N4, and six methyl substituents occur on one side of the macrocycle, while two carboxyl groups on the other side, and central copper(Ⅱ) ion forms a five-coordinated geometry.
基金supported by the National Natural Science Foundation of China(No.21061003)he International Collaborative Project of Guizhou Province(No.[2009]700104)the Natural Science Foundation of the Guizhou Province(No.(2012)2151)
文摘A novel [1+1] Schiff-base macrocyclic compound 3 has been synthesized from precursor 1, 1,3-bis(2'- formylphenoxy)-2-propanol, and precursor 2, resorcinol-bis(4-aminophenyl)ether, via condensation and cyclizaction using Ba2+ as template. The macrocycle 3 was further reduced giving saturated macrocycle 4. The structures of 3 and 4 were characterized by elemental analysis, ~H NMR, IR, and MS spectra, and their structures were determined via single crystal X-ray diffraction studies. X-ray diffraction analysis revealed that the macrocyclic compound 3 has a folded conformation, and the corresponding reduced product 4 adopts a twisted and folded conformation due to its flexible nature. ~ 2013 Bi-Xue Zhu. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.
基金the Natural Science Foundation of Shandong Province(No.Y2 0 0 2 B0 6 )
文摘A mixed-valence dinuclear manganese complex, [Mn ⅡMn ⅢL](ClO 4)·1/2MeOH, where L is a macrocyclic ligand derived from the cyclocondensation of sodium 2,6-diformyl-4-methylphenolate with N,N-bis(2-aminoethyl)-2-hydroxybenzyl amine, was obtained and its structure was determined by X-ray diffraction. The orange crystal is a monoclinic system with space group P2 1/c and lattice parameters a=1.1617(4), b=1.4005(3), c=1.4641(3) nm, β=113.03(2)°, and Z=2. The crystal structure shows that each pendant-arm is bonded in a bidentate fashion to the adjacent metal atom and that both the arms are on the same side of the macrocycle. The two Mn atoms are bridged by two μ 2-phenoxy oxygen atoms of the tetra-imine macrocycle, and each Mn atom, locating in a trigonal prismatic coordination environment(N 3O 3), is six-coordinated by the two imine nitrogen atoms, one tertiary nitrogen atom and a pendant phenol moiety apart from the two oxygen atoms.
文摘The synthesis of eight new arsamacrocyclic Polyethers was described. The structures of these compounds were characterized by elemental analysis, IR, H-1-NMR and MS.
文摘The first reported X-ray crystal structure of a new (2:2) macrocyclic thiocarbohydrazone, effectively derived from thiocarbohydrazide and di(2-formylphenoxy)ethylene is shown.
文摘The title compound, (C 34 H 54 N 2O 10 )[Eu(NO 3) 5](C 34 H 52 N 2O 10 =1,2 bis(2,3 benzo 10 aza 15 crown 5 N ethyleneoxy)ethane), was synthesized in acetonitrile solution and its crystal structure was determined by X ray analysis. The crystal crystallizes in monoclinic, space group P21/c with cell parameters a =1 1801(2) nm, b =2 3560(5) nm, c =1 7025(3) nm, β =99 67(3)°, V =4 6662(16) nm 3, Z =4, D c=1 581 g/cm 3. The europium ion is coordinated with ten oxygen atoms from five nitrato groups, and neither O atoms nor N atoms of the macrocyclic compound are bonded to the europium ion.
文摘Several novel Schiff base macrocyclic compounds containing thiophene were synthesized from d/ethyl 3,4-dialkoxythiophene-2,5-dicarboxylate, cyanuric chloride, diethylarnine and p-nitrophenol by reduction, oxidation, substitution and cyclization, and their structures were characterized by IR, NMR and electrospray ionization-rnass spectrorneter(ESI-MS). The studies on their UV-Vis absorption spectra show that Schiff base rnacrocycles 6-10 have selective recognition for Fe^3+.
基金Supported by the Hundred Talent Program of Chinese Academy of Sciences and the National Natural Science Foundation of China(No.21272225).
文摘Two macrocyclic polyoxazoles with different sizes and numbers of side chains were designed and synthesized from the linear-type precursors obtained by the iterative application of oxazole formation reaction via effective trimerization or dimerization respectively under highly diluted conditions in one pot.
基金supported the National Natural Science Foundation of China (No. 21801139)Natural Science Foundation of Jiangsu Province (No. BK20180942)+1 种基金the Natural Science Foundation of Nantong University (No. 03083004)the large instruments open foundation of Nantong university (1No. KFJN1814)
文摘Supramolecular polymers, which combined of the supramolecular chemistry and polymer science, are constructed from monomers together by reversible noncovalent interactions. Supramolecular polymers in aqueous solution are especially important due to their superior biocompatibility and environmental adaptation, which determined they have wide applications in various areas, such as drug delivery, selfhealing, shape memory. Macrocyclic compounds, such as cyclodextrins, calixarenes, cucurbiturils and pillar[n]arenes, are the most used building blocks in the preparation of supramolecular polymers.Macrocycle-based supramolecular polymers, which introduce the host-guest interaction in the system,endow these polymers with interesting and smart physical-chemical properties. In this review, we summarized recent studies about supramolecular polymers in aqueous solution based on macrocyclic compounds.
基金the National Natural Science Foundation of China(No.21272225)the Key Lab of Synthetic Chemistry of Natural Substances,Shanghai Institute of Organic Chemistry,is acknowledged.
文摘We present the design and synthesis of polyoxazole-based macrocycles containing a phosphonate group.A reliable route was established that allows for convenient and versatile incorporation of various phosphonate functionalities such as phosphonate ester,acid,and salt at the macrocyclic ring periphery.Such unprecedented macrocyclic compounds are anticipated to be appealing candidates as telomerase inhibitors.
基金The synthesis of clathrochelate complexes was supported by Russian Science Foundation(project 21-73-20145)G.E.Z.also thanks the RFBR(grants 19-33-60047)for the financial support。
文摘General and straightforward synthetic strategy towards the iron(Ⅱ)clathrochelates with functionalizing substituents in their apical capping and one of the three chelate ribbed fragments was developed.Their hexachloroclathrochelate precursors were prepared by the direct template condensation of dichloroglyoxime with a suitable boronic acid on the Fe^(2+) ion as a matrix and underwent a stepwise nucleophilic substitution with S_(2)-,N_(2)- or O_(2)-bis-nucleophiles,forming the alicyclic or aromatic N_(2)-,S_(2)-or O_(2)-six-membered fragments.Depending on the reaction conditions and precursor-to-dinucleophile molar ratios,iron(Ⅱ)clathrochelates with one(S,O and N),two(S,O and N)or three(S and O)X_(2)-six-membered ribbed substituent(s)were obtained.Their reactivity substantially decreases in a row:Cl_(6)-Cage>Cl_(4)X_(2)-Cage(where X=S,O or,especially,N)>Cl_(2)X_(4)-Cage(where X=S or O).The reactive monoribbed-functionalized clathrochelates underwent further chemical transformations giving the target macrobicyclic complexes with terminal vector groups.As follows from the single crystal XRD data,their FeN_(6)-coordination polyhedra possess the geometry intermediate between a trigonal prism and a trigonal antiprism(φ=21.3°—25.20°).Fe-N distances vary from 1.887(6)to 1.933(8)Å.Their 3D-molecules,the hydrophobic–hydrophilic balance in which can be tuned using a ribbed functionalization,form in the crystals the intermolecular specific halogen bonds and/or hydrophobic interactions.
基金T.O.gratefully appreciates the financial support from JSPSKAKENHI Grant NumbersJP15H00990,JP15KK0185,JP16H04130,JP17H05148,JP18H04510,JST PRESTO(JPMJPR1313),JST CREST(JPMJCR18R3)Kanazawa University CHOZEN Project.
文摘Pillar[n]arenes,which were first reported by our groupin2008,arepromisingmacrocycliccompounds in supramolecular chemistry.The simple,tubular,and highly symmetrical shape of pillar[n]arenes has allowed various supramolecular assemblies with well-defined structures to be constructed.