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1.
(1R,2S,6R)-2-Amino-6-hydroxycyclooctanecarboxylic acid (?)-10 was synthesized from (1R,2S)-2-aminocyclooct-5-enecarboxylic acid (+)-2 via an iodolactone intermediate, while (1R,2S,3R,4S)-2-amino-5,6-dihydroxycyclooctanecarboxylic acid (?)-12 was prepared by using the OsO4-catalyzed oxidation of Boc-protected amino ester (?)-5. The stereochemistry and relative configurations of the synthesized compounds were determined by 1D and 2D NMR spectroscopy (based on 2D NOE cross-peaks and 3J(H,H) coupling constants) and X-ray crystallography.  相似文献   

2.
To study the diverse coordination modes of the H2btib,three new coordination architectures,namely, [Ag(Hbtib)CH3CN]n(1),)[Ag(Hbtib)]n(2) and[Pb(btib)(CH3OH)2]n(3)(where H2btib=4-((2-butyl-5-(2- carboxy-3-(thiophen-2-yl)prop-1-enyl)-1H-imidazol-1-yl)methyl)benzoic acid) have been synthesized and characterized by elemental analysis,IR spectrum and single-crystal X-ray diffraction.Complex 1 exhibits 1D single chain structure,while 2 shows 1D double metal chain motif,and 3 features a 2D layer topology.Also,1,2 and 3 display strong emission band in the solid state at room temperature.  相似文献   

3.
Three novel Zn(II)/Cd(II) coordination polymers, [Cd2(bip)2(m-bdc)2(H2O)2·3H2O]n (1), [Zn2(bip)2(p-bdc)2·2.5H2O]n (2) and [Zn(bip) (p-bdc)·3H2O]n (3), where bip = 3,5-bis(imidazole-1-yl)pyridine, m-H2bdc = 1,3-benzenedicarboxylic acid, p-H2bdc = 1,4-benzenedicarboxylic acid, have been successfully synthesized under solvothermal conditions. The linkage of different ligands with Cd(II) ions in compound 1 affords a (3,5)-connected layer. Furthermore, 2D→3D parallel polycatenation occurs wherein the layers are polycatenated with the adjacent two parallel layers to form a 3D framework. In 2 and 3, the polycarboxylates act as pillars to combine the metal-bip chains, yielding the layered structures. These 2D networks are extended to the final 3D supramolecular architectures by π-π stacking interactions. The results show that bip can act as a versatile building block for the construction of various coordination polymers. Moreover, the fluorescent properties of 13 in the solid state at room temperature have been investigated.  相似文献   

4.
Two novel coordination polymers have been hydrothermally synthesized by reactions of Cu(II), Mn(II) salt with 2-carboxyethyl(phenyl)phosphinic acid (H2L), namely, [Cu(L)(H2O)]n (1) and [Mn(HL)2]n (2). Both compounds were well characterized by single crystal X-ray diffraction, elemental analysis, IR spectroscopic, power X-ray diffraction and magnetic studies. Compound 1 crystallizes in a noncentrosymmetric monoclinic Cc space group and presents an inorganic two-dimensional (2D) network, whereas compound 2 adopts a noncentrosymmetric Pca21 space group and exhibits a 2D layer structure. Magnetic studies reveal a dominant ferromagnetic interaction in 1, and weak antiferromagnetic coupling between the Mn(II) ions in 2 mediated by phosphinico group, respectively.  相似文献   

5.
Hydrothermal reactions of lead(II) acetate with phenylarsonic acid (H2L1) (or 4-hydroxy-3-nitrophenylarsonic acid, H3L2) and 5-sulfoisophthalic acid monosodium salt (NaH2SIP) (or 1,3,5-benzenetricarboxylic acid (H3BTC)) as the second metal linkers afforded three novel mixed-ligand lead(II) carboxylate-arsonates, namely, Pb5(SIP)2(L1)2(H2O) 1, Pb3(SIP)(L2)(H2O) 2 and Pb(H2L2)(H2BTC) 3. The structure of 1 features a complicated 3D network composed of 2D double layers of lead(II) sulfoisophthalate bridged by 1D chains of lead(II) arsonates along b-axis, forming large tunnels along b-axis which are occupied by phenyl rings of the arsonate ligands. In 2, the Pb(II) ions are bridged by {L2}3− anions into a 2D double layer whereas the interconnection of the Pb(II) ions via bridging and chelating SIP anions gave a 2D double layer. The cross-linkage of the above two building units leads to a complicated 3D network. In 3, the interconnection of the Pb(II) ions via bridging {H2L2} and {H2BTC} anions leads to a 1D double chain down a-axis. These 1D chains are further interconnected via hydrogen bonds among non-coordination carboxylate groups and arsonate oxygens into a 3D supramolecular architecture.  相似文献   

6.
Six new chiral triorganotin(IV) complexes, {(R3Sn)2[C3H6(COO)2]}n (R = Me: 1; Bu: 2), {(R3Sn)2[C4H8(COO)2]}n (R = Me: 3; Bu: 4), and {(R3Sn)2[C2H4O(COO)2]}n (R = Me: 5; Bu: 6) have been prepared by treatment of (R)-(+)-methylsuccinic acid, (S)-(+)-methylglutaric acid and l-(−)-malic acid, with the corresponding R3SnCl (R = Me, Bu) and sodium ethoxide in methanol. All the complexes were characterized by elemental analysis, FT-IR, NMR (1H, 13C, 119Sn) spectroscopy and TGA. Except for 3, all of the complexes were also characterized by X-ray crystallography. The structural analyses reveal that complexes 1 and 5 have 2D network structures in which (R)-(+)-methylsuccinic acid and l-(−)-malic acid act as tetradentate ligands coordinated to trimethyltin(IV) ions. Complexes 2 and 4 have 3D metal-organic framework structures in which the deprotoned acids serve as tetradentate ligands. Complex 6 adopts a 1D zigzag chain structure and forms a 2D supramolecular framework through intermolecular C-H?O interactions. In addition, the antitumor activities of complexes 1-6 have been studied. We also have measured the specific rotation of the chiral dicarboxylic acids and the organotin derivatives.  相似文献   

7.
A series of new metal-organic frameworks (MOFs) based on 9,10-bis(imidazol-1-ylmethyl)anthracene and four structurally related aromatic dicarboxylates, namely, [Cd(L)(o-bdc)]·1.25H2O (1), [Cd(L)(pydc)] (2), [Zn(L)(pydc)] (3), [Cd3(L)2(m-bdc)3] (4) and [Cd(L)(p-bdc)]·2H2O (5) (L = 9,10-bis(imidazol-1-ylmethyl)anthracene, o-H2bdc = 1,2-benzenedicarboxylic acid, H2pydc = 2,3-pyridinedicarboxylic acid, m-H2bdc = 1,3-benzenedicarboxylic acid, p-H2bdc = 1,4-benzenedicarboxylic acid) have been synthesized under hydrothermal conditions. Their structures have been determined by single-crystal X-ray diffraction analyses, and further characterized by infrared spectra (IR), elemental analyses and powder X-ray diffraction (PXRD). Compound 1 displays a two-dimensional (2D) layer structure, which is stabilized by intramolecular hydrogen-bonding interactions. Compounds 2 and 3 are isostructural and show 2D layer structures, which are further extended by intermolecular C-H···O hydrogen-bonding interactions to form 3D supramolecular frameworks. Compound 4 has a 2D layer structure with trinuclear units [Cd3(u3-O)2]6+. Compound 5 is a 3D three-fold interpenetrating framework with a Schläfli symbol (66·8). The structural differences of these compounds indicate that the anions play important roles in the resulting structures of the MOFs. The luminescent properties were also investigated for compounds 1-5.  相似文献   

8.
By control of mixed ligands with particular coordination sites, heterometallic coordination polymers, [Ln2(H2O)2Ag(C2O4)2(ina)3]n (Ln = Eu (1), Dy (2), Hina = isonicotinic acid) and {[LnAg(C2O4)(na)2]·2H2O}n (Ln = La (3), Tb (4), Hna = nicotinic acid), have been synthesized under hydrothermal conditions and characterized by elemental analysis, IR, thermogravimetric analysis (TGA), and single-crystal X-ray diffraction. These coordination polymers feature 3D pillar-layered coordination frameworks constructed from two-dimensional (2D) lanthanide–carboxylate layers and Ag(ina) or Ag(na) pillars. It is interesting that the in situ decarboxylation of pyridine-2,3-dicarboxylic acid into nicotinic acid was observed. The luminescent properties of 1 and 4 were also studied.  相似文献   

9.
Four coordination polymers associated with bent bis(imidazole) 1,3-bis(imidazol-l-yl-methyl)benzene (mbix) and isophthalic acid (H2ip) or 5-methylisophthalic acid (H2mip) ligands, formulated as {[Cd(mbix)(mip)]·H2O} n (1), {[Co(mbix)(mip)]·0.4H2O} n (2) [Ni(mbix)(mip)H2O] n (3) and [Ni(mbix)(ip)] n (4), were synthesized under hydrothermal conditions and characterized by physico-chemical and spectroscopic methods. Complexes 1 and 2 are isomorphous and exhibit a 1D loop-like chain. Complex 3 features a 2D (4,4) layer, which further extends into an unusual 2D (3,5)-connected 3,5L2 double-layered supramolecular network via classical O–H···O hydrogen bonding interactions. Complex 4 is a 3D network, which shows a rare binodal (3,5)-connected 3,5T1 framework. Moreover, the luminescence and catalytic properties of the complexes for the degradation of methyl orange by sodium persulfate in a Fenton-like process are reported.  相似文献   

10.
Three novel Cd(II) coordination polymers, namely, [Cd(Dpq)(1,8-NDC)(H2O)2][Cd(Dpq)(1,8-NDC)]·2H2O (1), [Cd(Dpq)(1,4-NDC)(H2O)] (2), and [Cd(Dpq)(2,6-NDC)] (3) have been obtained from hydrothermal reactions of cadmium(II) nitrate with the mixed ligands dipyrido [3,2-d:2′,3′-f]quinoxaline (Dpq) and three structurally related naphthalene-dicarboxylate ligands [1,8-naphthalene-dicarboxylic acid (1,8-H2NDC), 1,4-naphthalene-dicarboxylic acid (1,4-H2NDC), and 2,6-naphthalene-dicarboxylic acid (2,6-H2NDC)]. Single-crystal X-ray diffraction analysis reveals that the three polymers exhibit novel structures due to different naphthalene-dicarboxylic acid. Compound 1 is a novel cocrystal of left- and right-handed helical chains and binuclear complexes and ultimately packed into a 3D supramolecular structure through hydrogen bonds and π-π stacking interactions. Compound 2 shows a 2D rectangular network (4,4) bridged by 1,4-NDC with two kinds of coordination modes and ultimately packed into a 3D supramolecular structure through inter-layer π-π stacking interactions. Compound 3 is a new 3D coordination polymer with distorted PtS-type network. In addition, the title compounds exhibit blue/green emission in solid state at room temperature.  相似文献   

11.
Two unusual pillared-layer 3d-4f Ln-Cu heterometallic coordination polymers, {[Ln2Cu5Br4(IN)7(H2O)6]·H2O}n (Ln=Eu (1) and Gd (2), HIN=isonicotinic acid), have been synthesized under hydrothermal conditions, and characterized by elemental analysis, IR, thermal analysis and single-crystal X-ray diffraction. The structure determination reveals that 1 and 2 are isostructural and feature a novel three-dimensional pillared-layer hetrometallic structure built upon the linkages of one-dimensional (1D) linear Ln-carboxylate chains, zero-dimensional (0D) Ln-carboxylate Ln2(IN)8 dimers, rare 1D zigzag [Cu5Br4]n inorganic chains and IN pillars. In both 3D structures, there are Ln-carboxylate layers resulted from the connections of 1D Ln-carboxylate chains and 0D Ln2(IN)8 dimers through O-H?O hydrogen bondings. The luminescent properties of 1 have been investigated. The magnetic properties of 1 and 2 have also been studied.  相似文献   

12.
Three new scorpionate nickel complexes [Tp*Ni(Hglu)(H2O)]·EtOH (1), Tp*Ni(Haze)(MeOH) (2), and Tp*Ni(HTA)(H2O) (3) (Tp*?=?hydrotris(3,5-dimethylpyrazolyl)borate) with different spanning dicarboxylo co-ligands (H2glu?=?glutaric acid, H2aze?=?azelaic acid, H2TA?=?tetradecane diacid) were synthesized by solution methods at room temperature. X-ray crystallographic analyses of complexes 1?C3 demonstrate that these three octahedral Ni scorpionate complexes each contain an anionic chelating dicarboxylic acid, O2C(CH2) n COOH, n?=?3, 7, and 12, respectively. The sixth coordination site is occupied by an ethanol, methanol, or water that is hydrogen bonded to the terminal carboxylic acid end of the anionic dicarboxylic acid ligand from a different Tp*Ni complex in the crystal lattice. Through these abundant hydrogen bond interactions, complexes 1 and 2 form 2D hydrogen bonding network structures, respectively, while complex 3 has a 1D infinite double-chain structure. The results of quantum mechanical calculations and thermogravimetric analyses on these complexes are presented and discussed.  相似文献   

13.
Three cobalt(II) coordination polymers {[Co(L1)(nda)(H2O)2]·2H2O} n (1), [Co(L2)(tbi)(H2O)] n (2) and [Co(L2)(bpdc)(H2O)] n (3) (L1 = 1,3-bis(5,6-dimethylbenzimidazol-1-yl)-2-propanol, L2 = 1,3-bis(benzimidazol-1-yl)-2-propanol, H2nda = 2,6-naphthalenedicarboxylic acid, H2tbi = 5-tert-butyl isophthalic acid and H2bpdc = 4,4′-biphenyldicarboxylic acid) were synthesized and characterized by physicochemical and spectroscopic methods. Complex 1 exhibits a 1D loop-like structure, which is further extended into a 3D 3,3,4T31 network through two O–H···O hydrogen bonding interactions. Complex 2 displays a 1D ladder-like chain, arranged into a 2D supramolecular network with 3,3,4L34 topology via classical O–H···O hydrogen bonding interactions, whereas complex 3 features a 2D 3,4L13 layer structure and further assembles into a 3D framework with a twofold interpenetrating sqc65 topology through O–H···O hydrogen bonding interactions. The fluorescence and catalytic properties of these complexes for the degradation of Congo red in a Fenton-like process have been investigated.  相似文献   

14.
Two metal–organic coordination polymers, {Co(bbbi)0.5(bm)(Hbtc)} n (1) and {Ag2(bbbi)2(ntp)(H2O)·4H2O} n (2), [bbbi = 1,1-(1,4-butanediyl)bis-1H-benzimidazole, bm = benzimidazole, H3btc = 1,2,4-trimellitic acid, and H2ntp = 2-nitroterephthalic acid], have been hydrothermally synthesized and characterized by physico-chemical and spectroscopic methods and single-crystal diffraction. 1 Features a 1D ladder-like chain and is further connected by O–H···O hydrogen bonding interactions to yield a 3D supramolecular architecture. 2 Possesses a 1D infinite zigzag chain connected by bbbi ligands in bis-monodentate mode, which is further extended into a 3D complicated supramolecular network by face-to-face ππ stacking interactions and O–H···O hydrogen bonds. Moreover, both compounds exhibit catalytic properties on degradation of methyl orange in Fenton-like process.  相似文献   

15.
Four coordination polymers, [Zn(pda)(bpy)(H2O)]n·nH2O (1), [Cd(pda)(prz)(H2O)]n (2), [Co3(μ3-OH)2(pda)2(pyz)]n·2nH2O (3) and [Pr2(pda)3(H2O)2]n (4) (H2pda=1,3-phenylendiacetic acid, bpy=4,4′-bipyridine, prz=piperazine and pyz=pyrazine) have been hydrothermally synthesized and characterized. Complex 1 is a 1D wheel-like chain structure, which is further extended into a 3D metal-organic supramolecular framework by H-bonds and π-π stacking interactions. Complex 2 is a 1D ladder-like chain structure, which is also further extended into a 3D metal-organic supramolecular framework by H-bonds. Complex 3 possess a 2D sheet structure with infrequent two pairs of double-helix chains. Complex 4 features a 3D structure. Both 1 and 2 display strong blue fluorescent emission at room temperature. Magnetic susceptibility measurements of complexes 3 and 4 exhibit antiferromagnetic interactions between the nearest metal ions, with C=9.99 and 3.43 cm3 mol−1 K, and θ=−23.9 and −46.3 K, respectively.  相似文献   

16.
Chemical investigation of a methanolic extract of leaves from Araucaria bidwillii (Araucariaceae) from Egypt afforded four new labdane diterpenoidal metabolites (14) together with one known diterpene, 7-oxocallitrisic acid (5), two triterpenoidal metabolites, 2-O-acetyl-11-keto-boswellic acid (6) and β-sitosterol-3-O-glucopyranoside (7), phloretic acid (8), and two methylated bisflavonoids, agathisflavone-4′,7,7″-trimethyl ether (9) and cupressuflavone-4′,7,7″-trimethyl ether (10). The new metabolites 14 were unambiguously identified by applying extensive 1D and 2D NMR spectroscopic studies as well as HRESIMS. The relative and absolute configurations of 14 were determined using ROESY and the modified Mosher's method, respectively. All isolated compounds were assessed for their antimicrobial, antitubercular and cytotoxic activities. Among the tested compounds, the new labdane diterpenes 14 revealed significant cytotoxic activity against mouse lymphoma L5178Y cell line with IC50 values ranging from 1.4 to 12.9 μM, respectively.  相似文献   

17.
The reactions of aromatic dicarboxylic acids and methyl-functionalized 4,4′-bipyridine ligands with metal salts under hydrothermal conditions generated four structurally diverse cobalt(II), zinc(II) and cadmium(II) coordination polymers, [Co(CH3-BDC)(dmbpy)0.5] n (1), [Cd(OH-HBDC)2(dmbpy)] n (2), [Zn(NDC)(dmbpy)] n , (3) and {[Cd(DBA)(dmbpy)0.5]·2H2O} n (4) (CH3–H2BDC = 5-methylisophthalic acid, OH–H2BDC = 5-hydroxyisophthalic acid, H2NDC = 1,4-naphthalenedicarboxylic acid, H2DBA = 4,4′-methylenedibenzoic acid, dmbpy = 2,2′-dimethyl-4,4′-bipyridine). All four complexes have been structurally characterized by X-ray crystallography. Complex 1 shows a 3D jsm topology structure with two 1D channels parallel to the a and b axes. Complex 2 has a zigzag chain in which the OH-HBDC ligands point alternately up and down. Complexes 3 and 4 show 2D (4,4) networks when the dinuclear metal centers and their ligands are regarded as nodes and linkers, respectively. Complex 3 also shows twofold interpenetration with 1D channels along the b axis. Two nets of complex 4 interlock in parallel, giving rise to a polycatenated layer (2D → 2D). Thermogravimetric and chemical stabilities, magnetic and luminescent properties of these complexes were investigated.  相似文献   

18.
Two new metal–organic coordination polymers {[Co(L1)(nip)]·H2O} n (1) and [Co(L2)(ip)] n (2) (H2ip = isophthalic acid, L1 = 1,3-bis(benzimidazol-1-ylmethyl)benzene, L2 = 1,4-bis(5-methylbenzimidazol-1-ylmethyl)benzene, H2nip = 5-nitroisophthalic acid) have been synthesized under hydrothermal conditions and characterized by physicochemical and spectroscopic methods as well as single-crystal X-ray diffraction analysis. The analysis reveals that complex 1 has a 1D double chain structure connected by L1 and nip2? ligands, which is further assembled into a 3D bbf (moganite network) supermolecular framework via two types of C–H···O hydrogen bond interactions. Complex 2 possesses a 3D MOF with a four-connected cds (CdSO4 network) topology. The fluorescence and catalytic properties of the complexes for the degradation of Congo red have been investigated.  相似文献   

19.
Reaction of Zn(NO3)2·6H2O with p-aminobenzoic acid in a 1:2 molar ratio under ethanol medium at room temperature affords a new three dimensional (3D) coordination polymer [Zn(PABA)2]·H2O (1) (PABA = p-aminobenzoic acid). Single-crystal X-ray diffraction reveals that 1 crystallizes in the orthorhombic system, space group P212121, a = 7.614(2), b = 11.133(3), c = 16.869(4). 1 adopts a 3D open framework with H2O molecules in the cavities. PABA, acting as bridging ligand as well as coordinating ligand, adopts a different coordination mode to bridge Zn atoms and form the 3D supramolecular structure which is further stabilized by N–H?O, O–H?O hydrogen bonding and π–π stacking interactions. Powder second-harmonic generation (SHG) efficiency measurement with Nd:YAG laser (1064 nm) radiation shows that the SHG efficiency of 1 is equivalent to KDP crystal. The present work also demonstrates that the framework of 1 is retained after removal of the guest H2O molecules, and the H2O molecules can be reintroduced into the framework, indicating that this complex may also be used to generate porous materials.  相似文献   

20.
Seven new Cd(II) complexes consisting of different phenanthroline derivatives and organic acid ligands, formulated as [Cd(PIP)2(dnba)2] (1), [Cd(PIP)(ox)]·H2O (2), [Cd(PIP)(1,4-bdc)(H2O)]·4H2O (3), [Cd(3-PIP)2(H2O)2]·4H2O (4), [Cd2(3-PIP)4(4,4′-bpdc)(H2O)2]·5H2O (5), [Cd(3-PIP)(nip)(H2O)]·H2O (6), [Cd2(TIP)4(4,4′-bpdc)(H2O)2]·3H2O (7) (PIP=2-phenylimidazo[4,5-f]1,10-phenanthroline, 3-PIP=2-(3-pyridyl)imidazo[4,5-f]1,10-phenanthroline, TIP=2-(2-thienyl)imidazo[4,5-f]1,10-phenanthroline, Hdnba=3,5-dinitrobenzoic acid, H2ox=oxalic acid, 1,4-H2bdc=benzene-1,4-dicarboxylic acid, 4,4′-H2bpdc=biphenyl-4,4′-dicarboxylic acid, H2nip=5-nitroisophthalic acid) have been synthesized under hydrothermal conditions. Complexes 1 and 4 possess mononuclear structures; complexes 5 and 7 are isostructural and have dinuclear structures; complexes 2 and 3 feature 1D chain structures; complex 6 contains 1D double chain, which are further extended to a 3D supramolecular structure by π-π stacking and hydrogen bonding interactions. The N-donor ligands with extended π-system and organic acid ligands play a crucial role in the formation of the final supramolecular frameworks. Moreover, thermal properties and fluorescence of 1-7 are also investigated.  相似文献   

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