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1.
Here we demonstrate the synthesis of telechelics with different spacer units and different numbers of metal-complexing units, like α-methoxy-ω-(2,2′:6′,2″-terpyrid-4′-yl)-poly(ethylenoxide)78 ( 1 ), bis(2,2′:6′,2″-terpyrid-4′-yl) di(ethylene glycol) ( 2 ), bis(2,2′:6′,2″-terpyrid-4′-yl)-poly(ethylene oxide)180 ( 3 ) and tris[(2,2′:6′,2″-terpyrid-4′-yl)-oligo (ethylenoxy-)3.33]glycerin ( 4 ) utilizing 4-chloro-2,2′:6′,2″-terpyridine. The complexation behaviour of a variety of metal-salts towards the telechelics was studied and different supramolecular architectures were investigated, such as symmetric polymeric complexes and linear coordination polymers. Furthermore, attempts have been undertaken to prepare metallo-supramolecular cross-linked systems. 相似文献
2.
Ferlay S Koenig S Hosseini MW Pansanel J De Cian A Kyritsakas N 《Chemical communications (Cambridge, England)》2002,(3):218-219
Using 4,4',4"-tricyanotriphenylmethanol 1 as a heterotetradentate tecton with C3v symmetry bearing three CN and one OH group, under self-assembly conditions a 3-D coordination network was obtained in the presence of Ag+ cations acting as a tetrahedral metallic tecton; due to the metrics of 1 (three long and one short distance between the central C atom and N and O coordination sites, respectively), the 3-D network is of pseudo-diamondoid type with different cavity sizes; although a two-fold homo-interpenetration is observed for the 3-D networks, the remaining space is occupied by CHCl3, MeOH solvent molecules and SbF6- anions. 相似文献
3.
The implementation of four bidentate building blocks into a high-denticity linker with a flexible spacer leads to a predisposed ligand that allows one to direct the self-assembly of 1D functional coordination polymers. This is illustrated by the assembly under mild conditions of the luminescent metal-organic framework [Tb(Htpabn)] . 14H2O infinity (1; H4tpabn = N,N,N',N'-tetrakis[(6-carboxypyridin-2-yl)methyl]butylenediamine). The X-ray crystal structure shows that the monoprotonated Htpabn binds two equivalent lanthanide ions to form a one-directional staircase chain. The high ligand denticity prevents solvent coordination and leads to a high luminescence quantum yield (Q = 39%), which is maintained after solvent removal. 相似文献
4.
Alexander M. Kirillov 《Coordination chemistry reviews》2011,255(15-16):1603-1622
The design of new coordination polymers is nowadays a challenging research topic that attracts increasing interest due to the unique structural and functional properties of such metal-organic materials. In contrast to the recognized use of some N-donor ligands for the construction of coordination polymers, the application of hexamethylenetetramine (hmt) as a simple, commercially available, water-soluble and highly versatile cagelike building block has so far been explored to a lesser extent, although a considerable number of hmt-driven metal-organic networks have been reported in the last few years. Given the high potential of hmt for future developments of this research field, the present review summarizes the main structural and topological types of coordination polymers bearing hmt. These compounds feature a high diversity of topologies that include linear, zigzag, double, triple and quadruple 1D chains, rectangular grids, flat and undulating 2D layers, as well as layer-pillared, octahedral, zeolite-like, honeycomb-like and other complex 3D nets, in which hmt acts as a linker or spacer, pillar or connector, stabilizer and/or supporting ligand. The most common synthetic strategies are reviewed, showing that a diversity of metal-organic networks can be generated by facile self-assembly routes in aqueous medium and using rather simple chemicals. The main types of auxiliary ligands necessary for the construction of hmt-driven coordination networks are also identified. The additional structural features such as the formation of supramolecular networks and water clusters are described, and the selected properties and potential applications of hmt-containing coordination polymers as porous, magnetic or photoluminescent materials are highlighted. 相似文献
5.
《Journal of Coordination Chemistry》2012,65(24):4031-4046
AbstractN,N′-Bis(pyridin-4-ylmethylene)naphthalene-1,5-diamine (L) acts as a bipyridine analogue linker ligand towards {Zn7(μ4-O)2(OAc)10}, {Zn2(NCS)2(OAc)2}, and {Zn(N3)2} nodes and allows construction of three new 1-D coordination polymers, the linear chain [Zn7(μ4-O)2(OAc)10(L)]n (1), [Zn(NCS)(OAc)(L)]n (2) in ladder-type geometry and the zigzag chain [Zn(N3)2(L)]n (3). Structural characterization reveals that in 1 acetate anionic ligands connect seven Zn(II) ions through the bridging coordination modes μ3-η1,η2 and μ2-η1,η1. The resulting heptanuclear node is located on an inversion center and therefore consists of four crystallographically distinct cations; their coordination spheres correspond to distorted octahedra or tetrahedra. The Zn(II) ions in polymer 2 exhibit distorted trigonal bipyramidal {ZnN3O2} coordination; μ2-η1,η1 coordinated acetate and terminal thiocyanate ligands lead to inversion-symmetric [Zn2(NCS)2(OAc)2] secondary building units (SBU), which are further linked by the N,N′-bipyridine analogue L. Terminal coordination of two anionic azide ligands and the bridging bipyridine L result in coordination polymer 3, in which the cations adopt distorted tetrahedral {ZnN4} coordination. In all crystalline solids 1–3, adjacent 1-D chains interact through π–π stacking and non-classical (C???H···O, C???H···π) hydrogen bonds, leading to 3-D supramolecular architectures. Differences in their 3-D arrangement are due to variations in the anionic co-ligands, subtle conformational differences in the semi-rigid linker and the variable coordination sphere about the zinc cations. Thermogravimetric investigations indicate differences in both thermal stability and decomposition mode. Natural bond orbital (NBO) analysis provides a convenient basis for investigating the intramolecular bonding interactions and delocalization effects in these molecular systems. Finally, solids 1–3 exhibit intense luminescence at room temperature. 相似文献
6.
Rafika Bouchene Sofiane Bouacida 《Acta Crystallographica. Section C, Structural Chemistry》2019,75(2):120-127
Two new coordination polymers, namely poly[[(3‐aminopyrazin‐4‐ium‐2‐carboxylate‐κ2N1,O)di‐μ‐chlorido‐cadmium(II)] monohydrate], {[CdCl2(C5H5N3O2)]·H2O}n, (1), and poly[2‐amino‐3‐carboxypyrazin‐1‐ium [(3‐aminopyrazine‐2‐carboxylato‐κ2N1,O)di‐μ‐chlorido‐cadmium(II)] monohydrate], {(C5H6N3O2)[Cd(C5H4N3O2)Cl2]·H2O}n, (2), have been synthesized from the reaction of cadmium(II) chloride and 3‐aminopyrazine‐2‐carboxylic acid (Hapca) under mild conditions in acidic media. The two coordination polymers have been characterized by single‐crystal X‐ray diffraction and show chloride‐bridged zigzag chains with octahedrally coordinated metal ions, where Hapca acts as a bidentate ligand via the π‐conjugated N atom and a carboxylate O atom. The chains are further interconnected via noncovalent interactions into three‐dimensional supramolecular networks. The dominant H…O and H…Cl interactions for both compounds were quantified using Hirshfeld surface analysis. The thermal stability and topological analysis of the two‐dimensional networks of (1) and (2) are also discussed. 相似文献
7.
Z.-W. Yan F. Li H.-F. Zeng S.-J. Luo T.-H. Li 《Journal of the Iranian Chemical Society》2010,7(4):978-985
A new lead coordination polymer [Pb(aip)]n (H2aip = 5-aminoisophthalic acid) was synthesized and characterized by IR, elemental and X-ray single-crystal analyses. X-ray crystallographic study of this complex revealed that H2aip ligand adopts a new coordination mode different from any reported modes in the title complex. The thermogravimetric experiment was carried out to examine the thermal stability, and the photoluminescence property of the title complex was investigated. 相似文献
8.
Three new silver sulfonate metal-organic frameworks are presented along with a design strategy for future generations. [[Ag6(mesitylenetrisulfonate)2(H2O)5].2H2O]infinity (1), [Ag4(durenetetrasulfonate)(H2O)2](infinity) (2), and [[Ag4(1,3,5,7-tetrakis(4,4'-sulfophenyl)adamantane)(H2O)2].1.3H2O]infinity (3) represent a series of open-framework silver sulfonate solids where the organic linker plays a key role in determining the overall structure. Compound 1 forms a pillared layered structure, while compounds 2 and 3 form 3-D nets derived from cross-linking of 1-D columns of silver sulfonates. All three solids incorporate water molecules, which can be removed to yield a solid stable to in excess of 300 degrees C. Powder X-ray diffraction studies and vapor sorption experiments show, for 1 and 2, that the solids retain their structure when guests are removed and, for all three, that water vapor is resorbed stoichiometrically by the solids. An idealized silver sulfonate framework is proposed, and upon comparison to the reported structures, guidelines are proposed for structural constraints in the design of future generations of 1-D and possibly 0-D aggregate structures. 相似文献
9.
Xiangru Meng Huayun Han Yaoting Fan Yu Zhu Chenxia Du 《Journal of organometallic chemistry》2003,679(2):153-161
Novel two-dimensional layered lanthanide(III)-ferrocenedicarboxylate coordination polymers {[M(η2-O2CFcCO2-η2)(μ2-η2-O2CFcCO2-η2-μ2)0.5(H2O)2]·mH2O}n (Fc=(η5-C5H4)Fe(η5-C5H4), M=Tb3+, m=2, 1; M=Eu3+, m=2, 2; M=Y3+, m=1, 3) with trapezium-shaped units and one-dimensional wave-shaped Cd(II)-ferrocenedicarboxylate polymer {[Cd(η2-O2CFcCO2-η2)(H2O)3]·4H2O}n (4) have been prepared and structurally characterized by single crystal diffraction. In polymers 1-3, each central metal ion (Tb(III), or Eu(III) or Y(III)) is located in a pseudo-capped-tetragonal prism coordination geometry, and ferrocenedicarboxylate anion ligands have two coordination modes (bidentate-chelating mode and tridentate-bridging mode). The magnetic behaviors for 1 and 2 are studied in the temperature range of 5.0-300 K. The results show that the paramagnetic behavior of 2 is mainly due to the effective spin-orbital coupling between the ground and excited states through the Zeeman perturbation, and the weak magnetic interaction between Eu3+ centers can be observed. In addition, compared with sodium ferrocenedicarboxylate, the fluorescent intensities of the polymers 1-4 are enhanced in the solid state. 相似文献
10.
Reaction between boric acid and guanidinium salts in methanolic solution at room temperature in the presence of various bases and anions gives well-formed solvated crystals of composition {[B(OCH3)4]3[C(NH2)3]4}+X-. The products in which X- = Cl- and PF6- are characterized by single-crystal X-ray diffraction. The tetramethoxyborate and guanidinium components form a highly symmetrical (cubic) hydrogen-bonded 3D network having the "boracite topology" [i.e., the (63)(6284) topology]. Highly disordered solvent molecules and anions occupy methyl-surfaced cavities and channels that represent more than 30% of the space. 相似文献
11.
The complexes of formulas Ln(pydc)(Hpydc) (Ln = Sm (1), Eu (2), Gd (3); H2pydc = pyridine-2,5-dicarboxylic acid) and Ln(pydc)(bc)(H2O) (Ln = Sm (4), Gd (5); Hbc = benzenecarboxylic acid) have been synthesized under hydrothermal conditions and characterized by elemental analysis, IR, TG analysis, and single-crystal X-ray diffraction. Compounds 1-3 are isomorphous and crystallize in the orthorhombic system, space group Pbcn. Their final three-dimensional racemic frameworks can be considered as being constructed by helix-linked scalelike sheets. Compounds 4 and 5 are isostructural and crystallize in the monoclinic system, space group P2(1)/c. pydc ligands bridge dinuclear lanthanide centers to form the three-dimensional frameworks featuring hexagonal channels along the a-axis that are occupied by one-end-coordinated bc ligands. From the topological point of view, the five three-dimensional nets are binodal with six- and three-connected nodes, the former of which exhibit a rutile-related (4.6(2))(2)(4(2).6(9).8(4)) topology that is unprecedented within coordination frames, and the latter two species display a distorted rutile (4.6(2))(2)(4(2).6(10).8(3)) topology. Furthermore, the luminescent properties of 2 were studied. 相似文献
12.
Zheng B Dong H Bai J Li Y Li S Scheer M 《Journal of the American Chemical Society》2008,130(25):7778-7779
By fine-tuning the reaction temperature to 5, 15, 30, and 50 degrees C, respectively, four different complexes, [Cd(HC4O4)2(H2O)4] (1), [Cd4(C4O4)4(H2O)16].(H2O)2 (2), [Cd(C4O4)(H2O)2] (3), and [Cd(C4O4)(H2O)2] (4), were formed successfully from the identical initial reaction mixture. Moreover, an unprecedented reversible interconversion among the four complexes at the corresponding reaction temperatures mediated by the mother liquor was observed. 相似文献
13.
《Journal of Coordination Chemistry》2012,65(11):1203-1211
Hydrothermal reactions of Nd(ClO4)3·6H2O, Gd(ClO4)3·6H2O and Er2O3 with H3NTA (nitrilotriacetic acid) afford three new lanthanide coordination polymers, {[Nd(NTA)(H2O)]· 2H2O} n (1), {[Gd(NTA)(H2O)]·2H2O} n (2) and {[Er(NTA)(H2O)]·H2O} n (3), characterized by elemental analysis and IR spectroscopy. X-ray single crystal structural analyses showed that 1 and 2 are an isomorphous 2D-layered framework containing the nine-coordinated Nd(III) (or Gd(III)), and woven into a 3D suprastructure by interlayer hydrogen bonding while 3 is a 3D structure with eight-coordinate Er(III). 相似文献
14.
A topological isomer based on Zn2 paddlewheel, dicarboxylate, and diamine ligands is synthesized by solvothermal methods after careful modulation of the reaction conditions. The new framework is characterized by a pillared Kagome net topology and possesses a sustainable pore structure with high surface area (approximately 2400 m2/g) and large hexagonal channels (approximately 15 A). 相似文献
15.
The hydrothermal reactions of metal precursors with aminotri(methylenephosphonic acid) yielded a series of similar structural coordination polymers of general formula {M[HN(CH2PO3H)3](H2O)3}n [M = Mg(II) (1), Mn(II) (2), Co(II) (3), Zn(II) (4) and Cd(II) (5)]. Compounds 1–5 were characterized by X-ray single crystal diffraction, elemental analyses, and thermogravimetric analyses. Compounds 1–5 all reveal the wave-like 1D chain structures and the structures are constructed by two types of eight-membered, square-like rings linked alternatively via the phosphonate oxygen atoms, generating double-channel systems. The magnetic studies of 2 and 3 reveal that antiferromagnetic interactions are mediated between the metal ions. 相似文献
16.
《Journal of Coordination Chemistry》2012,65(18):3274-3286
Hydrothermal reactions of lanthanide chloride, phosphonoacetic acid (H2O3PCH2COOH), and water in the presence of HCl provide a series of lanthanide coordination polymers. FT-IR spectra confirm that there are three kinds of structures among seven complexes, {[Ln2(O3PCH2CO2)2(H2O)3]?·?H2O}∞ (type I) (Ln?=?LaIII for 1; PrIII for 2; NdIII for 3 and EuIII for 4), [Ln(O3PCH2CO2)(H2O)2]∞ (type II) (Ln?=?TbIII for 5), and [Ln(O3PCH2CO2)(H2O)2]∞ (type III) (Ln?=?HoIII for 6 and YbIII for 7). Complexes 1–5 show 2-D 4,4,5,5-connected (44?·?62)(45?·?6)(46?·?64)(48?·?62) topology networks and 2-D 4-connected (44?·?62) topology networks and then are further linked into 3-D supramolecular networks by hydrogen-bonding interactions; 6 and 7 both exhibit a 3-D 4-connected (42?·?63?·?8) topology with 1-D dumbbell-shaped channels. The results indicate infrared spectroscopy is in accord with the result of single-crystal X-ray analysis. 相似文献
17.
《Journal of organometallic chemistry》2007,692(1-3):136-141
We report on the synthesis and crystal structures of two new zinc coordination polymers with 4,4′-oxybis(benzoate) (oba) ligands. Single crystals of [Zn2(oba)2(azpy)(dmf)2] · 6DMF(azpy = 4,4′-azopyridine) and [Zn2(oba)2(bpe)] · 2DMF · 4H2O (bpe = trans-1,2-bis(4-pyridyl)ethylene) were prepared by treatment of Zn(CH3COO)2 · 2H2O with the H2oba and bis-pyridine type ligands, azpy and bpe, respectively, in DMF. Compound [Zn2(oba)2(azpy)(dmf)2] · 6DMF has a unique ladder structure comprising of heteroorganic bridges, in which the Zn–oba chains construct the side rails, while the Zn–azpy–Zn parts construct the rungs of the ladder framework. Despite the large size of the cavities, these ladder chains stack without interpenetration, and the cavities in the ladder framework are partially connected to create one-dimensional channel-like cavities. Compound [Zn2(oba)2(bpe)] · 2DMF · 4H2O exhibits a three-dimensional coordination framework that is comprised of heteroorganic bridges. The framework is interwoven by two-dimensional layers of [Zn2(oba)2] and the Zn2–bpe chains. The three-dimensional framework, which contains large cavities, about 13 × 11 Å2 in area, has a high porosity and a density of only 0.53 g cm−3. 相似文献
18.
This paper reports two new coordination polymers formed by carboxylate-substituted benzoimidazole and formate ligands: [Mn(L)·(HCO2)]n (1) and [Co(L)·(HCO2)]n (2) (L = benzoimidazol-1-yl-acetate). Com-plexes 1 and 2 are isomorphous and adopt a new 3,6-connected three-nodal topology showing inter-esting magnetic properties: spin canted antiferromagnetism for MnⅡ complex 1, but simple antiferro-magnetic coupling for CoⅡ complex 2. 相似文献
19.
Domasevitch KV Gural'skiy IA Solntsev PV Rusanov EB Krautscheid H Howard JA Chernega AN 《Dalton transactions (Cambridge, England : 2003)》2007,(29):3140-3148
A new polydentate ligand 4,4'-bipyridazine (4,4'-bpdz) was prepared by employing inverse electron demand cycloaddition of 1,2,4,5-tetrazine. A unique combination of structural simplicity, ampolydentate character and efficient donor properties towards Cu(I), Cu(II) and Zn(II) provide wide new possibilities for the synthesis of coordination polymers incorporating the 4,4'-bpdz module either as a bi-, tri- or tetradentate connector between the metal ions. 1D coordination polymers Cu(2)(4,4'-bpdz)(CH(3)CO(2))(4) x 4H(2)O and Zn(4,4'-bpdz)(NO(3))(2), and interpenetrated (4,4)-nets in [Cu(4,4'-bpdz)(2)(H(2)O)(2)]S(2)O(6) were closely related to 4,4'-bipyridine compounds. 1D "ladder-like" polymer Cu(2)(4,4'-bpdz)(3)(CF(3)CO(2))(4) and the unprecedented 3D binodal net ({8(6)}{6(3);8(3)}) in [Cu(3)(4,4'-bpdz)(6)(H(2)O)(4)](BF(4))(6) x 6H(2)O were based upon a combination of linear and angular organic bridges. Complex [Cu(3)(OH)(2)(4,4'-bpdz)(3)(H(2)O)(2){CF(3)CO(2)}(2)](CF(3)CO(2))(2) x 2H(2)O has a "NbO-like" 3D topology incorporating discrete dihydroxotricopper(II) clusters linked by tri- and tetradentate ligands. The tetradentate function of the 4,4'-bpdz ligand was especially relevant for copper(I) complexes, which adopt layered Cu(2)X(2)(4,4'-bpdz) (X = Cl, Br) or 3D chiral framework (X = I) structures based upon infinite (CuX)(n) chains. The electron deficient character of the ligand was manifested by short anion-pi interactions (O-pi 3.02-3.20; Cl-pi 3.35 A), which may be involved as a factor for controlling the supramolecular structure. 相似文献
20.
Two new magnesium coordination polymers, [Mg(9,10-ADC)(H2O)2(DMF)2]n (1) and [Mg6(1,4-NDC)5(HCO2)4(DMF)(H2O)]n·2n[H2N(CH3)2]·2n(DMF) (2) (9,10-ADC = 9,10-anthracenedicarboxylate; 1,4-NDC = 1,4-naphthalenedicarboxylate) have been solvothermally synthesized. Compound 1 displays a one-dimensional linear chain structure, which is orderly constructed from magnesium metal cations connecting with carboxylic oxygen atoms of 9,10-H2ADC along the a axis. Compound 2 exhibits a three-dimensional framework composed of infinite chains of corner-sharing octahedral MgO6 with 1,4-NDC ligands forming one-dimensional channels along the a axis, where guest molecules reside. When guest molecules are removed, no structural transformation is found to occur, generating a robust structure with permanent porosity. The studies of CO2 absorption suggest that compound 2 is a promising adsorbent material for CO2. 相似文献