Examples Of Coordination Polymers Research Articles

Bringing a New Flexible Mercaptoacetic Acid Linker to the Design of Coordination Polymers.

Two new 3D coordination polymers (CPs), formulated as [Zn(p-XBT)]n (1H) and [Cd(p-XBT)]n (2H), were assembled from a virtually unexplored p-xylylene-bis(2-mercaptoacetic) acid linker (p-XBTA) and characterized by infrared spectroscopy (FTIR), powder X-ray diffraction (PXRD), thermal analysis methods (TG-DSC, TG-FTIR), single-crystal X-ray diffraction, and topological analysis. Two different synthetic strategies were explored, namely the precipitation (P) and hydrothermal (H) methods, resulting in a Zn(II) derivative [Zn(p-XBT)·H2O]n (1P) and its dehydrated analogue [Zn(p-XBT)]n (1H), respectively. In the Cd(II)-containing system, the same [Cd(p-XBT)]n (2P = 2H) products were generated by both synthetic methods. Upon dehydration, 1P undergoes a “crystal-to-crystal” phase transition in the 170−185 °C temperature range, producing an anhydrous polycrystalline sample (1H). Both CPs 1H and 2H are isostructural and feature polymeric 3D metal-organic nets of the cds topological type, which are driven by the 4-linked metal and p-XBT2− nodes. These compounds represent unique examples of coordination polymers derived from p-xylylene-bis(2-mercaptoacetic) acid, thus opening up the use of this flexible S,O-heterodonor building block in the design of polymeric metal-organic architectures.

2D-Coordination polymers based on 1H-indazole-4-carboxylic acid and transition metal ions: magnetic, luminescence and biological properties

Five novel multifunctional coordination polymers (CPs) based on 1H-indazole-4-carboxylic acid are reported. These complexes, the first examples of CPs with this novel ligand, show interesting magnetic, luminescence and biological properties.

Control of dimensionality in Manganese Coordination Polymers using rigid tetrahedral-shaped [1.1.1.1]metacyclophane ligands bearing benzoate coordinating sites: From homochiral 1D to 3D diamond-like structures

Solvothermal synthesis involving tetrasubstituted carboxylic derivatives of [1.1.1.1]metacyclophane (1–2) bearing rigid phenyl spacer, that inherently adopt the 1,3-Alternate conformation, with Manganese salts (acetate and nitrate) led to new 1D and 3D coordination polymers: {13-Mn9O3(CH3COO)6(C5H5N)12} (13-Mn9) and {2-Mn2(C3H7NO)2} (2-Mn2), respectively. The X-ray diffraction analysis revealed that: (i) ligand 1, containing meta-benzoate coordinating sites, forms a 1D chiral helicoidal Coordination Polymer (13-Mn9) with trinuclear metallic clusters (MnIIMnIII2(μ3-O)) acting as linear connection nodes; (ii) ligand 2, bearing para-benzoate moieties forms, a 3D diamond-like Coordination Polymer (2-Mn2) presenting Mn(II) polymeric chains bridged by tetrahedral-shaped ligand. The obtained Mn-based compounds are the first examples of coordination polymers based on tetrasubstituted [1.1.1.1]metacyclophane ligands bearing carboxylate coordinating groups.

Flexible bis(pyridyl-tetrazole) ligand-induced ring-containing metal–organic coordination polymers: synthesis, structures, and properties

Three coordination polymers (CPs), [Co(3-bptzp)(BDC)] (1), [Zn(3-bptzp)(BDC)] (2), and [Cd(3-bptzp)(BDC)] (3) (3-bptzp = 1,4-bis(5-(3-pyridyl)tetrazolyl)propane, H2BDC = 1,3-benzenedicarboxylic acid), were synthesized under hydrothermal conditions. The CPs were structurally characterized by single-crystal X-ray diffraction, infrared spectroscopy (IR), elemental analyses, and powder X-ray diffraction (PXRD). Complexes 1–3 represent the first examples of CPs based on the flexible bis(pyridyl-tetrazole) 3-bptzp. Structure analyses reveal that 1–3 are 1-D ring-containing polymeric chains. For 2 and 3, adjacent 1-D chains are extended to 2-D supramolecular networks by hydrogen bonding. Dye adsorption properties of 1–3, electrochemical properties of 1, and fluorescent-sensing behaviors of 2 and 3 have also been investigated.

Multifunctional Aromatic Carboxylic Acids as Versatile Building Blocks for Hydrothermal Design of Coordination Polymers

Selected recent examples of coordination polymers (CPs) or metal-organic frameworks (MOFs) constructed from different multifunctional carboxylic acids with phenyl-pyridine or biphenyl cores have been discussed. Despite being still little explored in crystal engineering research, such types of semi-rigid, thermally stable, multifunctional and versatile carboxylic acid building blocks have become very promising toward the hydrothermal synthesis of metal-organic architectures possessing distinct structural features, topologies, and functional properties. Thus, the main aim of this mini-review has been to motivate further research toward the synthesis and application of coordination polymers assembled from polycarboxylic acids with phenyl-pyridine or biphenyl cores. The importance of different reaction parameters and hydrothermal conditions on the generation and structural types of CPs or MOFs has also been highlighted. The influence of the type of main di- or tricarboxylate ligand, nature of metal node, stoichiometry and molar ratio of reagents, temperature, and presence of auxiliary ligands or templates has been showcased. Selected examples of highly porous or luminescent CPs, compounds with unusual magnetic properties, and frameworks for selective sensing applications have been described.

M-Carboranylphosphinate as Versatile Building Blocks To Design all Inorganic Coordination Polymers.

The first examples of coordination polymers of manganese(II) and a nickel(II) complex with a purely inorganic carboranylphosphinate ligand are reported, together with its exhaustive characterization. X-ray analysis revealed 1D polymeric chains with carboranylphosphinate ligands bridging two manganese(II) centers. The reactivity of polymer 1 with water and Lewis bases has also been studied.

Structures and applications of metal–organic frameworks featuring metal clusters

Metal–organic frameworks (MOFs), self-assembled from metal ions or metal clusters with organic ligands, are well known for their intriguing structure, permanent porosity, and tunable properties and have shown great prospect for various applications. In the present review, we mainly highlight recent significant examples of metal clusters in our team and provide a comprehensive review on the structure of metal cluster-based MOFs and their applications including for sensing metal ions, small molecules and gases, nitroaromatics and explosives, as well as many other applications. We classified two different coordination polymers: (i) homometallic coordination polymers (examples of coordination polymers with single and mixed types of secondary building units) and (ii) heterometallic coordination polymers (examples of coordination polymers based on metal–oxygen clusters and W–Cu–S clusters).

ChemInform Abstract: Water‐Induced Reversible SCSC or Solid‐State Structural Transformation in Coordination Polymers

AbstractReview: 58 refs.

Two Coordination Polymers Constructed from 5‐(4‐Pyridyl)‐1H‐tetrazole Ligands with Different Organic Carboxylates: Structure and Luminescence Properties

AbstractTwo coordination polymers (CPs), namely, [Cu(Hptz)2(Hhba)2]n (1) [Hptz = 5‐(4‐pyridyl)‐1H‐tetrazole, H2hba = 2‐hydroxybenzoic acid] and [Zn3(ptz)2(hpa)2]n (2) (H2hpa = 2‐hydroxy‐2‐phenylacetic acid), were synthesized by solvothermal reactions. Both complexes were characterized by elemental analysis, infrared spectroscopy, powder X‐ray diffraction, thermogravimetric analysis, and single‐crystal X‐ray diffraction analysis. Compound 1 exhibits a 2D (4,4) network, where each layer connects to four adjacent layers to construct a 3D supramolecular framework. Compound 2 has a 3D framework structure composed of 1D SUBs, which are formed by both carboxyl and tetrazole groups. The complexes represent two rare examples of CPs constructed from Hptz and organic carboxyl acid ligands. Complex 2 exhibits intense, red‐shifted emissions in the visible region at room temperature.

Construction of Two New Mixed‐ligand Coordination Polymers based on 2,2′‐Dimethylbiphenyl‐4,4′‐dicarboxylic Acid

AbstractTwo mixed‐ligand coordination polymers (CPs) based on a biphenyl‐based dicarboxylate ligand and 4,4′‐bipyridine or imidazole co‐ligand, namely, [Co(DMBDA)(bpy)]n (1) (H2DMBDA = 2,2′‐dimethylbiphenyl‐4,4′‐dicarboxylic acid, bpy = 4,4′‐bipyridine) and [Zn(DMBDA)(Im)]n (2) (Im = imidazole), were obtained under hydrothermal conditions. Compound 1 exhibits a new (4,6)‐connected network with a {44·610·8}{44·62} Schläfli symbol, whereas compound 2 shows a 4‐connected NbO‐type topology. These coordination polymers represent two rare examples of CPs based on 2,2′‐dimethylbiphenyl‐4,4′‐dicarboxylic acid. The solid‐state luminescent behaviors of the novel CPs were also investigated at room temperature.

Lanthanide coordination polymers with pyridyl-N-oxide or carboxylate functionalised host ligands

The first examples of coordination polymers of hard-donor functionalised cyclotriveratrylene ligands with the lanthanide(III) cations are reported, these include 1D 3-connected ladder structures and a 2D decorated kagome dual.

ChemInform Abstract: Coordination Polymers Constructed from Oligonuclear Nodes

AbstractReview: 44 refs.

Coordination Polymers Constructed from Oligonuclear Nodes

The node-and-spacer approach is widely employed in crystal engineering to construct coordination polymers. It consists of self-assembly processes involving mononuclear cationic species and exo-dentate ligands. We enlarged this strategy using preformed homo- and heterometallic complexes as nodes. The presence of two or more metal ions within a node leads to novel network topologies, as well as to new properties, arising from the intra- and internode interactions. This paper reviews some representative examples of coordination polymers obtained in our laboratory and constructed from: i) binuclear alkoxo-bridged complexes; ii) heterometallic 3d-3d' and 3d-4f complexes.

Structures, Photoluminescence, and Photocatalytic Properties of Six New Metal−Organic Frameworks Based on Aromatic Polycarboxylate Acids and Rigid Imidazole-Based Synthons

Six metal−organic coordination polymers, [Cu(bdc)(bimb)]n (H2bdc = 1,4-benzenedicarboxylate; bimb = 4,4′-bis(1-imidazolyl)biphenyl) (1), [Cu3(btc)2(bimb)2·(H2O)3]n (H3btc = 1,3,5-benzenetricarboxylate) (2), [M3(btc)2(bimb)2·(H2O)4]n (M = Mn for 3, Co for 4, Cd for 5), and [Cd(btcH)(bimb)]n (6) were obtained under hydrothermal conditions and characterized structurally. The networks exhibit a variety of topologies: compound 1 exhibits a triply interpenetrating three-dimensional (3D) framework with a distorted primitive cubic (α-Po) single net; compounds 2−5 are isomorphic, which possess a trinodal 4-connected 3D framework; compound 6 has a two-dimensional (3,4)-connected framework. In addition, the thermal stabilities for 1−6 and the photoluminescence properties for 5 and 6 were examined. An anionic organic dye X3B was selected as a model pollutant in aqueous media to evaluate the photocatalytic effectiveness of isostructural compounds 3 and 4, and the results indicated compounds 3 and 4 represent rare examples of coordination polymers that exhibit high photocatalytic activity for dye degradation under UV light and show good stability toward photocatalysis. The difference in catalytic activity between 3 and 4 arises from the discrepancy in central metal ions of the two compounds.

Interpenetrating Metal−Organic Frameworks Assembled from Polypyridine Ligands and Cyanocuprate Catenations

Two three-dimensional coordination polymers, [(CuCN)3(4-pyBpy)]n (1) and [(CuCN)4(3-pyBpy)]n (2), as rare examples of coordination polymers of nonchelating quaterpyridines, demonstrating 4- and 2-fold interpenetrations, respectively, were isolated from solvothermal reactions of 2,6-bis(4-pyridyl)-4,4′-bipyridine (4-pyBpy) and 2,6-bis(3-pyridyl)-4,4′-biyridine (3-pyBpy) with CuCN in DMF and were structurally characterized.

Synthesis, Structures, and Magnetic Properties of Metal-Coordination Polymers with Benzenepentacarboxylate Linkers

Three hybrid organic-inorganic coordination polymers with benzenepentacarboxylate (BPCA) linkers, [Co3(C6H(COO)5)(OH)(H2O)3] (1-Co), [Zn3(C6H(COO)5)(OH)(H2O)3] (2-Zn), and [Co5(C6H(COO)5)2(H2O)12].(H2O)12 (3-Co), were synthesized hydrothermally and were characterized structurally and magnetically. 1-Co and 2-Zn are isostructural [C2/c; Z=8; 1-Co, a=19.5350(6) A, b=10.4494(4) A, and c=13.2353(5) A, beta=97.2768(8) degrees; 2-Zn, a=19.5418(9) A, b=10.3220(10) A, and c=13.4660(10) A, beta=98.455(10) degrees] with three-dimensional structures that contain [M6] secondary building units bridged by BPCA ligands. A different cobalt-based compound, 3-Co, forms at lower pH and lower reaction temperature. Its structure [P21/c; Z=2; a=12.6162(2) A, b=11.3768(2) A, and c=15.3401(3) A, beta=91.539(1) degrees] is a more loosely packed framework with free (noncoordinated) carboxylic groups pointing at water-filled cavities in the framework. The magnetic phase diagram of 1-Co established through detailed magnetic measurements shows a metamagnetic transition below TN=3.8 K. The less-packed compound 3-Co, on the other hand, remains paramagnetic above 1.9 K. The three compounds are the first examples of coordination polymers with benzenepentacarboxylate linkers and fill the gap of coordination polymers involving benzenepolycarboxylate linkers of the general type C6H6-n(COOH)n, where n=2-6.

Novel Coordination Polymers Based on the Tetrathioterephthalate Dianion as the Bridging Ligand

The first examples of coordination polymers based on the tetrathioterephthalate dianion as the bridging ligand are reported. Two novel compounds, [M(S(2)CC(6)H(4)CS(2))(DMF)(2)](DMF) (M = Zn, Mn; DMF = dimethylformamide), have been synthesized, and their structural and optical properties were investigated.

Ligand Concentration Controlled Supramolecular Isomerism in Two CuSCN Based Coordination Polymers with in Situ Synthesized 4,4‘-Dipyridylsulfide as a Co-Ligand

Reactions of CuCl2, 4-pyridylthiol, and NH4SCN in mixed acetonitrile and water solutions at 140 °C and 96 h led to two polymorphs of CuSCN coordination polymers with stoichiometry [Cu2(SCN)2(dps)]∞ (dps = 4,4‘-dipyridyl sulfide). The dps ligand is generated in situ via desulfation coupling of 4-pyridinethiol during the hydrothermal treatment. Polymorph 1 is a two-dimensional (2D) tubular sheet constructed by an unprecedented [CuSCN]∞ column and dps ligand. The [CuSCN]∞ column can be described as two zigzag chains arranged with approximate C2v symmetry, one chain being connected to the other by Cu−S contacts. An alternative description of the [CuSCN]∞ column is the stacking of [CuSCN]2 dimers, alternately rotated by 90° and linked by Cu−N contacts. Polymorph 2 is a 2D planar sheet constructed by [Cu(SCN)]∞ staircase chains and dps ligands. The [CuSCN]∞ staircase can be viewed as an alternating fusion of four-membered Cu−S−Cu−S rings and eight-membered Cu−S−C−N−Cu−S−C−N rings. The two polymorphs are very rare examples of coordination polymers that exhibit a similar local coordination geometry of metal and the same topology but different CuSCN structural motifs. Interestingly, 1 and 2 show quite different photoluminescent properties: the former has emission maxima at 538 nm assigned to a ligand-centered excited state, while the latter shows emission maxima at 636 nm tentatively attributed to both ligand-to-metal and metal-centered transitions.

Channel-containing structures generated from linear coordination polymer chains containing [formula omitted]-bidentate ligands and Cu–Cu dimetal units

Four new one-dimensional coordination polymers containing the dimetal cluster Cu 2(OAc) 4 have been synthesized by reacting Cu(OAc) 2 ⋅ H 2O with two different N , N ′ -bidentate ligands. Reaction of the flexible ligand, 1,2-bis(4-pyridyl)ethane ( L 1), with the copper starting material produced two, co-crystallizing coordination polymers: catena-Poly[Cu 2(OAc) 4( L 1)] ⋅ 2H 2O ( 1) and catena-Poly[Cu 2(OAc) 4( L 1)]. In the solid state, 1 (monoclinic, C2/c, a = 24.9471 ( 17 ) Å , b = 13.3539 ( 9 ) Å , c = 8.8050 ( 6 ) Å , β = 93.6480 ( 10 ) ° , V = 2927.4 ( 3 ) Å 3 , Z = 4 ) features linear chains which are organized into layers. These layers stack along the crystallographic c-axis forming small hexagonal channels occupied by the solvent of crystallization. Compound 2 (triclinic, P-1, a = 7.6263 ( 6 ) Å , b = 8.5283 ( 6 ) Å , c = 9.8633 ( 6 ) Å , α = 74.1070 ( 10 ) ° , β = 68.2160 ( 10 ) ° , γ = 74.0090 ( 10 ) ° , V = 561.96 ( 7 ) Å 3 , Z = 1 ) also features linear chains of the coordination polymer, but differs from 1 in that the chains are packed so as to leave no significant channels. Reaction of the rigid ligand, 1,4-bis(4-pyridyl)buta-1,3-diyne ( L 2), with the copper starting material also afforded two co-crystallizing coordination polymers: catena-Poly[Cu 2(OAc) 4( L 2)] ( 3) and catena-Poly[Cu 2(OAc) 4( L 2)] ⋅ solvents ( 4). 3 (monoclinic, P2 1/m, a = 9.8065 ( 9 ) Å , b = 12.3793 ( 11 ) Å , c = 9.9408 ( 9 ) Å , β = 107.6009 ( 17 ) ° , V = 1150.29 ( 18 ) Å 3 , Z = 2 ), like 2, features linear chains and contains no significant solvent accessible void space. 4 (monoclinic, C2/c, a = 28.9810 ( 16 ) Å , b = 12.9301 ( 7 ) Å , c = 8.6954 ( 5 ) Å , β = 98.8010 ( 10 ) ° , V = 3220.0 ( 3 ) Å 3 , Z = 4 ) also consists of linear chains of the coordination polymer. However, the overall topology of 4 is identical to that of 1, with the generated hexagonal channels containing crystallographically unidentifiable solvents of crystallization. Compounds 1 and 2 and compounds 3 and 4 are pairs of polymorphic coordination polymers neglecting the solvents of crystallization in 1 and 4. The compounds, which represent four new examples of coordination polymers containing dimetal units, have been characterized by IR, elemental analysis, and thermogravimetric analysis in addition to X-ray crystallography.

Structural diversity in two-dimensional coordination polymers constructed from simple building-blocks; a rare example of coordination polymer polymorphs structurally characterised from multiple crystals

A family of two-dimensional coordination polymers formed from the reaction of Cd(NO(3))(2) with pyrazine or pyrimidine is reported, including rare examples of polymorphic coordination polymers which crystallise as multiple crystals. Six coordination polymers have been structurally characterised, four for pyrazine and two for pyrimidine-based systems, all of which form two-dimensional arrays utilising pyrazine/pyrimidine bridging, in some instances in combination with nitrate bridging. The compounds form either 4(4) grids (1,3,4,5), or in one instance, a 6(3) herringbone sheet structure (2). In the case of 3, two polymorphs have been identified, 3a and 3b, in which the three-dimensional arrangements of the coordination polymers differ only in the relative ordering of adjacent two-dimensional sheets. It was found that these two polymorphs crystallise in a simultaneous fashion such that each crystal studied was found to contain regions of both polymorphs and was believed to be a multiple crystal. Assessment of the phase purity of the product from the reaction of Cd(NO(3))(2) with either pyrazine or pyrimidine indicates that compounds 1and 5 are not formed when the products are formed by rapid precipitation but only when using slow-diffusion methods. It is also apparent that in almost all instances more than one product is formed from a given reaction thereby illustrating the complexity of coordination polymer formation even when using simple building-blocks. For the crystal engineer this complexity is perhaps best illustrated by the simultaneous formation of 3a and 3b where no chemical interactions differentiate the two polymorphs, presenting a seemingly insurmountable complexity in the engineering of these systems.