Eindimensionale Kupfer(II)-Koordinationspolymere: Kristall-Engineering durch variable Verknüpfungsmuster [1] / One Dimensional Copper(II) Coordination Polymers: Crystal Engineering through Variable Types of Linkage [1]

1997 ◽  
Vol 52 (1) ◽  
pp. 125-134 ◽  
Author(s):  
Rolf W. Saalfrank ◽  
Roland Harbig ◽  
Oliver Struck ◽  
Frank Hampel ◽  
Eva Maria Peters ◽  
...  

Reaction of a methanolic copper(II) acetate solution with tetrazolyl enol derivatives 2a or 2b leads to the formation of the corresponding lD-coordination polymer 1∞[CuL2] 3a and pseudo 1D-coordination polymer [CuL2]2 3b, respectively. On the contrary, reaction of 2c with methanolic copper(II) acetate solution yields OH-bridged 1D-coordination polymer 1∞[CuL2(MeOH)2 3c. Single-crystal X-ray diffraction of the supramolecular species 3 established unequivocally the structures of the stairlike coordination compounds. Reaction of a methanolic copper(II) acetate solution with amidotetrazole derivative 6 leads to the formation of the lD-coordination polymer 1∞ [CuL2] 7. The structure of 7 has been established by X-ray structure analysis

Molecules ◽  
2021 ◽  
Vol 26 (17) ◽  
pp. 5400
Author(s):  
Roman D. Marchenko ◽  
Taisiya S. Sukhikh ◽  
Alexey A. Ryadun ◽  
Andrei S. Potapov

Coordination polymers with a new rigid ligand 1,3-bis(1,2,4-triazol-1-yl)adamantane (L) were prepared by its reaction with cadmium(II) or silver(I) nitrates. Crystal structure of the coordination polymers was determined using single-crystal X-ray diffraction analysis. Silver formed two-dimensional coordination polymer [Ag(L)NO3]n, in which metal ions are linked by 1,3-bis(1,2,4-triazol-1-yl)adamantane ligands, coordinated by nitrogen atoms at positions 2 and 4 of 1,2,4-triazole rings. Layers of the coordination polymer consist of rare 18- and 30-membered {Ag2L2} and {Ag4L4} metallocycles. Cadmium(II) nitrate formed two kinds of one-dimensional coordination polymers depending on the metal-to-ligand ratio used in the synthesis. Coordination polymer [Cd(L)2(NO3)2]n was obtained in case of a 1:2 M:L ratio, while for M:L = 2:1 product {[Cd(L)(NO3)2(CH3OH)]·0.5CH3OH}n was isolated. All coordination polymers demonstrated ligand-centered emission near 450 nm upon excitation at 370 nm.


2018 ◽  
Vol 74 (6) ◽  
pp. 734-741 ◽  
Author(s):  
Olga Drath ◽  
Robert W. Gable ◽  
Colette Boskovic

The combination of cobalt, 3,5-di-tert-butyldioxolene (3,5-dbdiox) and 1-hydroxy-1,2,4,5-tetrakis(pyridin-4-yl)cyclohexane (tpch) yields two coordination polymers with different connectivities, i.e. a one-dimensional zigzag chain and a two-dimensional sheet. Poly[[bis(3,5-di-tert-butylbenzene-1,2-diolato)bis(1,5-di-tert-butyl-4-oxocyclohexa-2,5-dien-1-yl-3-olato)[μ4-1-hydroxy-1,2,4,5-tetrakis(pyridin-4-yl)cyclohexane]cobalt(III)]–ethanol–water 1/7/5], {[Co2(C14H20O2)4(C26H24N4O)]·7C2H5OH·5H2O} n or {[Co2(3,5-dbdiox)4(tpch)}·7EtOH·5H2O} n , is the second structurally characterized example of a two-dimensional coordination polymer based on linked {Co(3,5-dbdiox)2} units. Variable-temperature single-crystal X-ray diffraction studies suggest that catena-poly[[[(3,5-di-tert-butylbenzene-1,2-diolato)(1,5-di-tert-butyl-4-oxocyclohexa-2,5-dien-1-yl-3-olato)cobalt(III)]-μ-1-hydroxy-1,2,4,5-tetrakis(pyridin-4-yl)cyclohexane]–ethanol–water (1/1/5)], {[Co(C14H20O2)2(C26H24N4O)]·C2H5OH·5H2O} n or {[Co(3,5-dbdiox)2(tpch)]·EtOH·5H2O} n , undergoes a temperature-induced valence tautomeric interconversion.


Molecules ◽  
2021 ◽  
Vol 26 (4) ◽  
pp. 1101
Author(s):  
Anirban Karmakar ◽  
Anup Paul ◽  
Elia Pantanetti Sabatini ◽  
M. Fátima C. Guedes da Silva ◽  
Armando J. L. Pombeiro

The new coordination polymers (CPs) [Zn(μ-1κO1:1κO2-L)(H2O)2]n·n(H2O) (1) and [Cd(μ4-1κO1O2:2κN:3,4κO3-L)(H2O)]n·n(H2O) (2) are reported, being prepared by the solvothermal reactions of 5-{(pyren-4-ylmethyl)amino}isophthalic acid (H2L) with Zn(NO3)2.6H2O or Cd(NO3)2.4H2O, respectively. They were synthesized in a basic ethanolic medium or a DMF:H2O mixture, respectively. These compounds were characterized by single-crystal X-ray diffraction, FTIR spectroscopy, thermogravimetric and elemental analysis. The single-crystal X-ray diffraction analysis revealed that compound 1 is a one dimensional linear coordination polymer, whereas 2 presents a two dimensional network. In both compounds, the coordinating ligand (L2−) is twisted due to the rotation of the pyrene ring around the CH2-NH bond. In compound 1, the Zn(II) metal ion has a tetrahedral geometry, whereas, in 2, the dinuclear [Cd2(COO)2] moiety acts as a secondary building unit and the Cd(II) ion possesses a distorted octahedral geometry. Recently, several CPs have been explored for the cyanosilylation reaction under conventional conditions, but microwave-assisted cyanosilylation of aldehydes catalyzed by CPs has not yet been well studied. Thus, we have tested the solvent-free microwave-assisted cyanosilylation reactions of different aldehydes, with trimethylsilyl cyanide, using our synthesized compounds, which behave as highly active heterogeneous catalysts. The coordination polymer 1 is more effective than 2, conceivably due to the higher Lewis acidity of the Zn(II) than the Cd(II) center and to a higher accessibility of the metal centers in the former framework. We have also checked the heterogeneity and recyclability of these coordination polymers, showing that they remain active at least after four recyclings.


Author(s):  
Ahmet Karadag ◽  
Hümeyra Pasaoglu ◽  
Gökhan Kastas ◽  
Orhan Büyükgüngör

AbstractThe cyano-bridged heteronuclear coordination polymer of zinc(II)/nickel(II) has been prepared by N-(2-hydroxyethyl)-ethylendiamine (hydet-en), alternatively named 2-(2-aminoethylamino)-ethanol and characterised by IR and thermal analysis. In the bimetallic complex, the decomposition of hydet-en ligands is seen to be endothermic whereas that of the cyano ligands is found to be exothermic. The crystal structure of the complex has been determined by single-crystal X-ray diffraction. The crystal structure of the zinc(II)-nickel(II) complex consists of a one-dimensional polymeric chain –Zn(hydet-en)


2019 ◽  
Vol 75 (11) ◽  
pp. 1475-1481 ◽  
Author(s):  
Wenlong Lan ◽  
Zhen Zhou ◽  
Jie Li ◽  
Yong Dou ◽  
Xiaoyun Hao ◽  
...  

A new cyanide-bridged FeIII–MnII heterobimetallic coordination polymer (CP), namely catena-poly[[[N,N′-(1,2-phenylene)bis(pyridine-2-carboxamidato)-κ4 N,N′,N′′,N′′′]iron(III)]-μ-cyanido-κ2 C:N-[bis(4,4′-bipyridine-κN)bis(methanol-κO)manganese(II)]-μ-cyanido-κ2 N:C], {[FeMn(C18H12N4O2)(CN)2(C10H8N2)2(CH3OH)2]ClO4} n , (1), was prepared by the self-assembly of the trans-dicyanidoiron(III)-containing building block [Fe(bpb)(CN)2]− [bpb2− = N,N′-(1,2-phenylene)bis(pyridine-2-carboxamidate)], [Mn(ClO4)2]·6H2O and 4,4′-bipyridine, and was structurally characterized by elemental analysis, IR spectroscopy, single-crystal X-ray crystallography and powder X-ray diffraction (PXRD). Single-crystal X-ray diffraction analysis shows that CP 1 possesses a cationic linear chain structure consisting of alternating cyanide-bridged Fe–Mn units, with free perchlorate as the charge-balancing anion, which can be further extended into a two-dimensional supramolecular sheet structure via inter-chain π–π interactions between the 4,4′-bipyridine ligands. Within the chain, each MnII ion is six-coordinated by an N6 unit and is involved in a slightly distorted octahedral coordination geometry. Investigation of the magnetic properties of 1 reveals an antiferromagnetic coupling between the cyanide-bridged FeIII and MnII ions. A best fit of the magnetic susceptibility based on the one-dimensional alternating chain model leads to the magnetic coupling constants J 1 = −1.35 and J 2 = −1.05 cm−1, and the antiferromagnetic coupling was further confirmed by spin Hamiltonian-based density functional theoretical (DFT) calculations.


2017 ◽  
Vol 41 (3) ◽  
pp. 1179-1185 ◽  
Author(s):  
N. N. Adarsh ◽  
Amarnath Chakraborty ◽  
Màrius Tarrés ◽  
Surjendu Dey ◽  
Fernando Novio ◽  
...  

A metallosupramolecular cage and a one-dimensional coordination polymer have been synthesized and structurally characterized by single crystal X-ray diffraction.


1996 ◽  
Vol 51 (3) ◽  
pp. 399-408 ◽  
Author(s):  
Rolf W. Saalfrank ◽  
Roland Harbig ◽  
Oliver Struck ◽  
Eva-Maria Peters ◽  
Hans Georg von Schnering

Abstract Reaction of a methanolic copper(II) acetate solution with tetrazolyl enol derivatives 2a (HL2) or 2b (HL3) leads to the formation of the corresponding 2D-coordination polymers 4 (∞2 [CuL22]) and 5 (∞2 [CuL23]), respectively. Single-crystal X-ray diffraction of the supramolecular species 4 and 5 established unequivocally the structures of the regioisomeric coordination polymers. On the contrary, reactions of 2c (HL4) with methanolic copper(II) acetate solution and 2b (HL3) with methanolic zinc(II) acetate solution yield mononuclear chelate complexes 11 ([CuL42]) and 12 ([ZnL23(MeOH)2]). The structures of 11 and 12 have been established by X-ray structure analysis.


2006 ◽  
Vol 59 (1) ◽  
pp. 40 ◽  
Author(s):  
Luís Cunha-Silva ◽  
Ruksanna Ahmad ◽  
Michaele J. Hardie

New crystalline coordination networks based on Ag(i) and N-bridging ligands — pyrazine (pyz), 4,4′-bipyridine (bpy), and 2,3-bis-(2-pyridyl)pyrazine (bppz) — incorporating carborane monoanions (CB11H12)− or [Co(C2B9H11)2]− were isolated and characterized using single crystal X-ray diffraction, microanalysis, and infrared spectroscopy. All the complexes with the bpy and bppz ligands reveal 1D coordination infinite chains involving the Ag(i) and the ligands, and layered extended structures with rows of carborane anions between the layers of chains. Interestingly, two polymorphs of the complex [Ag(bpy)(CH3CN)][Co(C2B9H11)2] were observed. The complex [Ag(pyz)(CH3CN)2][Co(C2B9H11)2] shows a 1D coordination polymer, while the pyz complex with the smaller carborane anion {[Ag(pyz)](CB11H12)} exhibits a 3D coordination network structure with four Ag···H−B interactions between the silver centre and carborane anions.


Molecules ◽  
2018 ◽  
Vol 24 (1) ◽  
pp. 6 ◽  
Author(s):  
Na Zhao ◽  
Yu Li ◽  
Jinzhong Gu ◽  
Tiago Fernandes ◽  
Marina Kirillova ◽  
...  

Two new copper(II) coordination compounds, namely a 1D coordination polymer [Cu(µ-cpna)(phen)(H2O)]n (1) and a discrete tetracopper(II) derivative [Cu(phen)2(H2O)]2[Cu2(µ-Hdppa)2(Hdppa)2] (2), were hydrothermally synthesized from copper(II) chloride as a metal source, 5-(4-carboxyphenoxy)nicotinic acid (H2cpna) or 5-(3,4-dicarboxylphenyl)picolinic acid (H3dppa) as a principal building block, and 1,10-phenanthroline (phen) as a crystallization mediator. Compounds 1 and 2 were isolated as air-stable microcrystalline solids and fully characterized by elemental and thermogravimetric analyses, IR spectroscopy, powder and single-crystal X-ray diffraction. In the solid state, the structure of 1 discloses the linear interdigitated 1D coordination polymer chains with the 2C1 topology. The crystal structure of an ionic derivative 2 shows that the mono- and dicopper(II) units are extended into the intricate 1D hydrogen-bonded chains with the SP 1-periodic net (4,4)(0,2) topology. Thermal stability and catalytic properties of 1 and 2 were also investigated. In fact, both Cu derivatives act as efficient homogeneous catalysts (catalyst precursors) for the mild oxidation of cycloalkanes by hydrogen peroxide to give the corresponding alcohols and ketones; the substrate scope and the effects of type and amount of acid promoter as well as bond-, regio-, and stereo-selectivity features were investigated.


2018 ◽  
Vol 73 (12) ◽  
pp. 1023-1028
Author(s):  
Ying Zhang ◽  
Ai-Quan Jia ◽  
Jing-Jing Zhang ◽  
Zhifeng Xin ◽  
Qian-Feng Zhang

AbstractTwo coordination polymers, [Mn2(μ-O2PPh2)2(η1-O2PPh2)2(η1-HOCH3)2(μ-bpe)2·CH3OH]n (1) and [Mn2(μ-O2PPh2)4(μ-bpe)2]n (2), were assembled in single-pot reactions from [Mn(CH3COO)2·4H2O], Ph2P(O)OK and trans-1,4-bis(4-pyridyl)ethene (bpe). The products were characterized by single-crystal X-ray diffraction, which revealed a one-dimensional metal-organic ladder type in 1 and a two-dimensional rectangular grid type in 2. Both 1 and 2 are constructed from six-coordinate Mn(II) nodes that adopt distorted octahedral (MnN4O2) environments; the adjacent nodes are connected by the μ-bpe linkers in 1 or μ-bpe and μ-O2PPh2 linkers in 2 to form different metal-organic networks. The catalytic property of complex 1 for selective thioether oxidation was also investigated in this work.


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