scholarly journals Pyrene Carboxylate Ligand Based Coordination Polymers for Microwave-Assisted Solvent-Free Cyanosilylation of Aldehydes

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.

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.


2018 ◽  
Vol 74 (2) ◽  
pp. 218-223 ◽  
Author(s):  
Ning-Ning Ji ◽  
Zhi-Qiang Shi ◽  
Hai-Liang Hu

The design and synthesis of coordination polymers with a self-penetrating architecture has attracted much interest not only due to their interesting structures but also due to their potential applications. 5,5′-Bis(pyridin-4-yl)-2,2′-bithiophene (bpbp), as a conjugated bithiophene ligand, can exhibit trans and cis conformations and this can lead to the construction of a self-penetrating architecture. In addition, the semi-rigid ancillary ligand 4,4′-oxybis(benzoic acid) (H2oba) can adopt different coordination modes, resulting in coordination polymers with high-dimensional skeletons. A new CdII coordination polymer based on mixed ligands, namely poly[diaquapentakis[μ-5,5′-bis(pyridin-4-yl)-2,2′-bithiophene-κ2 N:N′]bis(nitrato-κ2 O,O′)tetrakis(μ3-4,4′-oxydibenzoato)-κ10 O:O,O′:O′′,O′′′;κ6 O:O′:O′′-pentacadmium(II)], [Cd5(C14H14O5)4(NO3)2(C18H12N2S2)5(H2O)2] n , (I), has been synthesized under solvothermal conditions and characterized by single-crystal X-ray diffraction, IR spectroscopy and elemental analysis. Single-crystal X-ray diffraction indicates that there are three crystallographically independent CdII cations, three bpbp ligands, two deprotonated oba2− ligands, one nitrate ligand and one coordinated water molecule in the asymmetric unit. One CdII centre is seven-coordinated, exhibiting a distorted {CdN2O5} pentagonal bipyramidal geometry, while the other two Cd centres are both six-coordinated, showing slightly distorted {CdN2O4} octahedral geometries. The most interesting feature is the co-existence of trans and cis conformations in a single net, allowing structural interpenetration via self-threading and yet the expected self-penetrating structure was obtained. Topological analysis shows that the whole three-dimensional framework can be classified as a 3-nodal (4,6,6)-c net with Schläfli symbol {613.82}2{66}, which is a new topology. Furthermore, the luminescence properties of (I) were examined in the solid state at room temperature.


2021 ◽  
Vol 0 (0) ◽  
Author(s):  
Long Tang ◽  
JiaoWei Nan ◽  
YuFei Zheng ◽  
JiJiang Wang ◽  
XiangYang Hou ◽  
...  

Abstract A new cobalt-based coordination polymer (CP), [Co(Htatb)(1,4-bib)]·DMF (1), has been hydrothermally synthesized from CoCl2 ·6H2O, 4,4′,4′′-s-triazine-2,4,6-tribenzoic acid (H3tatb), and 1,4-bis(1-imidazoly)benzene (1,4-bib). The product has been characterized by IR spectroscopy, elemental and thermogravimetric analysis, and single-crystal X-ray diffraction. In compound 1, the Htatb ligand links three CoII ions resulting in a double-strand chain structure, further bridged through the 1,4-bib ligands to generate a 2D structure with channels. The fluorescence and cyclovoltammetry characteristics of compound 1 have also been investigated.


CrystEngComm ◽  
2018 ◽  
Vol 20 (38) ◽  
pp. 5677-5687 ◽  
Author(s):  
Andrew R. LaDuca ◽  
Robert L. LaDuca

Hydrothermal reaction of cadmium nitrate, bis(4-pyridylmethyl)piperazine (4-bpmp), and a variety of cyclohexyldicarboxylate ligands generated three new coordination polymer solids that were structurally characterized via single-crystal X-ray diffraction.


Materials ◽  
2021 ◽  
Vol 14 (7) ◽  
pp. 1786
Author(s):  
Carla Queirós ◽  
Chen Sun ◽  
Ana M. G. Silva ◽  
Baltazar de Castro ◽  
Juan Cabanillas-Gonzalez ◽  
...  

The development of straightforward reproducible methods for the preparation of new photoluminescent coordination polymers (CPs) is an important goal in luminescence and chemical sensing fields. Isophthalic acid derivatives have been reported for a wide range of applications, and in addition to their relatively low cost, have encouraged its use in the preparation of novel lanthanide-based coordination polymers (LnCPs). Considering that the photoluminescent properties of these CPs are highly dependent on the existence of water molecules in the crystal structure, our research efforts are now focused on the preparation of CP with the lowest water content possible, while considering a green chemistry approach. One- and two-dimensional (1D and 2D) LnCPs were prepared from 5-aminoisophthalic acid and Sm3+/Tb3+ using hydrothermal and/or microwave-assisted synthesis. The unprecedented LnCPs were characterized by single-crystal X-ray diffraction (SCRXD), powder X-ray diffraction (PXRD), Fourier transform infrared (FT-IR) spectroscopy and scanning electron microscopy (SEM), and their photoluminescence (PL) properties were studied in the solid state, at room temperature, using the CPs as powders and encapsulated in poly(methyl methacrylate (PMMA) films, envisaging the potential preparation of devices for sensing. The materials revealed interesting PL properties that depend on the dimensionality, metal ion, co-ligand used and water content.


2013 ◽  
Vol 803 ◽  
pp. 80-84
Author(s):  
Yu Qi Liu ◽  
Yong Yang ◽  
Rui Yang ◽  
Xiao Jun Xu

A novel metalorganic coordination polymer, namely [Co3(bpd)5.5(NCS)6(NH3)]n2H2O (1) (bpd=1,4-bis (4-pyridyl)-2,3-diaza-1,3-butadiene), has been synthesized and characterized by elemental analyses, infrared spectroscopy, and single-crystal X-ray diffraction. Compound 1 presents 2D[3,4,-connected 3-nodal net with the point symbol (4268210)(4462)(8210). In addition, four identical 2D single nets is interlocked with each other in parallel, thus directly leading to the formation of a polycatenated layer (2D2D).


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)


2018 ◽  
Vol 74 (11) ◽  
pp. 1434-1439
Author(s):  
Hong-Tao Zhang ◽  
Xiao-Long Wang

In recent years, much initial interest and enthusiasm has focused on the self-assembly of coordination polymers due to the aesthetics of their crystalline architectures and their potential applications as new functional materials. As part of an exploration of chiral coordination polymers, a new twofold interpenetrated two-dimensional (2D) coordination polymer, namely, poly[[tetraaquabis[μ3-(2R,2′R)-2,2′-(benzene-1,4-dicarboxamido)dipropionato-κ5 O,O′:O′′,O′′′:O′′]dicadmium(II)] trihydrate], {[Cd2(C14H14N2O6)2(H2O)4]·3H2O} n , has been synthesized by the reaction of Cd(CH3COO)2·2H2O with the designed ligand (2R,2′R)-2,2′-(benzene-1,4-dicarboxamido)dipropionic acid (H2 L). The compound has been structurally characterized by elemental analysis, IR spectroscopy, powder X-ray diffraction and single-crystal X-ray diffraction analysis. In the crystal structure, each CdII cation binds to three carboxylate groups from two crystallographically independent L 2− dianions. Four carboxylate groups link two crystallographically independent cadmium cations into a 4,4-connected secondary building unit (SBU). The resulting SBUs are extended into a two-dimensional folding sheet via the terephthalamide moiety of the ligand as a spacer, which can be simplified as a (4,4)-connected 4,4L15 net with the point symbol (3.53.62)(32.52.62). In the lattice, two independent folding sheets interpenetrate each other to yield a double-sheet layer. The resulting 2D layers pack in parallel arrays through intermolecular hydrogen bonds and interlayer π–π interactions. The thermal stability and photoluminescence properties of the title compound have been investigated and it exhibits an enhanced fluorescence emission and a longer lifetime compared with free H2 L.


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