Cooperative metal–ligand influence on the formation of coordination polymers, and conducting and photophysical properties of Tl(i) β-oxodithioester complexes

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.

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Tuning the Photophysical Properties of Cyclometalated Ir(III) Complexes by a Trifluoroacetyl Group

Zeitschrift für Naturforschung B ◽

10.1515/znb-2012-0306 ◽

2012 ◽

Vol 67 (3) ◽

pp. 213-218 ◽

Cited By ~ 1

Author(s):

Bihai Tong ◽

Jiayan Qiang ◽

Qunbo Mei ◽

Hengshan Wang ◽

Qianfeng Zhang ◽

...

Keyword(s):

Single Crystal ◽

Electron Acceptor ◽

Photophysical Properties ◽

Red Shift ◽

Luminescence Spectra ◽

X Ray Diffraction ◽

X Ray ◽

Absorption And Luminescence Spectra ◽

Homo Lumo

Four cationic Ir(III) complexes, [Ir(dpq)2(bpy)]PF6 (1), [Ir(dpq)2(phen)]PF6 (2), [Ir(tfapq)2- (bpy)]PF6 (3), and [Ir(tfapq)2(phen)]PF6 (4) (dpqH = 2,4-diphenylquinoline, tfapqH = 2-(4ʹ-trifluoroacetylphenyl)- 4-phenylquinoline, bpy = 2,2ʹ-bipyridine, phen = 1,10-phenanthroline) have been synthesized and fully characterized. The structure of 4 was also confirmed by single-crystal X-ray diffraction. The electron-acceptor character of the trifluoroacetyl unit leads to a reduced HOMO-LUMO gap and consequently a red-shift of the UV/Vis absorption and luminescence spectra. The solvophobic character of the trifluoroacetyl unit gives rise to a molecule assembly in solution.

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Assembly of Three Lanthanide Coordination Polymers from 2-(4-Carboxybenzyloxy) Benzoic Acid Ligand: Synthesis, Structure, and Fluorescent Properties

Australian Journal of Chemistry ◽

10.1071/ch19314 ◽

2020 ◽

Vol 73 (1) ◽

pp. 16

Author(s):

Shu-Ju Wang ◽

Yi-Hui Jiang ◽

Han-Lin Wu ◽

Li-Xin You ◽

Gang Xiong ◽

...

Keyword(s):

Benzoic Acid ◽

Single Crystal ◽

Coordination Polymers ◽

Lanthanide Ions ◽

Solvothermal Reaction ◽

X Ray Diffraction ◽

Fluorescent Properties ◽

Single Crystal Diffraction ◽

X Ray ◽

1D Chain

Three new coordination polymers, {[Ln(cbb)(Hcbb)(DMF)·H2O]n, Ln=Sm (1), Eu (2), Tb(3), H2cbb=2-(4-carboxybenzyloxy) benzoic acid, DMF=N,N-dimethylformamide}, have been synthesised by a solvothermal reaction and structurally characterised by infrared spectroscopy, elemental analysis, thermogravimetry analysis, and X-ray single-crystal diffraction. The results of single-crystal X-ray diffraction indicate that the coordination polymers 1–3 are isostructural, belong to a triclinic system, space group P-1, and show 1D chain structures through the H2cbb ligands connecting adjacent lanthanide ions. In addition, the fluorescence properties of polymers 1–3 were also investigated.

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The Syntheses and Structures of Two New Zn(II) Complexes Based on 3-Nitrobenzoato Ligand

Advanced Materials Research ◽

10.4028/www.scientific.net/amr.807-809.2671 ◽

2013 ◽

Vol 807-809 ◽

pp. 2671-2674

Author(s):

Ying Bing Lu ◽

Fang Mei Jian ◽

Shuang Jin

Keyword(s):

Single Crystal ◽

Coordination Polymers ◽

Stacking Interactions ◽

X Ray Diffraction ◽

X Ray ◽

Face To Face ◽

Π Interactions ◽

Carboxylate Groups ◽

Supramolecular Chain ◽

Supramolecular Layer

Two new Zn (II) coordination polymers with 3-nitrobenzoato ligands have been prepared, and their structures have been characterized by single-crystal X-ray diffraction techniques. The structure of [Zn (3-nbz)2(μ-4,4'-bpy)]n(1) (3-nbz = 3-nitrobenzoato, 4,4'-bpy = 4,4'-bipyridine) shows 1-D chains originating from terminal 3-nbz ligands andμ-4,4'-bpy molecules. The chains are further connected through face-to-face π stacking interactions to genenate a 2-D supramolecular layer. In Zn (3-nbz)2(2,2'-bpy) (2) (2,2'-bpy = 2,2'-bipyridine), carboxylate groups exhibit chelated bidentate to give discrete mononuclear units, which are linked by face-to-face π-π and C-H···π interactions to produce a 1-D supramolecular chain.

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

Zeitschrift für Naturforschung B ◽

10.1515/znb-1997-0124 ◽

1997 ◽

Vol 52 (1) ◽

pp. 125-134 ◽

Cited By ~ 6

Author(s):

Rolf W. Saalfrank ◽

Roland Harbig ◽

Oliver Struck ◽

Frank Hampel ◽

Eva Maria Peters ◽

...

Keyword(s):

Coordination Polymer ◽

Single Crystal ◽

Coordination Polymers ◽

Crystal Engineering ◽

Coordination Compounds ◽

Acetate Solution ◽

X Ray Diffraction ◽

One Dimensional ◽

X Ray ◽

1D Coordination Polymer

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

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A Series of Enthalpy/Entropy-Driven Reversible Dissolution/Reorganization Equilibriums in the System of Cu(NO3)2–HL–GdX3–H2O (HL=5-methylpyrazine-2-carboxylic acid; X=Cl, Br, NO3, ClO4)

Australian Journal of Chemistry ◽

10.1071/ch13675 ◽

2014 ◽

Vol 67 (11) ◽

pp. 1679

Author(s):

Sheng Zhang ◽

Qi Yang ◽

Xiangyu Liu ◽

Gang Xie ◽

Qing Wei ◽

...

Keyword(s):

Thermal Stability ◽

Magnetic Property ◽

Structural Analysis ◽

Carboxylic Acid ◽

Single Crystal ◽

Coordination Polymers ◽

X Ray Diffraction ◽

X Ray ◽

2D Network ◽

Thermal Stability Of

Five coordination polymers, [Cu(L)2]n (1), {[Cu(L)(Cl)(H2O)]·H2O}2n (2), [KCu(L)(μ-Cl)2]n (3), [Cu(L)(Br)H2O]n (4), and {[Cu0.5(HL)(H2O)](NO3)·H2O}2n (5) (HL = 5-methylpyrazine-2-carboxylic acid) were obtained by reactions of a pyramidal CuII-containing ligand, {[Cu(L)2(H2O)]·3H2O}n (LCu), with Gd(ClO4)3·6H2O, GdCl3·6H2O, GdCl3·6H2O/KCl, GdBr3·6H2O, or Gd(NO3)3·6H2O in water. Structural analysis reveals that the structures of these compounds range from a 0D block to a 2D network with modification of the environment of the CuII ions compared with LCu. Interestingly, there occurred a series of reversible dissolution/reorganization equilibriums between the initial reactants and the final products 1–5, which were determined as enthalpy/entropy driven chemical equilibriums by single crystal X-ray diffraction and microcalorimetry. In addition, the thermal stability of 1–4 and the magnetic property of 2 are discussed.

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Coordination Polymers of Scandium(III) and Thiophenedicarboxylic Acid

Russian Journal of Coordination Chemistry ◽

10.1134/s1070328421090062 ◽

2021 ◽

Vol 47 (9) ◽

pp. 593-600

Author(s):

A. A. Lysova ◽

V. A. Dubskikh ◽

K. D. Abasheeva ◽

A. A. Vasileva ◽

D. G. Samsonenko ◽

...

Keyword(s):

Ir Spectroscopy ◽

Single Crystal ◽

Diffraction Analysis ◽

Coordination Polymers ◽

Elemental Analysis ◽

Metal Organic Frameworks ◽

X Ray Diffraction ◽

Phase Purity ◽

X Ray ◽

Metal Organic

Abstract Three new metal−organic frameworks based on scandium(III) cations and 2,5-thiophenedicarboxylic acid (H2Tdc) are synthesized: [Sc(Tdc)(OH)]·1.2DMF (I), [Sc(Tdc)(OH)]·2/3DMF (II), and (Me2NH2)[Sc3(Tdc)4(OH)2]·DMF (III) (DMF is N,N-dimethylformamide). The structures of the compounds are determined by single-crystal X-ray structure analysis (CIF file CCDC nos. 2067819 (I), 2067820 (II), and 2067821 (III)). The chemical and phase purity of compound I is proved by elemental analysis, thermogravimetry, X-ray diffraction analysis, and IR spectroscopy.

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Synthesis, Crystal Structure, and Luminescence of Cadmium(II) and Silver(I) Coordination Polymers Based on 1,3-Bis(1,2,4-triazol-1-yl)adamantane

Molecules ◽

10.3390/molecules26175400 ◽

2021 ◽

Vol 26 (17) ◽

pp. 5400

Author(s):

Roman D. Marchenko ◽

Taisiya S. Sukhikh ◽

Alexey A. Ryadun ◽

Andrei S. Potapov

Keyword(s):

Crystal Structure ◽

Coordination Polymer ◽

Metal Ions ◽

Single Crystal ◽

Diffraction Analysis ◽

Coordination Polymers ◽

Two Dimensional ◽

X Ray Diffraction ◽

One Dimensional ◽

X Ray

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.

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Zn/Ni and Zn/Pd Heterobimetallic Coordination Polymers with [SSC-N(CH2COO)2]3− Ligands

Crystals ◽

10.3390/cryst10060505 ◽

2020 ◽

Vol 10 (6) ◽

pp. 505 ◽

Cited By ~ 1

Author(s):

Phil Liebing ◽

Florian Oehler ◽

Juliane Witzorke

Keyword(s):

Coordination Polymers ◽

Thermal Analyses ◽

X Ray Diffraction ◽

Sequential Approach ◽

X Ray ◽

Ir And Nmr Spectroscopy ◽

Carboxylate Groups ◽

Polymeric Chains ◽

Polymeric Structures ◽

Mode A

In the construction of heterobimetallic coordination polymers based on dithiocarbamato–carboxylate (DTCC ligands), platinum as a thiophilic metal center can be replaced by the cheaper nickel or palladium. The compounds Zn[Pd(HL)2] and Zn2[M(L)2] (M = Ni, Pd; L = {SSC-N(CH2COO)2}3−) were prepared in a sequential approach starting from K3(L). The products were characterized by IR and NMR spectroscopy, thermal analyses, and single-crystal X-ray diffraction. The products decompose under nitrogen between 300 and 400 °C. Zn[Pd(HL)2] · 6H2O forms polymeric chains in the solid state, and the Zn2[M(L)2] · 14H2O (M = Ni, Pd) exhibit two-dimensional polymeric structures, each being isotypic with the respective Zn/Pt analogs. While the carboxylate groups in all these products are coordinated to zinc in a κO-monodentate mode, a structural variant of Zn2[Ni(L)2] having κO:κO′-briding carboxylate groups was also obtained. Exchange of the metal sites in the two Ni/Zn compounds was not observed, and these compounds are therefore diamagnetic.

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Syntheses, structures and magnetic properties of two CoII/NiII isostructural coordination polymers based on an asymmetric semirigid tricarboxylate ligand

Acta Crystallographica Section C Structural Chemistry ◽

10.1107/s2053229621012973 ◽

2022 ◽

Vol 78 (1) ◽

Author(s):

Shao-Dong Li ◽

Feng Su ◽

Cheng-Yong Zhou ◽

Qi-Long Hu ◽

Ya-Qi Li ◽

...

Keyword(s):

Magnetic Properties ◽

Ir Spectroscopy ◽

Single Crystal ◽

Coordination Polymers ◽

Two Dimensional ◽

X Ray Diffraction ◽

Magnetic Studies ◽

Thermogravimetric Analyses ◽

X Ray ◽

Elemental Analyses

Two new isostructural complexes, namely, poly[aqua[μ3-2-(4-carboxyphenoxy)terephthalato-κ3 O 1:O 4:O 4′](1,10-phenanthroline-κ2 N,N′)cobalt(II)], [Co(C15H8O7)(C12H8N2)(H2O)] n or [Co(μ3-Hcpota)(phen)(H2O)] n , I, and poly[aqua[μ3-2-(4-carboxyphenoxy)terephthalato-κ3 O 1:O 4:O 4′](1,10-phenanthroline-κ2 N,N′)nickel(II)], [Ni(C15H8O7)(C12H8N2)(H2O)] n or [Ni(μ3-Hcpota)(phen)(H2O)] n , II, have been synthesized by solvothermal reactions. Complexes I and II were fully characterized by IR spectroscopy, elemental analyses, thermogravimetric analyses, and powder and single-crystal X-ray diffraction. They both present two-dimensional structures based on [M 2(μ-COO)2]2+ (M = CoII or NiII) dinuclear metal units with a fes topology and a vertex symbol (4·82). Interestingly, the positions of the two dimeric metal motifs and the two partially deprotonated Hcpota2− ligands reproduce regular flying butterfly arrangements flipped upside down and sharing wings in the ab plane. Magnetic studies indicate antiferromagnetic interactions (J = −5.21 cm−1 for I and −11.53 cm−1 for II) in the dimeric units, with Co...Co and Ni...Ni distances of 4.397 (1) and 4.358 (1) Å, respectively, that are related to double syn–anti carboxylate bridges.

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