Supramolecular porous frameworks of two Ni(II) coordination polymers with varying structures, porosities, and magnetic properties

Zhou, Yue; Zhang, Yang-Lu; Zhang, Qian; Yang, Shun-Yi; Wei, Xian‐Wen; Tian, Zhengfang; Shao, Dong

doi:10.1016/j.poly.2022.116078

Cited by 12 publications

(2 citation statements)

References 60 publications

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“…For the octahedral hexaaqua cations, the average Zn–O and Ni–O bond lengths are in the range of 2.049–2.067 Å and 2.087–2.090 Å, respectively (Tables S1 and S2, SI). These bond distances reveal the diamagnetic low spin state of the Zn 2+ ion in 1 while the paramagnetic high spin state of the Ni 2+ ion in 2 . , The most striking structural characteristic for both the materials is their complementary and extensive hydrogen-bonding interactions within the complexes (Figure b,c). Around the [M(H 2 O) 6 ] 2+ (M = Zn for 1 , Ni for 2 ) units, there are twelve O–H···O contacts between the coordination water molecules and the six surrounding carboxylates and two coordinated water molecules from adjoining [M(H 2 O) 6 ] 2+ cations (Figure a).…”

Section: Results and Discussionmentioning

confidence: 94%

Metalo Hydrogen-Bonded Organic Frameworks Self-Assembled by Charge-Assisted Synthons for Ultrahigh Proton Conduction

Shao

Shi

Liu

et al. 2023

Crystal Growth & Design

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Hydrogen-bonded organic frameworks (HOFs) have been well recognized for constructing solid-state proton-conducting materials due to their inherent well-defined H-bonded networks; however, the design and synthesis of stable HOFs showing ultrahigh superprotonic conductivity is still challenging. Herein, we reported a facile and effective synthetic strategy to build high proton-conducting metalo hydrogenbonded organic−inorganic frameworks (MHOFs) through charge-assisted inorganic and organic synthons. The supramolecular self-assembly of simple metal salts and tetracarboxylic acids gives rise to two hydrogen-bonded frameworks, [M(H 2 O) 6 ][H 2 tcba] (M = Zn 2+ , Ni 2+ ; H 4 tcba = 1,2,4,5-benzenetetracarboxylic acid). X-ray crystallography and gas adsorption confirmed the nonporous nature of the HOIFs. Variable-temperature single-crystal and powder X-ray diffraction experiments reveal the thermal and water stability of the supramolecular structures sustained by exclusively charge-assisted hydrogen bonds. The high density of carboxylic acid groups and coordinated water molecules provide ample protons and hydrophilic environments for efficient proton transport; therefore, variable-temperature and -humidity electrochemical impedance spectroscopy revealed that MHOFs are good supramolecular proton conductors with conductivities up to 1.1 × 10 −2 and 2.1 × 10 −2 S•cm −1 for 1 and 2, respectively, at 80 °C under 97% RH. Our study demonstrates great potential of charge-assisted inorganic and organic synthons in the design and construction of proton-conducting HOIFs.

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Section: Results and Discussionmentioning

confidence: 94%

Metalo Hydrogen-Bonded Organic Frameworks Self-Assembled by Charge-Assisted Synthons for Ultrahigh Proton Conduction

Shao

Shi

Liu

et al. 2023

Crystal Growth & Design

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“…These interactions may significantly affect the magnetic properties of the system compared to identical single metallic units. Molecular materials can be multifunctional compounds, such as magnets, which combine magnetic ordering with chirality, conductivity and porosity, and even with two of such additional properties [ 1 , 13 , 14 , 15 , 16 , 17 ].…”

Section: Introductionmentioning

confidence: 99%

Structural Diversity, XAS and Magnetism of Copper(II)-Nickel(II) Heterometallic Complexes Based on the [Ni(NCS)6]4− Unit

et al. 2023

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The new heterometallic compounds, [{Cu(pn)2}2Ni(NCS)6]n·2nH2O (1), [{CuII(trien)}2Ni(NCS)6CuI(NCS)]n (2) and [Cu(tren)(NCS)]4[Ni(NCS)6] (3) (pn = 1,2-diaminopropane, trien = triethylenetetramine and tren = tris(2-aminoethylo)amine), were obtained and characterized by X-ray analysis, IR spectra, XAS and magnetic measurements. Compounds 1, 2 and 3 show the structural diversity of 2D, 1D and 0D compounds, respectively. Depending on the polyamine used, different coordination polyhedron for Cu(II) was found, i.e., distorted octahedral (1), square pyramidal (2) and trigonal bipyramidal (3), whereas coordination polyhedron for nickel(II) was always octahedral. It provides an approach for tailoring magnetic properties by proper selection of auxiliary ligands determining the topology. In 1, thiocyanate ligands form bridges between the copper and nickel ions, creating 2D layers of sql topology with weak ferromagnetic interactions. Compound 2 is a mixed-valence copper coordination polymer and shows the rare ladder topology of 1D chains decorated with [CuII(tren)]2+ antennas as the side chains attached to nickel(II). The ladder rails are formed by alternately arranged Ni(II) and Cu(I) ions connected by N2 thiocyanate anions and rungs made by N3 thiocyanate. For the Cu(I) ions, the tetrahedral thiocyanate environment mixed N/S donor atoms was found, confirming significant coordination spheres rearrangement occurring at the copper precursor together with the reduction in some Cu(II) to Cu(I). Such topology enables significant simplification of the magnetic properties modeling by assuming magnetic coupling inside {NiIICuII2} trinuclear units separated by diamagnetic [Cu(NCS)(SCN)3]3− linkers. Compound 3 shows three discrete mononuclear units connected by N-H…N and N-H…S hydrogen bonds. Analysis of XAS proves that the average ligand character and the covalency of the unoccupied metal d-based orbitals for copper(II) and nickel(II) increase in the following order: 1 ® 2 ® 3. In 1 and 2, a weak ferromagnetic coupling between copper(II) and nickel(II) was found, but in 2, additional and stronger antiferromagnetic interaction between copper(II) ions prevailed. Compound 3, as an ionic pair, shows, as expected, a spin-only magnetic moment.

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Sensitive and rapid sensing of dimetridazole in food and environmental samples using a water-stable luminescent zwitterionic Cd(Ⅱ) metal-organic framework

Wang

Dong

Zhao

et al. 2023

Journal of Molecular Structure

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Supramolecular porous frameworks of two Ni(II) coordination polymers with varying structures, porosities, and magnetic properties

Cited by 12 publications

References 60 publications

Metalo Hydrogen-Bonded Organic Frameworks Self-Assembled by Charge-Assisted Synthons for Ultrahigh Proton Conduction

Metalo Hydrogen-Bonded Organic Frameworks Self-Assembled by Charge-Assisted Synthons for Ultrahigh Proton Conduction

Structural Diversity, XAS and Magnetism of Copper(II)-Nickel(II) Heterometallic Complexes Based on the [Ni(NCS)6]4− Unit

Sensitive and rapid sensing of dimetridazole in food and environmental samples using a water-stable luminescent zwitterionic Cd(Ⅱ) metal-organic framework

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