Anion exchange coupled with the reduction and dimerisation of a copper(<scp>ii</scp>) nitrate complex of tripyridyl dithioether via a single-crystal-to-single-crystal transformation

Lee, Hyeong-Hwan; Park, In‐Hyeok; Kim, Seulgi; Lee, Eunji; Ju, Huiyeong; Jung, Jong Hwa; Ikeda, Mari; Habata, Yoichi; Lee, Shim Sung

doi:10.1039/c6sc05341f

Cited by 15 publications

(4 citation statements)

References 62 publications

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“…Herein, we designed and attempted coordination variation of Cu(II) using flexible ligands that have terminal carboxylic functional groups with an expectation that such ligands would be guided more promptly by water solvent and coordinate differently under more or less hydrophilic solvent environments when approaching Cu(II), allowing modulation of the coordination structure depending on the solvent composition (Scheme ). Compared to rigid ligands, the flexible ligands are advantageous for our strategy as they are easier to respond to the coordination environment around the metals. − …”

Section: Introductionmentioning

confidence: 99%

Solvent-Effected Coordination Variation of Flexible Ligands to Cu(II) for the Formation of 1D and 2D Secondary Building Units for Metal–Organic Frameworks

2021

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Producing more than one structure from the same set of metal and ligand precursors will grant structural diversity in metal−organic framework (MOF) systems. One of the biggest obstacles of getting structural diversity for the late transition metals is that the coordination mode is pretty much fixed by nature. Herein, we show that two different coordination modes to Cu(II) are possible for flexible ligands containing hydrophilic terminal groups through solvent guidance. It is demonstrated that trans,trans-muconic acid (H 2 muco) ligands coordinate to Cu(II) to form Cu(II) muconate MOFs having a 1D chain structure and a 2D plane structure in water-rich and DMF-rich water−DMF mixed solvent systems, respectively. It is suggested that the interaction between ligands and solvent is responsible for the selective coordination. A similar result was observed from the attempts using the fumaric acid ligand. Our results provide a new direction to obtain diverse secondary building units for the construction of diverse MOFs.

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Section: Introductionmentioning

confidence: 99%

Solvent-Effected Coordination Variation of Flexible Ligands to Cu(II) for the Formation of 1D and 2D Secondary Building Units for Metal–Organic Frameworks

2021

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“…But with SMe 2 and PPh 3 , other tetranuclear partially opened isomeric forms are also known, such as the flowerbasket-shaped 2D polymer [(Me 2 S) 3 {Cu 4 (µ-I) 4 }] n or the open chair (open cubane tetramer) Cu 4 I 4 (PPh 3 ) 4 cluster [17][18][19]. With N,S coordinating site ligands, dinuclear complexes featuring [Cu 2 I 2 ] rhomboids are formed in most cases [20][21][22][23][24].…”

Section: Introductionmentioning

confidence: 99%

4,4-Bis(isopropylthio)-1,1-diphenyl-2-azabuta-1,3-diene Adducts with Cadmium(II), Mercury(II) and Copper(I) Iodides: Crystal, Molecular and Electronic Structures of d10 Transition Metal Chelate Complexes

Kinghat,

Khatyr,

Knorr

et al. 2023

Chemistry

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The thioether-functionalized 2-azabutadiene (iPrS)2C=C(H)-N=CPh2 L ligates to CdI2 and HgI2 to form the chelate compounds [CdI2{(iPrS)2C=C(H)-N=CPh2] (1) and [HgI2(iPrS)2C=C(H)-N=CPh2] (2). Their crystal structures were solved via X-ray diffraction. Both crystallize in the non-centrosymmetric space groups: monoclinic P21 (1) and orthorhombic P212121 (2), respectively. The closed-shell d10 metal centers are four-coordinated (two iodides and S and N coordinating atoms from the ligand L) in both complexes. The geometrical indexes τ indicate that a highly distorted trigonal pyramidal is adopted for 1 and a seesaw geometry for 2. The comparative nature of metal–ligand bonds is discussed on the basis of metric parameters and of QT-AIM (quantum theory of atoms in molecules) calculations. L was also treated with CuI to obtain the dinuclear species [LCu(μ2-I2)CuL] (3), in which the two Cu(I) centers are linked by a short metal–metal bond. The geometric and electronic properties of 3 are compared with those of 1 and 2.

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“…Recently, MOFs have shown great potential as promising electrode materials . Except the ligand, the redox-active metal center can accommodate multiple electrons. − Moreover, the structural flexibility can buffer the large volume change during repeated discharging/charging processes and hence overcoming the degradation problems caused by the volume change. , The challenges of classic MOFs as electrode materials are their limited channel for lithium ion diffusion and obstruction of the pore window by organic solvents . To solve these issues, an alternative way is the application of one-dimensional coordination polymers (CPs) as electrode materials.…”

Section: Introductionmentioning

confidence: 99%

Transition-Metal-Triggered High-Efficiency Lithium Ion Storage via Coordination Interactions with Redox-Active Croconate in One-Dimensional Metal–Organic Anode Materials

Zhang¹,

Cheng²,

Shi³

2018

ACS Appl. Mater. Interfaces

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Coordination polymers (CPs) have powerful competence as anode materials for lithium-ion batteries (LIBs) owing to their structural diversity, tunable functionality, and facile and mild synthetic conditions. Here, we show that two isostructural one-dimensional croconate-based CPs, namely, [M(CO)(HO)] (M = Mn for 1 and Co for 2; CO = croconate dianion), can work as high-performance electrode materials for rechargeable LIBs. By means of the coordination between the redox-active transition metal ion and the ligand, the anode materials were stable in the electrolyte and showed high capacities, impressive rate capabilities, and excellent cycling performance during the discharging/charging processes. The chain-based supramolecular structures of the CPs also make them stand out from a crowd of porous three-dimensional molecular materials due to their free channels between the chains for lithium ion diffusion. When tested in a voltage window of 0.01-2.4 V at 100 mA g, CPs 1 and 2 demonstrated high discharge specific capacities of 729 and 741 mA h g, respectively. The synergistical redox reactions on both metal centers and the organic moieties play a crucial role in the high electrochemical performance of CPs 1 and 2. After undergoing elevated discharging/charging rates to 2 A g, the electrodes could finally recover their capabilities as those in the initial stage when the current rate was back to 100 mA g, indicating excellent rate performance and outstanding cycling stabilities of the materials.

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Anion exchange coupled with the reduction and dimerisation of a copper(ii) nitrate complex of tripyridyl dithioether via a single-crystal-to-single-crystal transformation

Abstract: We report that the anion exchange induced conversion of the oxidation state of the central metal and the dimerisation in the complex via an SCSC transformation.

Cited by 15 publications

References 62 publications

Solvent-Effected Coordination Variation of Flexible Ligands to Cu(II) for the Formation of 1D and 2D Secondary Building Units for Metal–Organic Frameworks

Solvent-Effected Coordination Variation of Flexible Ligands to Cu(II) for the Formation of 1D and 2D Secondary Building Units for Metal–Organic Frameworks

4,4-Bis(isopropylthio)-1,1-diphenyl-2-azabuta-1,3-diene Adducts with Cadmium(II), Mercury(II) and Copper(I) Iodides: Crystal, Molecular and Electronic Structures of d10 Transition Metal Chelate Complexes

Transition-Metal-Triggered High-Efficiency Lithium Ion Storage via Coordination Interactions with Redox-Active Croconate in One-Dimensional Metal–Organic Anode Materials

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