Novel heptanuclear copper(<scp>i</scp>) iodide cluster with a pinwheel shape

Cheon, Sanghun; Kim, Tae Ho; Jeon, Youngeun; Kim, Jineun; Park, Ki‐Min

doi:10.1039/c2ce26664d

Cited by 27 publications

(12 citation statements)

References 27 publications

(12 reference statements)

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“…The emissions from CPs 1 – 3 might be assigned to metal‐to‐ligand charge‐transfer (MLCT) and cluster center (CC) excited states, with some mixing of the halide‐to‐ligand charge‐transfer (XLCT) and iodide‐to‐copper charge‐transfer (XMCT) characters 13. The photoluminescence properties of stair‐step complex 1 are similar to those of a pinwheel‐shaped Cu 7 I 7 cluster complex with an N/S donor ligand, which shows a partial stair‐step Cu 4 I 4 structure 10b. The emission maximum of 2 is similar to those of cubane Cu 4 I 4 cluster complexes reported in the literature 14.…”

Section: Methodsmentioning

confidence: 98%

Reversible Transformation between Cubane and Stairstep Cu₄I₄ Clusters Using Heat or Solvent Vapor

Cho

Jeon

Lee

et al. 2014

Chemistry A European J

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The controlled self-assembly of CuI and an asymmetric ligand with mixed N/S donors, 2-(tert-butylthio)-N-(pyridin-3-yl)acetamide (L), afforded three Cu(I) coordination polymers (CPs), [Cu4I4L2(MeCN)2]n (1), [Cu4I4L2]n (2), and {[Cu4I4L2]⋅MeOH}n (3). X-ray analyses showed that CPs 1-3 are supramolecular isomers with 1, 2, and 3D structures, respectively. CP 1 adopts a stairstep Cu4I4 cluster, whereas CPs 2 and 3 are composed of cubane-like Cu4I4 clusters. Crystal-to-crystal transformations of 1 to 2 and 3 showed reversible transformations between different Cu4I4 clusters using heat or solvent (acetonitrile or methanol) vapor. CP 2 was reversibly transformed to 3 by the addition of methanol and heat. Therefore, the transformations between supramolecular isomers 1, 2, and 3 are completely reversible.

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Section: Methodsmentioning

confidence: 98%

Reversible Transformation between Cubane and Stairstep Cu₄I₄ Clusters Using Heat or Solvent Vapor

Cho

Jeon

Lee

et al. 2014

Chemistry A European J

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“…It contains two crystallographically independent discrete (0D) dinuclear molecules differing in the Cu•••Cu distances of 2.7222(6) and 2.9198 (7). 71 Influence of the Stereochemistry. In order to study the influence of the stereochemistry around the CC bond of the olefinic dithioether, the isomeric ligand Z-PhS(CH 2 CH CHCH 2 )SPh (L2) was prepared and reacted with CuI in MeCN.…”

Section: ■ Introductionmentioning

confidence: 99%

1,4-Bis(arylthio)but-2-enes as Assembling Ligands for (Cu₂X₂)_n (X = I, Br; n = 1, 2) Coordination Polymers: Aryl Substitution, Olefin Configuration, and Halide Effects on the Dimensionality, Cluster Size, and Luminescence Properties

Bonnot

Knorr

Guyon

et al. 2016

Crystal Growth & Design

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CuI reacts with E-PhS(CH2CHCHCH2)SPh, L1, to afford the coordination polymer (CP) [Cu2I2{μ-E-PhS(CH2CHCHCH2)SPh}2] n (1a). The unprecedented square-grid network of 1 is built upon alternating two-dimensional (2D) layers with an ABAB sequence and contains rhomboid Cu2(μ2-I)2 clusters as secondary building units (SBUs). Notably, layer A, interconnected by bridging L1 ligands, contains exclusively dinuclear units with short Cu···Cu separations [2.6485(7) Å; 115 K]. In contrast, layer B exhibits Cu···Cu distances of 2.8133(8) Å. The same network is observed when CuBr reacts with L1. In the 2D network of [Cu2Br2{μ-E-PhS(CH2CHCHCH2)SPh}2] n (1b), isotype to 1a, one square-grid-type layer contains Cu2(μ2-Br)2 SBUs with short Cu···Cu contacts [2.7422(6) Å at 115K], whereas the next layer incorporates exclusively Cu2(μ2-Br)2 SBUs with a significantly longer Cu···Cu separation [2.9008(10) Å]. The evolution of the crystallographic parameters of 1a and 1b was monitored between 115 and 275 K. Conversely, the isomeric Z-PhS(CH2CHCHCH2)SPh ligand L2 reacts with CuI to form the 2D CP [Cu4(μ3-I)4(μ-Z-PhS(CH2CHCHCH2)SPh}2] n (2a) with closed-cubane SBUs. A dinuclear zero-dimensional complex [Cu2Br2{μ-Z-PhS(CH2CHCHCH2)SPh}2] (2b) is formed when CuBr is reacted with L2. Upon reaction of E-TolS(CH2CHCHCH2)STol, L3, with CuI, the 2D CP [{Cu(μ3-I)}2(μ-L3)] n containing parallel-arranged infinite inorganic staircase ribbons, is generated. When CuX reacts with Z-TolS(CH2CHCHCH2)STol, L4, the isostructural 2D CPs [Cu2X2{μ-Z-TolS(CH2CHCHCH2)STol}2] (4a X = I; 4b X = Br) are formed. In contrast to the CPs 1a,b, the layers based on rhombic grids of 4a,b incorporate Cu2(μ2-X)2 SBUs featuring uniformly identical Cu···Cu distances within each layer. The TGA traces showed that all these materials are stable up to ∼200 °C. Moreover, the photophysical properties have been studied, including absorption, emission, excitation spectra, and emission lifetimes at 298 and 77 K. The spectra were interpreted using density functional theory (DFT) and time-dependent DFT calculations.

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“…The PL behaviors of the copper(I) halide complexes have been known to be sensitive to many factors including the Cu···Cu separations, shapes, and donor atoms. ,− Since isomers 6 and 7 showed different photophysical properties under the UV lamp in our preliminary work, their solid-state PL spectra were obtained at room temperature (Figure ). The crystalline solid of isomer 6 with the cubane tetramer exhibits a strong yellow emission with the maximum at 560 nm, which according to the literature on the cubane tetramer complex of thioether ligands is dominated by a cluster-centered (CC) emission with a mixed halide-to-ligand charge transfer (XLCT) character. , Similar emission bands (530–560 nm) originating from the Cu 4 I 4 cubane-type cluster also have been reported by us ,, and the D. Li group .…”

Section: Resultsmentioning

confidence: 99%

Coordinative Networking of Thiacalix[4]-bis-monothiacrown-5 with Hard, Borderline, and Soft Metal Salts via Exo- and Endo/Exo-Coordination

Habata

Jung

et al. 2021

Crystal Growth & Design

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Coordinative networks of thiacalix[4]-bis-monothiacrown-5 (L) whose infinite structures span from one (1D) to three dimensions (3D) with hard (K+), borderline (Cd2+), and soft (Cu+, Hg2+) metal salts are reported. First, mercury(II) salts afforded straight and zigzag 1D coordination polymers of type [(Hg2X4)(L)] n (1: X = Cl and 2: X = SCN), respectively, with an L-Hg2X4-L-Hg2X4 pattern. When cadmium(II) salts (CdX2) (3: X = Br and 4: X = I) were used, the bromo complex 3 exhibited an infinite 2D structure with square lattice (sql) topology, in which trilooped Cd4Br8 cluster acts as a four-connected node. In contrast, the iodo complex 4 showed a 1D polymeric chain similar to 1. A mixture of KI and CdI2 gave an exceptional discrete complex of type {[(K2 L)CdI3]2[K2 L](CdI4)2·2CH3CN} (5) with five separated parts involving two identical endo/exocyclic heteronuclear complex units. Interestingly, the CuI complexation yielded a mixture of two supramolecular isomers (6 and 7) of type [(Cu4I4)(L)2] n , each of which was separated with the naked eye under a UV lamp due to their drastically different photoluminescence properties; isomer 6 is emissive while isomer 7 is nonemissive. Isomer 6 features an infinite 3D network with threefold interpenetrated diamodoid (dia) topology in which Cu4I4 cubane tetramers act as 4-connected nodes, while isomer 7 is a non-interpenetrated 2D network with sql topology incorporating Cu4I4 stepped cubane tetramers as 4-connected nodes. Consequently, the borderline and soft metal ions bind to the S-donor on the O4S1-crown loop in an exocyclic mode to form low to high dimensional coordinative networks, with S-bridges in the thiacalix rim remaining uncoordinated mainly because of the weak basicity and rigid conformation. This work also demonstrates the supramolecular isomers incorporating two types of Cu4I4 tetramers which exhibit different photophysical properties as a good example not only for the crystal engineering of the exocoordinated networking but also for the structure–function relationship.

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Novel heptanuclear copper(i) iodide cluster with a pinwheel shape

Cited by 27 publications

References 27 publications

Reversible Transformation between Cubane and Stairstep Cu₄I₄ Clusters Using Heat or Solvent Vapor

Reversible Transformation between Cubane and Stairstep Cu₄I₄ Clusters Using Heat or Solvent Vapor

1,4-Bis(arylthio)but-2-enes as Assembling Ligands for (Cu₂X₂)_n (X = I, Br; n = 1, 2) Coordination Polymers: Aryl Substitution, Olefin Configuration, and Halide Effects on the Dimensionality, Cluster Size, and Luminescence Properties

Coordinative Networking of Thiacalix[4]-bis-monothiacrown-5 with Hard, Borderline, and Soft Metal Salts via Exo- and Endo/Exo-Coordination

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Novel heptanuclear copper(i) iodide cluster with a pinwheel shape

Cited by 27 publications

References 27 publications

Reversible Transformation between Cubane and Stairstep Cu4I4 Clusters Using Heat or Solvent Vapor

Reversible Transformation between Cubane and Stairstep Cu4I4 Clusters Using Heat or Solvent Vapor

1,4-Bis(arylthio)but-2-enes as Assembling Ligands for (Cu2X2)n (X = I, Br; n = 1, 2) Coordination Polymers: Aryl Substitution, Olefin Configuration, and Halide Effects on the Dimensionality, Cluster Size, and Luminescence Properties

Coordinative Networking of Thiacalix[4]-bis-monothiacrown-5 with Hard, Borderline, and Soft Metal Salts via Exo- and Endo/Exo-Coordination

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Reversible Transformation between Cubane and Stairstep Cu₄I₄ Clusters Using Heat or Solvent Vapor

Reversible Transformation between Cubane and Stairstep Cu₄I₄ Clusters Using Heat or Solvent Vapor

1,4-Bis(arylthio)but-2-enes as Assembling Ligands for (Cu₂X₂)_n (X = I, Br; n = 1, 2) Coordination Polymers: Aryl Substitution, Olefin Configuration, and Halide Effects on the Dimensionality, Cluster Size, and Luminescence Properties