Metallorganische Verbindungen des Kupfers

Schulte, Petra; Gröger, Gunther; Behrens, Ulrich

doi:10.1016/s0022-328x(99)00070-4

Cited by 9 publications

(6 citation statements)

References 18 publications

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“…When Cu-S coordinations also occur, porous or non-porous 2D frameworks are systematically generated [23,24]. This preference for Cu(η 2 -C≡C) linkage over Cu-S is again fully consistent with earlier literature observation mentioned above [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18]. However, very rare examples of 2D and 3D CPs produced with alkynylcontaining dithioethers (here RC 6 H 4 SCH 2 C≡CCH 2 C 6 H 4 R; R = H, CH 3 ) and CuX salts (X = I in this case) through Cu-S only, also exist (2 examples) [25,26].…”

Section: Exhibits Such An Example ([Cu 4 I 4 ]L1supporting

confidence: 87%

“…There is a wealth of examples dated from the 1990's where copper halide salts selectively coordinate the alkynyl function (η 2 -C≡C) over the thioether one in bidentate (R-C ≡C•••S-R′) ligands to form organometallic species with a dandling uncoordinated thioether [1][2][3][4][5][6][7][8][9][10][11][12][13]. However, this trend does not exclude the several examples where both coordination centers are used to generate polymetallic (cyclic and acyclic) species and polymeric solids [14][15][16][17][18]. The bis(phenylacetylene) motif (PhC≡C─C≡CPh) is also known to efficiently bind copper halides (CuX; X = Cl) in a (η 2 -C≡C) fashion [19,20].…”

Section: Introductionmentioning

confidence: 99%

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Completely Unexpected Coordination Selectivity of Copper Iodide for Thioether Over Ethynyl

et al. 2018

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The reactivity of the tetradentate ligand bis(p-thiomethylphenylacetylene) (MeSC 6 H 4 C≡C-C≡CC 6 H 4 SMe; L2) towards the CuI salt is compared to that for the known organometallic analogue trans-bis(p-thiomethylethynylbenzene)bis(trimethylphosphine)platinum(II) (trans-Pt(PMe 3) 2 (C≡CC 6 H 4 SMe) 2 ; L1). While L1 with CuI form a highly luminescent porous 2D coordination polymer (CP) of general formula ([Cu 4 I 4 ]L1 • EtCN) n (CP1; Juvenal et al. in Inorg Chem 55:11096-11109, 2016) exhibiting both Cu(η 2-C≡C) and Cu-S bonds, L2 reacts with CuI to produce a luminescent non-porous 2D CP exhibiting the general formula ([Cu 4 I 4 ]{L2} 3) n , CP2, which does not use the highly expected Cu(η 2-C≡C) linkage, relying strictly upon Cu-S coordination. An examination of the X-ray structures for both L2 and CP2 indicates that CP2 network is built upon an expansion of the L2 lattice (plane sliding and slight L2-L2 distance separation) resembling to a sort of template effect. CP2 has been characterized by TGA, UV-Vis, emission spectroscopy, and photophysics, which are accompanied by DFT and TDDFT computations.

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Section: Exhibits Such An Example ([Cu 4 I 4 ]L1supporting

confidence: 87%

Section: Introductionmentioning

confidence: 99%

Completely Unexpected Coordination Selectivity of Copper Iodide for Thioether Over Ethynyl

et al. 2018

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“…3). Within the cluster core, the Cu-I bond lengths range between 2.6391 (12) and 2 The TGA trace for the polymer 1 (Fig. 4) exhibits two endothermic steps.…”

Section: Methodsmentioning

confidence: 99%

Rigidity effect of the dithioether spacer on the size of the luminescent cluster (Cu₂I₂)_n(n = 2, 3) in their coordination polymers

et al. 2009

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Treatment of CuI with the flexible PhS(CH(2))(4)SPh dithioether ligand in MeCN solution affords the strongly luminescent metal-organic 2D coordination polymer [Cu(4)I(4){mu-PhS(CH(2))(4)SPh}(2)](n) (). The interpenetrated 2D network of is built upon by Cu(4)(mu(3)-I)(4) cubane-like clusters as secondary building units (SBUs), which are interconnected via bridging 1,4-bis(phenylthio)butane ligands. In contrast, the auto-assembly reaction of the unsaturated semi-flexible PhSCH(2)C[triple bond, length as m-dash]CCH(2)SPh ligand with CuI results in formation of the 3D metallopolymer [(Cu(6)I(6)){mu-PhSCH(2)C[triple bond, length as m-dash]CCH(2)SPh}(3)](n) (). The SBUs of luminescent consist of discrete Cu(6)(mu(3)-I)(6) hexagon prisms, which are coordinated with bridging 1,4-bis(phenythio)butyne ligands via Cu-S bonds. Contrary to the other rare literature-known examples of metallopolymers incorporating Cu(6)X(6) SBUs as connecting nodes, the CuCu interactions of [2.8484(6) A] are markedly shorter, being close to the sum of the Van der Waals radii of two Cu atoms ( approximately 2.8 A). The photophysics of these compounds, which exhibit reversible luminescence thermochromism, has been investigated in detail. The solid-state luminescence spectra of and feature at room temperature intense emissions around 560 and 555 nm, respectively. The luminescence properties of the unusual Cu(6)(mu(3)-I)(6) hexagon prism motif are rationalized by means of DFT and TDDFT computations.

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“…The polymer composition is independent on the CuI/ ligand ratio. In contrast to some other thioether ligands possessing an alkyne function, [54] 6 (m 3 -X) 6 py 6 ] n (X ¼ Cl, Br, I), involving this unusual motif have been reported so far. [55,56] In the latter luminescent material, a pyridine-functionalized triethyl-benzene spacer links the cluster nodes.…”

Section: Scheme 15mentioning

confidence: 98%

Luminescent Coordination Polymers Built Upon Cu₄X₄ (X=Br,I) Clusters and Mono‐ and Dithioethers

Harvey

Knorr

2010

Macromol. Rapid Commun.

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This paper focuses on the syntheses, structures, and luminescence properties of 1D, 2D, and 3D coordination polymers built upon the tetranuclear Cu(4) X(4) clusters and mono- and dithioether assembling ligands. A review of the relevant literature is presented along with our own results stressing on the salient features of the interactions between the CuI salt as the starting material and the thioethers. Among the features, the solvato- (lost or gain of a monothioether or solvent molecule) and luminescence thermochromism (temperature dependence of the emission) of the solids, and the enhanced versatility of the CuI salt to form clusters of different nuclearity (Cu(2) I(2) , Cu(4) I(4) , Cu(6) I(6) ) and structures (closed cubane, partially open "flower-basket-like" cubane, and open cubane) upon the reaction conditions and ligands, are described. The steady state and time-resolved solid-state emission and excitation spectra (at 298 and 77 K) as well as the emission lifetimes are examined. Simple and apparently "innocent" modification may have a drastic effect on the polymer network and cluster structures, but this paper finds no obvious trend for the moment except for the ligand rigidity. The rhombic Cu(2) I(2) and closed-cubane Cu(4) I(4) clusters are the most encountered motifs whereas the open-flower-basket Cu(4) I(4) cubane and the hexagonal Cu(6) I(6) clusters are scarce.

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Metallorganische Verbindungen des Kupfers

Cited by 9 publications

References 18 publications

Completely Unexpected Coordination Selectivity of Copper Iodide for Thioether Over Ethynyl

Completely Unexpected Coordination Selectivity of Copper Iodide for Thioether Over Ethynyl

Rigidity effect of the dithioether spacer on the size of the luminescent cluster (Cu₂I₂)_n(n = 2, 3) in their coordination polymers

Luminescent Coordination Polymers Built Upon Cu₄X₄ (X=Br,I) Clusters and Mono‐ and Dithioethers

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Metallorganische Verbindungen des Kupfers

Cited by 9 publications

References 18 publications

Completely Unexpected Coordination Selectivity of Copper Iodide for Thioether Over Ethynyl

Completely Unexpected Coordination Selectivity of Copper Iodide for Thioether Over Ethynyl

Rigidity effect of the dithioether spacer on the size of the luminescent cluster (Cu2I2)n(n = 2, 3) in their coordination polymers

Luminescent Coordination Polymers Built Upon Cu4X4 (X=Br,I) Clusters and Mono‐ and Dithioethers

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Rigidity effect of the dithioether spacer on the size of the luminescent cluster (Cu₂I₂)_n(n = 2, 3) in their coordination polymers

Luminescent Coordination Polymers Built Upon Cu₄X₄ (X=Br,I) Clusters and Mono‐ and Dithioethers