Luminescent Oligomeric and Polymeric Copper Coordination Compounds Assembled by Thioether Ligands

Knorr, Michael; Guyon, Fabrice

doi:10.1002/9780470604090.ch3

Cited by 14 publications

(12 citation statements)

References 167 publications

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“…On many occasions, the facile control of the SBU structure, globular vs quasi-planar , mainly cubane Cu 4 I 4 L 4 vs rhomboid Cu 2 I 2 L 4 , has been performed by simply adjusting the stoichiometric ratio Cu atom/S atom, thus controlling the luminescence properties ( on or off ). ,, Generally, the SBU geometry consists of a distinct cluster, but on rare occasions, the SBU motif exhibits a polymeric 1D-[CuI] n skeleton (Figure ). These 1D-[CuI] n motifs are accordion ribbon, , zigzag ribbon, staircase ribbon, and polycubane, , and again, these quasi-planar SBUs are either weakly emissive or non-emissive (accordion, zigzag, and staircase ribbons). Concurrently, the globular polycubane SBU exhibits an intense emission.…”

Section: Introductionmentioning

confidence: 93%

“…Structures of the 1D-[CuI] n SBUs encountered in neutral mono- and dithioether/CuI-containing CPs (S = sulfur atom of the thioether ligand). − …”

Section: Introductionmentioning

confidence: 99%

“…33,35,36 geometry consists of a distinct cluster, but on rare occasions, the SBU motif exhibits a polymeric 1D-[CuI] n skeleton (Figure 1). These 1D-[CuI] n motifs are accordion ribbon, 37,38 zigzag ribbon, 39 staircase ribbon, 40 and polycubane, 36,41 and again, these quasi-planar SBUs are either weakly emissive or non-emissive (accordion, zigzag, and staircase ribbons). Concurrently, the globular polycubane SBU exhibits an intense emission.…”

Section: ■ Introductionmentioning

confidence: 99%

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A Fused Poly(truncated rhombic dodecahedron)-Containing 3D Coordination Polymer: A Multifunctional Material with Exceptional Properties

et al. 2021

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The design of new and inexpensive metal-containing functional materials is of great interest. Herein is reported a unique thermochromic near-IR emitting coordination polymer, 3D-[Cu8I8(L1)2] n , CP2, which is formed when ArS(CH2)4SAr (L1, Ar = 4-C6H4OMe) reacts with 2 equiv of CuI in EtCN. In MeCN, CP1 ([Cu4I4(L1)(MeCN)2] n , consisting of an alternating [-Cu4I4-L1-Cu4I4-L1-] n chain where the Cu4I4 cubane units bear two metal-bound MeCN molecules, is formed. Heat-driven elimination of these MeCN’s in solid CP1 also leads to CP2 through a predisposed organization of the Cu4I4 units prone to fusion after MeCN eliminations (i.e., a rare case of template effect). The CP2 structure exhibits parallel 1D-(Cu8I8) n chains, (z-axis; designated 1D-[CuI] n ) as secondary building units (SBU) held together by parallel thioether ligands (x,y-axes), forming a nonporous 3D network. The structure of this 1D-[CuI] n SBU is unprecedented and consists of a series of fused and twisted open Cu4I4 cubanes forming a fused poly(truncated rhombic dodecahedron). Unexpectedly, the compact 3D CP2 exhibits a solid-to-solid phase transition at 100 °C and a hysteresis of ∼20 °C. CP1 emits intensively (298 K: λemi = 564 nm; Φe = 0.35), whereas CP2 presents a strongly red-shifted weaker emission (298 K: λemi ∼ 740 nm, Φe < 0.0001). Moreover, CP2, which is stable over long periods of time, exhibits thermochromism where the emission intensity of the near-IR band decreases significantly at the benefit of a ligand-centered phosphorescence at 415 nm. Altogether, these properties listed above make CP2 exceptional. The low-energy singlet and triplet excited states have been assigned to ligand/metal-to-ligand charge transfer based on DFT and TD-DFT computations.

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Section: Introductionmentioning

confidence: 93%

“…Structures of the 1D-[CuI] n SBUs encountered in neutral mono- and dithioether/CuI-containing CPs (S = sulfur atom of the thioether ligand). − …”

Section: Introductionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

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A Fused Poly(truncated rhombic dodecahedron)-Containing 3D Coordination Polymer: A Multifunctional Material with Exceptional Properties

et al. 2021

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“…Concurrently, the reaction of PhSCH 2 CH 2 SPh with CuI resulted in formation of the metallopolymer [(CuI) 2 {μ-PhS(CH 2 ) 2 SPh} 2 ] n , whose 2D-network is built up upon dimeric Cu 2 I 2 units, which are interconnected via bridging dithioether ligands . Using the more flexible 1,4-PhS(CH 2 ) 4 SPh dithioether ligand afforded the strongly luminescent metal–organic 2D coordination polymer [Cu 4 I 4 {μ-PhS(CH 2 ) 4 SPh} 2 ] n whose interpenetrated 2D network is built upon by Cu 4 (μ 3 -I) 4 cubane-like clusters as secondary building units (SBUs), interconnected via bridging bis(phenylthio)butane ligands. , …”

Section: Introductionmentioning

confidence: 99%

Construction of (CuX)_2n Cluster-Containing (X = Br, I; n = 1, 2) Coordination Polymers Assembled by Dithioethers ArS(CH₂)_mSAr (Ar = Ph, p-Tol; m = 3, 5): Effect of the Spacer Length, Aryl Group, and Metal-to-Ligand Ratio on the Dimensionality, Cluster Nuclearity, and the Luminescence Properties of the Metal–Organic Frameworks

et al. 2012

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Reaction of CuI with bis(phenylthio)propane in a 1:1 ratio yields the two-dimensional coordination polymer [{Cu(μ(2)-I)(2)Cu}{μ-PhS(CH(2))(3)SPh}(2)](n) (1). The 2D-sheet structure of 1 is built up by dimeric Cu(2)I(2) units, which are connected via four bridging 1,3-bis(phenylthio)propane ligands. In contrast, treatment of 2 equiv of CuI with 1,3-bis(phenylthio)propane in MeCN solution affords in a self-assembly reaction the strongly luminescent metal-organic 2D-coordination polymer [Cu(4)I(4){μ-PhS(CH(2))(3)Ph}(2)](n) (2), in which cubane-like Cu(4)(μ(3)-I)(4) cluster units are linked by the dithioether ligands. The crystallographically characterized one-dimensional (1D) compound [{Cu(μ(2)-Br)(2)Cu}{μ-PhS(CH(2))(3)SPh}(2)](n) (3) is obtained using CuBr. The outcome of the reaction of PhS(CH(2))(5)SPh with CuI also depends of the metal-to-ligand ratio employed. Mixing CuI and the dithioether in a 2:1 ratio results in formation of [Cu(4)I(4){μ-PhS(CH(2))(5)Ph}(2)](n) (4) in which cubane-like Cu(4)(μ(3)-I)(4) clusters are linked by the bridging dithioether ligand giving rise to a 1D necklace structure. A ribbon-like 1D-polymer with composition [{Cu(μ(2)-I)(2)Cu}{μ-PhS(CH(2))(5)SPh}(2)](n) (5), incorporating rhomboid Cu(2)I(2) units, is produced upon treatment of CuI with 1,5-bis(phenylthio)pentane in a 1:1 ratio. Reaction of CuBr with PhS(CH(2))(5)SPh produces the isomorphous 1D-compound [{Cu(μ(2)-Br)(2)Cu}{μ-PhS(CH(2))(5)SPh}(2)](n) (6). Strongly luminescent [Cu(4)I(4){μ-p-TolS(CH(2))(5)STol-p}(2)](n) (7) is obtained after mixing 1,5-bis(p-tolylthio)pentane with CuI in a 1:2 ratio, and the 2D-polymer [{Cu(μ(2)-I)(2)Cu}(2){μ-p-TolS(CH(2))(5)STol-p}(2)](n) (8) results from reaction in a 1:1 metal-to-ligand ratio. Under the same reaction conditions, 1D-polymeric [{Cu(μ(2)-Br)(2)Cu}{μ-p-TolS(CH(2))(5)STol-p}(2)](n) (9) is formed using CuBr. This study reveals that the structure of the self-assembly process between CuX and ArS(CH(2))(m)SAr ligands is hard to predict. The solid-state luminescence spectra at 298 and 77 K of 2 and 4 exhibit very strong emissions around 535 and 560 nm, respectively, whereas those for 1 and 5 display weaker ones at about 450 nm. The emission lifetimes are longer for the longer wavelength emissions (>1.0 μs arising from the cubane species) and shorter for the shorter wavelength ones (<1.4 μs arising from the rhomboid units). The Br-containing species are found to be weakly fluorescent.

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“…In the context of our on-going study on the assembly of CPs and MOFs by reaction of aromatic and aliphatic dithioethers RS(CH 2 ) n SR (n = 1-8) with CuX salt (X = I, Br, Cl), we have described in series of papers the construction and structural features of numerous molecular clusters and coordination networks, with dimensionalities varying from 0D-3D [18][19][20][21][22][23][24][25]. The occurrence of polynuclear (CuX) n clusters as secondary building units (SBUs) often confers these materials, notably in the case of (CuI) n SBUs, interesting luminescence properties [26].…”

Section: Introductionmentioning

confidence: 99%

1,3-Dithiolane and 1,3-Ferrocenyl-dithiolane as Assembling Ligands for the Construction of Cu(I) Clusters and Coordination Polymers

Raghuvanshi

Dargallay

Knorr

et al. 2017

J Inorg Organomet Polym

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Luminescent Oligomeric and Polymeric Copper Coordination Compounds Assembled by Thioether Ligands

Cited by 14 publications

References 167 publications

A Fused Poly(truncated rhombic dodecahedron)-Containing 3D Coordination Polymer: A Multifunctional Material with Exceptional Properties

A Fused Poly(truncated rhombic dodecahedron)-Containing 3D Coordination Polymer: A Multifunctional Material with Exceptional Properties

1,3-Dithiolane and 1,3-Ferrocenyl-dithiolane as Assembling Ligands for the Construction of Cu(I) Clusters and Coordination Polymers

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