Coordination Polymers with Group 15/16 Element Building Blocks

Wächter, Joachim

doi:10.1016/b978-0-08-097774-4.00139-x

Cited by 4 publications

(1 citation statement)

References 131 publications

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“…The design of coordination polymers with a predictable secondary building unit (SBU) and dimensionality is a quasi-impossible task, but the quest remains of great interest for the discovery of new materials with desired properties such as gas adsorption, − sensing, − thermo-chromism, − magnetism, − conductivity, − redox-activity, , catalysis, ,− nonlinear optical behavior, , and luminescence. ,− Recent reviews on CPs formed by mono- and dithioethers with CuX salts (X = Cl, Br, I) − revealed that, when X = I, the SBU had a strong tendency to form closed cubanes (Cu 4 I 4 ) and 1D staircase polymeric structures, whereas the rhomboid Cu 2 X 2 S 4 SBU is predominately noted when X = Cl or Br. The key property is that the cubanes show luminescence regardless of the ligand, whereas the rhomboids and staircase motifs are almost always weakly or not emissive. ,, Also, the presence of 2D and 3D CPs increases drastically when semirigid or rigid dithioethers are used as assembling ligands. ,, The interest in 2D and 3D CPs stems from the possibility to form MOF-like materials .…”

Section: Introductionmentioning

confidence: 99%

Control of Structures and Emission Properties of (CuI)_n 2-Methyldithiane Coordination Polymers

et al. 2018

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A structurally unique and strongly luminescent non-porous 3D coordination polymer (CP) [Cu 8 I 8 (methyldithiane) 4 ] n , CP3, has been prepared in a quasi-anticipated manner from 2-methyl-1,3-dithiane, L1, and CuI. This CP incorporates the unprecedented Cu 8 I 8 cluster built upon two side-fused open cubanes. The crystal structure of CP3 has been determined at 100, 150, 200, 250, 300, 350 and 400 K to study the temperature dependence of the Cu•••Cu distances. Two other topological 1D and 2D CPs isomers of formula [{Cu 2 I 2 }(L1) 2 ] n featuring dinuclear {Cu 2 ( 2 -I) 2 } rhomboids were also obtained independently by control of the reaction conditions. These two CPs convert into CP3 in hot PrCN thus indicating that this latter material is the thermodynamic product. While CP1 and CP2 are not emissive, CP3 exhibits an intense luminescence due to the incorporation of the octanuclear Cu 8 I 8 clusters as secondary building units (SBUs) within the network. The photophysical properties of CP3 have been investigated and rationalized by means of DFT and TDDFT computing. Furthermore, the thermal stability of these materials has been studied by ATG and DSC analyses. The Raman spectra of CP1-3 have been recorded in the solid state in the 50 -500 cm -1 region.

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Section: Introductionmentioning

confidence: 99%

Control of Structures and Emission Properties of (CuI)_n 2-Methyldithiane Coordination Polymers

et al. 2018

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Das Potential von Molybdänkomplexen mit unsubstituierten heterodiatomaren Gruppe‐15‐Elementen als Linker in der supramolekularen Chemie

et al. 2019

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Die Reaktion von tetraedrischen Molybdän‐Komplexen mit unsubstituierten heterodiatomaren Gruppe‐15‐Elementen [Cp2Mo2(CO)4(μ,η2:η2‐PE)] (Cp=C5H5, E=As (1), Sb (2)) mit CuI‐Halogeniden ergab sieben präzedenzlose, neutrale Supramoleküle. In Abhängigkeit von den Mo2PE‐Einheiten und den CuI‐Halogeniden werden die Oligomere [⟨{Cp2Mo2(CO)4}{μ4,η2:η2:η2:η1‐PE}⟩4⟨{CuX}{Cu(μ‐X)}⟩2] (E=As (X=Cl (3), Br (4)); E=Sb (X=Cl (6), Br (7))) oder die 1D‐Koordinationspolymere [{Cp2Mo2(CO)4}{μ4,η2:η2:η1:η1‐PAs}{Cu(μ‐I)}]n (5) und [{Cp2Mo2(CO)4}{μ4,η2:η2:η2:η1‐PSb}2{Cu(μ‐X)}3]n (X=I (8), Br (9)) erhalten. Diese Festkörper‐Aggregate sind die ersten und einzigen Beispiele, die über die metallorganischen heterodiatomaren Mo2PE‐Komplexe 1 und 2 als Verbindungseinheiten verfügen. DFT‐Rechnungen zeigen, dass die Komplexe 1 und 2 eine neue Klasse von gemischten Donorliganden darstellen, die an CuI‐Zentren über das freie P‐Elektronenpaar und die P‐E‐Sigma‐Bindung koordinieren und dabei eine bisher nicht beobachtete Koordinationsform aufweisen.

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The Potential of Molybdenum Complexes Bearing Unsubstituted Heterodiatomic Group 15 Elements as Linkers in Supramolecular Chemistry

et al. 2019

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The reactions of tetrahedral molybdenum complexes bearing unsubstituted heterodiatomic Group 15 elements, [Cp2Mo2(CO)4(μ,η2:η2‐PE)] (Cp=C5H5; E=As (1), Sb (2)), with CuI halides afforded seven unprecedented neutral supramolecular assemblies. Depending on the Mo2PE units and the CuI halide, the oligomers [⟨{Cp2Mo2(CO)4}{μ4,η2:η2:η2:η1‐PE}⟩4⟨{CuX}{Cu(μ‐X)}⟩2] (E=As (X=Cl (3), Br (4)); E=Sb (X=Cl (6), Br (7))) or the 1D coordination polymers [{Cp2Mo2(CO)4}{μ4,η2:η2:η1:η1‐PAs}{Cu(μ‐I)}]n (5) and [{Cp2Mo2(CO)4}{μ4,η2:η2:η2:η1‐PSb}2{Cu(μ‐X)}3]n (X=I (8), Br (9)) are accessible. These solid‐state aggregates are the first and only examples featuring the organometallic heterodiatomic Mo2PE complexes 1 and 2 as linking moieties. DFT calculations demonstrate that complexes 1 and 2 present a unique class of mixed‐donor ligands coordinating to CuI centers via the P lone pair and the P−E σ‐bond, revealing an unprecedented coordination mode.

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Coordination Polymers with Group 15/16 Element Building Blocks

Cited by 4 publications

References 131 publications

Control of Structures and Emission Properties of (CuI)_n 2-Methyldithiane Coordination Polymers

Control of Structures and Emission Properties of (CuI)_n 2-Methyldithiane Coordination Polymers

Das Potential von Molybdänkomplexen mit unsubstituierten heterodiatomaren Gruppe‐15‐Elementen als Linker in der supramolekularen Chemie

The Potential of Molybdenum Complexes Bearing Unsubstituted Heterodiatomic Group 15 Elements as Linkers in Supramolecular Chemistry

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Coordination Polymers with Group 15/16 Element Building Blocks

Cited by 4 publications

References 131 publications

Control of Structures and Emission Properties of (CuI)n 2-Methyldithiane Coordination Polymers

Control of Structures and Emission Properties of (CuI)n 2-Methyldithiane Coordination Polymers

Das Potential von Molybdänkomplexen mit unsubstituierten heterodiatomaren Gruppe‐15‐Elementen als Linker in der supramolekularen Chemie

The Potential of Molybdenum Complexes Bearing Unsubstituted Heterodiatomic Group 15 Elements as Linkers in Supramolecular Chemistry

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Control of Structures and Emission Properties of (CuI)_n 2-Methyldithiane Coordination Polymers

Control of Structures and Emission Properties of (CuI)_n 2-Methyldithiane Coordination Polymers