Molecules with an M4X4 core.  IV.  Crystallographic detection of a step configuration for the tetracopper tetraiodide core in tetrameric triphenylphosphinecopper(I) iodine, [PPh3CuI]4

Churchill, Melvyn Rowen; DeBoer, Barry G.; Donovan, Daniel J.

doi:10.1021/ic50145a036

Cited by 106 publications

(42 citation statements)

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“…There do not appear to be any identifiable trends in these bond lengths with the nature of the neutral ligand. The Cu-P distances, average = 2.247(5) A, are the same as those found with t~rtiary phosphines in similar structures, namely, 2.24 to 2.27 A (17,20). The phenylphosphine ligands display no unusual features in bond leng!hs or angles.…”

Section: Molecular Structuresupporting

confidence: 67%

“…The CuI bond lengths, average = 2.665 (18) A, are in the range normal!y found for tetrahedrally coordinated copper (I) (2.62-2.81 A) (10,17,20). There do not appear to be any identifiable trends in these bond lengths with the nature of the neutral ligand.…”

Section: Molecular Structurementioning

confidence: 57%

“…Apparent deviations in the C-C bond distances from the expected 1.395 A, especially for those between meta and para carbon atoms, may result from systematic errors caused by rigid-body thermal motions. Specifically, wagging motions of the phenylphosphine groups may cause the C-C bond lengths furthest from the point of attachment of the ligand to the Cu atom to be systematically low (20).…”

Section: Molecular Structurementioning

confidence: 99%

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Complex formation between cuprous iodide and phenyl phosphine: a nuclear magnetic resonance and X-ray crystallographic study

Batchelor¹,

Birchall²,

Faggiani³

1985

Can. J. Chem.

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, 928 (1985). The X-ray crystal structure of di-p,-iodobis[bis(phenylphosphine)co~per(I)] has been determined: R, = 0.0460. The crystals were monoclinic, space group Cc, a = 10.625(2) A, b = 25.1 15(8) A, c = 1 1.361(2) A, P = 105.929(15)", fw = 821.28, and Z = 4. The molecular structure consists of two C U I ( C~H~P H~)~ units bridged via the iodines so that each copper achieves tetrahedral coordination. Nuclear magnetic resonance data provides evidence that the phenylphosphines remain coordinated in solution but undergo rapid exchange at room temperature. qui sont relites par les iodes d'une fa~on telle que chaque atome de cuivre atteint une coordination tCtraCdrique. Sur la base des donnCes de la rmn, on peut affirmer que, en solution, les phCnylphosphines restent coordinnkes mais qu'elles subissent un Cchange rapide a la temptrature ambiante.[Traduit par le journal] Introduction phine, arsine) appeared to be potentially useful for investigaAlthough basicity and donor ability are well known propertions concerning the relative importance of steric and electronic ties of trivalent compounds of the group 5 elements there has factors because a large number of X-ray crystallographic been relatively little investigation of the coordination chemistry studies have shown that the steric bulk of both the neutral of hydrides and organohydrides of these elements other than nitrogen. Presumably this is because the tertiary derivatives, especially the triphenyl compounds, are much easier to work with and much less susceptible to oxidation. While it is reasonable to expect that the coordination chemistry of primary and secondary phosphines will be very similar to that of tertiary derivatives potential differences do exist. For example, there is evidence for the dissociation of P-H bonds with resultant formation of phosphido complexes (1). Also it has been noted that the order of basicity for phosphines is

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Section: Molecular Structuresupporting

confidence: 67%

Section: Molecular Structurementioning

confidence: 57%

Section: Molecular Structurementioning

confidence: 99%

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Complex formation between cuprous iodide and phenyl phosphine: a nuclear magnetic resonance and X-ray crystallographic study

Batchelor¹,

Birchall²,

Faggiani³

1985

Can. J. Chem.

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“…20 Stoichiometric quantities of CuI (1 mmol, 0190 g) and PPh 3 (1 mmol, 0.262 g)were refluxed for 1 h in chloroform and the hot, clear solution filtered. On slow cooling and solvent evaporation, the product separate as colourless crystal…”

Section: Synthesis Of [Cui(pph 3 )] 4 Formmentioning

confidence: 99%

Polymorph and isomer conversion of complexes based on CuI and PPh₃easily observed via luminescence

et al. 2012

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Reactions between copper(I) iodide and triphenylphosphine have been explored in solution and in the solid state and six luminescent coordination complexes have been obtained and characterized by X-ray diffraction and UV-vis spectroscopy and photophysics. Solid-state reactions of CuI with PPh(3) in different conditions (kneading, vapour digestion) and stoichiometries resulted in the formation of high ratio ligand:metal compounds while tetrameric structures could be obtained only by solution reactions. Crystal structures were determined by single crystal X-ray diffraction while purity of the bulk product was checked by powder diffraction (XRPD). Three different tetrameric structures with 1:1 stoichiometry have been synthesized: two closed cubane-type polymorphs [CuI(PPh(3))](4) (form 1a) and [CuI(PPh(3))](4) (form 1b) and an open step-like isomer [CuI(PPh(3))](4) (form 2). The conversions between the polymorphs and isomers have been studied and characterized by XRPD. The most stable form [CuI(PPh(3))](4) (form 1b) can convert into the open step-like isomer [CuI(PPh(3))](4) (form 2) in a slurry experiment with EtOH or CH(2)Cl(2) or AcCN and converts back into [CuI(PPh(3))](4)1b when exposed to vapors of toluene. At room temperature all the tetrameric compounds exhibit luminescence in the solid state and, notably, the two polymorphs show a dissimilar dual emission at low temperature. The luminescence features in the solid state seem to be peculiarly related to the presence of the aromatic phosphine ligand and depend on the Cu-Cu distance in the cluster.

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“…2 was obtained by recrystallizing 3 in dichloromethane. All compounds were obtained as colorless crystals (Experimental Section), and the crystal structures were determined by single-crystal XRD analysis at 150 K. In all the structures, solvent molecules are included, and the formulas are [Cu 6 I 6 (PPh 2 (CH 2 ) 3 PPh 2 ) 3 ]·2 CH 2 Cl 2 (1·2 Note that the synthesis of 2 has been already reported in the literature by refluxing CuI and PPh 3 in chloroform 22 or by mechanosynthesis method. 27 In the former case, a crystal structure of 2 has been determined but without solvent included.…”

Section: ■ Introductionmentioning

confidence: 99%

Geometry Flexibility of Copper Iodide Clusters: Variability in Luminescence Thermochromism

Benito¹,

Goff²,

Nocton³

et al. 2015

Inorg. Chem.

139

144

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An original copper(I) iodide cluster of novel geometry obtained by using a diphosphine ligand is reported and is formulated [Cu6I6(PPh2(CH2)3PPh2)3] (1). Interestingly, this sort of "eared cubane" cluster based on the [Cu6I6] inorganic core can be viewed as a combination of the two known [Cu4I4] units, namely, the cubane and the open-chair isomeric geometries. The synthesis, structural and photophysical characterisations, as well as theoretical study of this copper iodide along with the derived cubane (3) and open-chair (2) [Cu4I4(PPh3)4] forms, were investigated. A new polymorph of the cubane [Cu4I4(PPh3)4] cluster is indeed presented (3). The structural differences of the clusters were analyzed by solid-state nuclear magnetic resonance spectroscopy. Luminescence properties of the three clusters were studied in detail as a function of the temperature showing reversible luminescence thermochromism for 1 with an intense orange emission at room temperature. This behavior presents different feature compared to the cubane cluster and completely contrasts with the open isomer, which is almost nonemissive at room temperature. Indeed, the thermochromism of 1 differs by a concomitant increase of the two emission bands by lowering the temperature, in contrast to an equilibrium phenomenon for 3. The luminescence properties of 2 are very different by exhibiting only one single band when cooled. To rationalize the different optical properties observed, density functional theory calculations were performed for the three clusters giving straightforward explanation for the different luminescence thermochromism observed, which is attributed to different contributions of the ligands to the molecular orbitals. Comparison of 3 with its [Cu4I4(PPh3)4] cubane polymorphs highlights the sensibility of the emission properties to the cuprophilic interactions.

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Molecules with an M4X4 core. IV. Crystallographic detection of a step configuration for the tetracopper tetraiodide core in tetrameric triphenylphosphinecopper(I) iodine, [PPh3CuI]4

Cited by 106 publications

References 0 publications

Complex formation between cuprous iodide and phenyl phosphine: a nuclear magnetic resonance and X-ray crystallographic study

Complex formation between cuprous iodide and phenyl phosphine: a nuclear magnetic resonance and X-ray crystallographic study

Polymorph and isomer conversion of complexes based on CuI and PPh₃easily observed via luminescence

Geometry Flexibility of Copper Iodide Clusters: Variability in Luminescence Thermochromism

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Molecules with an M4X4 core. IV. Crystallographic detection of a step configuration for the tetracopper tetraiodide core in tetrameric triphenylphosphinecopper(I) iodine, [PPh3CuI]4

Cited by 106 publications

References 0 publications

Complex formation between cuprous iodide and phenyl phosphine: a nuclear magnetic resonance and X-ray crystallographic study

Complex formation between cuprous iodide and phenyl phosphine: a nuclear magnetic resonance and X-ray crystallographic study

Polymorph and isomer conversion of complexes based on CuI and PPh3easily observed via luminescence

Geometry Flexibility of Copper Iodide Clusters: Variability in Luminescence Thermochromism

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Polymorph and isomer conversion of complexes based on CuI and PPh₃easily observed via luminescence