17585-86-3Relevant academic research and scientific papers
Thermoluminescent Antimony-Supported Copper-Iodo Cuboids: Approaching NIR Emission via High Crystallographic Symmetry
Taylor, William V.,Cammack, Claudina X.,Shubert, Sofia A.,Rose, Michael J.
, p. 16330 - 16345 (2019)
We report the syntheses, structures, and luminescence properties of a series of copper-iodo cuboids supported by L-type antimony ligands. The cuboids are of general formula [(SbR3)4Cu4(I)4] (1-4, 8), where SbR3 is a series of homoleptic and heteroleptic stibines containing both phenyl and a variety of alkyl substituents (R = Cy, iPr, tBu, Ph); triphenyl, iPr2Ph, and Me2Ph stibines resulted in the formation of dimers of type [(SbR3)4(Cu)2(I)2] (5-7). While similar luminescent copper-halide cubes have been studied, the corresponding "heavy-atom" congeners have not been studied, and ligation of such heavy-atom moieties is often associated with long-lived triplet states and low-energy absorption and emission profiles. Overall, two obligate parameters are found to imbue NIR emission: (i) short Cu-Cu bonds and (ii) high crystallographic symmetry; both of these properties are found only in [(SbiPr3)4Cu4(I)4] (1, in I23; λem = 711 nm). The correlation between NIR emission and high crystallographic symmetry (which intrinsically includes high molecular symmetry)-versus only molecular symmetry-is confirmed by the counterexample of the molecularly symmetric tBu-substituted cuboid [(SbtBu3)4Cu4(I)4] (3, λem = 588 nm, in R-3), which crystallizes in the lower symmetry trigonal space group. Despite the indication that the stronger donor strength of the SbtBu3 ligand should red-shift emission beyond that of the SbiPr3-supported cuboid, the emission of 3 is limited to the visible region. To further demonstrate the connection between structural parameters and emission intensity, X-ray structures for 1 and 3 were collected between 100 and 300 K. Lastly, DFT calculations for 1 on its singlet (S0) and excited triplet state (T1) demonstrate two key factors necessary for low-energy NIR emission: (i) a significant contraction of the interconnected Cu4 intermetallic contacts [～2.45 → 2.35 ?] and (ii) highly delocalized (and therefore low-energy) A1 symmetry HOMO/LUMO orbitals from which the emission occurs. Thus, any molecular or crystallographic distortion of the Cu4 core precludes the formation of highly symmetric (and low-energy) HOMO/LUMO orbitals in T1, thereby inhibiting low-energy NIR emission.
Aqueous electrochemistry of quaternary organoantimony ions
Kok, Gregory L.,Morris, Michael D.
, p. 2146 - 2150 (1972)
The series of quaternary organoantimony ions, (CH3)m(C6H5)m-4Sb + (m = 1-4), has been studied in aqueous solution using dc polarography, cyclic voltammetry, and controlled potential electrolysis. Tetramethylantimony ion undergoes a single two-electron reduction to trimethylantimony and methane. The other three ions in the series are reduced in two one-electron steps. The first electron transfer involves the formation of an antimony(IV) species which rapidly reacts with the electrode metal to form an organomercury radical and a trivalent organoantimony compound. The organomercury radical disproportionates to form a diorganomercury compound. The second electron transfer gives trivalent organoantimony compounds and hydrocarbons. In two of the three possible cases both methyl and phenyl groups are lost by the antimony. The relative losses are different following the first and second electron transfer. Two factors govern the loss of the hydrocarbon group: the stability of the resulting hydrocarbon radical or carbanion and the stability of the resulting antimony compounds.
Syntheses, Structures, and Characterization of Nickel(II) Stibines: Steric and Electronic Rationale for Metal Deposition
Taylor, William V.,Xie, Zhu-Lin,Cool, Nicholas I.,Shubert, Sofia A.,Rose, Michael J.
, p. 10364 - 10374 (2018/08/28)
Reactions of the homoleptic and heteroleptic antimony ligands SbiPr3, SbiPr2Ph, SbMe2Ph, and SbMePh2 with NiI2 generate rare NiII stibine complexes in either square planar or trigonal bipyramidal (TBP) geometries, depending on the steric size of the ligands. Tolman electronic parameters were calculated (DFT) for each antimony ligand to provide a tabulated resource for the relative strengths of simple antimony ligands. The electronic absorbance spectra of the square planar complexes exhibit characteristic bands [λmax ≈ 560 nm (17 900 cm-1), ? ≈ 4330 M-1 cm-1] at lower energies compared to the reported phosphine complexes, indicating the weak donor strength of the stibine ligands and resultant low-energy ligand field d→d transitions. The square planar complex Ni(I)2(SbiPr3)2 reacts with CO to form the TBP complex Ni(I)2(SbiPr3)2(CO). Lastly, the complexes were investigated for nickel metal deposition on Si|Cu(100 nm) substrates. The complexes with the strongest donating ligand, SbiPr3, deposited the purest layer of NiCu alloy according to the balanced reaction Ni(I)2(SbIIIiPr3)2 → Ni0 + SbV(iPr3)I2; the iodinated SbV byproduct was unambiguously detected in the supernatant by 1H NMR and mass spectrometry. Complexes with weaker ligands (poor I2 acceptors/scavengers) resulted undesired deposition of iodine and CuI on the surface. This work thus serves as a guide for the design and synthesis of 3d metal complexes with neutral, heavy main-group donors that are useful for metal deposition applications.
Synthesis and properties of new ditertiary stibines based upon o-, m- or p-xylyl and m- or p-phenylene backbones and their complexes with tungsten, iron and nickel carbonyls
Levason, William,Matthews, Melissa L.,Reid, Gillian,Webster, Michael
, p. 51 - 58 (2007/10/03)
High yield syntheses for 1,2-, 1,3-, and 1,4-xylyl distibines (1,2-C6H4(CH2SbMe2)2, 1,3-C6H4(CH2 SbMe2)2, 1,4-C6H4(CH2 SbMe2)2, respectively) from Me2SbCl (conveniently made in situ from Me2PhSb and HClgas) and the appropriate di-Grignard are reported. The 1,3- and 1,4-phenylene distibines, 1,3-C6H4(SbMe2)2 and 1,4-C6H4(SbMe2)2, were made similarly. The new ligands have been characterised by mass spectrometry, 1H and 13C{1H} NMR spectroscopy, and by the preparation of methiodide derivatives. The crystal structures of 1,4-C6H4(CH2 SbMe2)2 and [1,3-C6H4(CH2 SbMe3)2]I2 have been determined. The synthesis of 1,2-C6H4-(CH2 SbPh2)2 has been achieved similarly in modest yield and the distibine converted into the tetra-iodo-derivative 1,2-C6H4(CH2SbPh2 I2)2. The coordination modes available to these ligands have been probed by the synthesis and characterisation of complexes with nickel, iron and tungsten carbonyls. The crystal structure of [{Fe(CO)4}2-{μ-1,3-C6H4 (CH2SbMe2)2}] has been determined. The spectroscopic properties of these carbonyl derivatives have been compared with those of complexes of other antimony ligands, and in some cases with diphosphine and diarsine complexes, to probe the electronic properties of the new ligands.
Novel syntheses of Me2SbX (X = Cl, I) and crystal structures of Me2SbI and [(Me3Si)2CH]2SbCl
Breunig,Althaus,Roesler,Lork
, p. 1137 - 1140 (2008/10/08)
The crystal structures of Me2SbI (Me = CH3) and [(Me3Si)2CH]2SbCl have been determined by X-ray methods. Both molecules are pyramidal. The Me2SbI molecules are associated to chains through
ORGANOSTIBINES AS LIGANDS. SYNTHESIS OF DIMETHYL(Α-PICOLYL)STIBINE, DIMETHYL(8-QUINOLYL)STIBINE, AND (R;S)-METHYLPHENYL(8-QUINOLYL)STIBINE AND SOME TRANSITION METAL DERIVATIVES
Shewchuk, Eric,Wild, Stanley Bruce
, p. 181 - 192 (2007/10/02)
The unsymmetrical mono-tertiary stibines dimethyl(α-picolyl)stibine (picstib), dimethyl(8-quinolyl)stibine (quinstib), and (R; S)-methylphenyl(8-quinolyl)-stibine (R; S-quinstib) have been synthesised and the square-planar complexes , MX2(q
