Sterically Hindered Luminescent PtII–Phosphite Complexes for Electroluminescent Devices

Pt^II complexes with one bulky, sterically demanding, tertiary phosphite ancillary ligand and a coordinating chromophore are herein presented. The phosphite ligand, tris(2,4‐di‐tert‐butylphenyl) acts as a bidentate ligand coordinating the platinum ion through the central phosphorus atom and a cyclometalating carbon atom of one of the substituents. The two free phenoxy moieties lie above and below the coordination plane, leading to steric hindrance that avoids aggregation and provides solubility in organic solvents. The other two coordination sites on the central metal ion are occupied by a chromophoric ligand, which is responsible for the energy of the luminescent excited state. This separation of functions, on the two coordinated ligands, allows the use of a wider range of luminophores with good luminescent properties, maintaining the control of the intermolecular interactions with the non‐chromophoric ligand. Based on this approach we were able to achieve a bright deep blue emission (λ=444 nm, Φ_em=0.38) from a complex with a tailored ligand, which was then used for the fabrication of an electroluminescent device. In addition commercially available luminophores were also employed to synthesize green emitters.     

Pair correlation and equidistribution on manifolds

This study is motivated by a series of recent papers that show that, if a given deterministic sequence in the unit interval has a Poisson pair correlation function, then the sequence is uniformly distributed. Analogous results have been proved for point sequences on higher-dimensional tori. The purpose of this paper is to describe a simple statistical argument that explains this observation and furthermore permits a generalisation to bounded Euclidean domains as well as compact Riemannian manifolds.     

Diaryldichalcogenide radical cations

One-electron oxidation of two series of diaryldichalcogenides (C₆F₅E)₂ (13a–c) and (2,6-Mes₂C₆H₃E)₂ (16a–c) was studied (E = S, Se, Te). The reaction of 13a and 13b with AsF₅ and SbF₅ gave rise to the formation of thermally unstable radical cations [(C₆F₅S)₂]˙⁺ (14a) and [(C₆F₅Se)₂]˙⁺ (14b) that were isolated as [Sb₂F₁₁]^– and [As₂F₁₁]^– salts, respectively. The reaction of 13c with AsF₅ afforded only the product of a Te–C bond cleavage, namely the previously known dication [Te₄]²⁺ that was isolated as [AsF₆]^– salt. The reaction of (2,6-Mes₂C₆H₃E)₂ (16a–c) with [NO][SbF₆] provided the corresponding radical cations [(2,6-Mes₂C₆H₃E)₂]˙⁺ (17a–c; E = S, Se, Te) in the form of thermally stable [SbF₆]^– salts in nearly quantitative yields. The electronic and structural properties of these radical cations were probed by X-ray diffraction analysis, EPR spectroscopy, and density functional theory calculations and other methods.     

Adsorption of I2 by Macrocyclic Polyazadithiophenolato Complexes Mediated by Charge‐Transfer Interactions

The macrocyclic complex [Ni₂(L)(OAc)]ClO₄ ( 1 ) adsorbs up to 17 molar equivalents (>270 wt %) of iodine, although it does not exhibit permanent porosity. Vibrational spectroscopic and crystallographic studies reveal that two I₂ molecules are captured by means of thiophenolate→I₂ charge‐transfer interactions, which enable the diffusion and sorption of further I₂ molecules in a polyiodide‐like network. The efficient sorption and desorption characteristics make this material suitable for accommodation, sensing, and slow release of I₂.