Fluoride Anion Complexation by a Triptycene‐Based Distiborane: Taking Advantage of a Weak but Observable C−H⋅⋅⋅F Interaction

Fluoride anion complexation impacts a number of areas ranging from sensing to nucleophilic fluorination chemistry. Described here is a new bidentate Lewis acid consisting of two stiborane units connected by a 1,8‐triptycenediyl backbone. This neutral derivative captures fluoride with an unprecedented affinity for a neutral, water‐compatible Lewis acid. Structural, spectroscopic and computational studies demonstrate that fluoride anion binding is assisted by the formation of a C−H⋅⋅⋅F hydrogen bond which involves a methine group of the 1,8‐triptycenediyl backbone.     

Gas-Chromatographie von Tl, Se, Te, Hg, As, Sb, Bi, Sn als Phenylverbindungen

Zusammenfassung Die Phenylverbindungen von Thallium, Selen, Tellur, Quecksilber, Arsen, Antimon, Wismut und Zinn sind zur gas-chromatographischen Analyse dieser Elemente geeignet. Sie entstehen bis auf Thalliumtriphenyl quantitativ beim Umsatz der aus saurer Lösung extrahierten Diäthyldithiocarbamidate mit magnesiumorganischen Verbindungen. Gas-chromatographisch lassen sich die Phenylverbindungen aller acht Elemente mit einer Säule unter Verwendung eines Temperaturprogramms trennen. Im Falle des Quecksilberdiphenyls konnte keine vollständige Elution erreicht werden.Vortrag anläßlich der Tagung Euroanalysis I, 28. 8.–1. 9. 1972 in Heidelberg.     

CsSbF2SO4: An Excellent Ultraviolet Nonlinear Optical Sulfate with a KTiOPO4 (KTP)‐type Structure

A novel noncentrosymmetric (NCS) polar fluoride sulfate, CsSbF₂SO₄, was obtained by ionothermal synthesis. A meticulously designed co‐substitution approach was used to successfully replace the [TiO₆]^8? and [PO₄]^3? functional groups in KTiOPO₄ (KTP) with [SbO₄F₂]^7? and [SO₄]^2? units, respectively. The structure of CsSbF₂SO₄ features a pseudo‐3D framework consisting of interconnected 1D [SbF₂O₂SO₄]^5? chains of corner‐sharing [SbO₄F₂]^7? octahedra and [SO₄]^2? tetrahedra. The title compound exhibits a sharply enlarged band gap compared to its parent compound, KTP, benefitting from the introduction of F^? ions and the displacement of Sb³⁺ cations. Second harmonic generation (SHG) measurements manifested that CsSbF₂SO₄ is phase‐matchable and revealed a strong SHG response of about 3.0 KH₂PO₄ (KDP), which is the highest value reported for any metal sulfate reported to date. The reported fluoride sulfate is a promising near ultraviolet (UV) nonlinear optical (NLO) material.