Fluorinated Tetraarylethenes: Universal Tags for the Synthesis of Solid State Luminogens.

The aggregation-induced emission properties of tetraarylethenes (TAEs) have led to numerous applications in chemistry, biology, and materials science. Herein, we describe two fluorinated tetraarylethenes, which can be employed as universal tags for the synthesis of solid state luminogens. The tags are accessible in one or two steps from commercially available starting materials. Facile coupling reactions with ubiquitous substrates such as thiols, alcohols, amines, phosphines, aldehydes, and enamines allow preparing a wide range of TAE conjugates, including tagged amino acids, peptides, carbohydrates, steroids, and commercial polymers.

Towards Naked Zinc(II) in the Condensed Phase: A Highly Lewis Acidic ZnII Dication Stabilized by Weakly Coordinating Carborate Anions.

The employment of the hexyl-substituted anion [HexCB11 Cl11 ]- allowed the synthesis of a ZnII species, Zn[HexCB11 Cl11 ]2 , 3, in which the Zn2+ cation is only weakly coordinated to two carborate counterions and that is soluble in low polarity organic solvents such as bromobenzene. DOSY NMR studies show the facile displacement of at least one of the counterions, and this near nakedness of the cation results in high catalytic activity in the hydrosilylation of 1-hexene and 1-methyl-1cyclohexene. Fluoride ion affinity (FIA) calculations reveal a solution Lewis acidity of 3 (FIA=262.1 kJ mol-1 ) that is higher than that of the landmark Lewis acid B(C6 F5 )3 (FIA=220.5 kJ mol-1 ). This high Lewis acidity leads to a high activity in catalytic CO2 and Ph2 CO reduction by Et3 SiH and hydrogenation of 1,1-diphenylethylene using 1,4-cyclohexadiene as the hydrogen source. Compound 3 was characterized by multinuclear NMR spectroscopy, mass spectrometry, single crystal X-ray diffraction, and DFT studies.