Microscopy Reveals: Impact of Lithium Salts on Elementary Steps Predicts Organozinc Reagent Synthesis and Structure.

Lithium chloride is known to promote the direct insertion of metallic zinc powder into organohalides in the practical synthesis of organozinc reagents, but the reason for its special ability is poorly understood. Pioneering a combined approach of single-metal-particle fluorescence microscopy with 1H NMR spectroscopy, we herein show that the effectiveness of different lithium salts toward solubilizing intermediates on the surface of zinc metal establishes a previously unknown reactivity correlation that predicts the propensity of that salt to promote macroscale reagent synthesis and also predicts the solution structure of the ultimate organozinc reagent. A salt-free pathway is also identified. These observations of an organometallic surface intermediate, its elementary-step reactivity, and the impact of various synthetic conditions (salt, salt-free, temperature, stirring, and time) on its persistence, are uniquely available from the sensitivity and spatial localization ability of the microscopy technique. These studies unify previously disparate observations under a single unified mechanistic framework. This framework enables the rational prediction of salt effects on multiple steps in organozinc reagent synthesis and reactivity. This is an early example of single-particle microscopy characterization of elementary steps providing predictive power in reaction development by gaining a sensitive and selective spectral handle on an important intermediate, highlighting the role of this next generation of analytical tools in the development of synthetic chemistry.

Control of Lanthanide Coordination Environment: Synthesis, Structure, and Oxygen-Sensitive Luminescence Properties of an Eight-Coordinate Tb(III) Complex.

Coordination environment of the Tb(3+) ion in oxygen-sensitive luminescent complexes can be successfully controlled through the size of alkyl substituents on ligands {((RMe)ArOH)4cyclen} (R = tBu or Me; cyclen = 1,4,7,10-tetraazacyclododecane); a newly prepared eight-coordinate complex 1(tBu) shows higher oxygen sensitivity (KSV = 17 600) and lower luminescence quantum yield (Φ = 0.67 under N2) than those of the previously reported seven-coordinate analogues 1(Me) and [{((MeMe)ArO)3tacn}Tb(III)(THF)] (KSV = 12 600 and 8300, Φ = 0.91 and 0.91 under N2, respectively; tacn = 1,4,7-triazacyclononane; THF = tetrahydrofuran). The oxygen-sensitive mechanism is discussed on the basis of the photophysical properties of the corresponding Gd(III) complexes.

An oxygen-sensitive luminescent Dy(iii) complex.

This paper presents the first dysprosium(iii) complex, [{((MeMe)ArO)3tacn}Dy(III)(THF)] (1(Dy)), that shows oxygen-sensitive luminescence. The synthesis, structure and oxygen-sensitive luminescence properties of 1(Dy) are reported (Φ = 0.050 and τ = 17.7 µs under N2, Φ = 0.011 and τ = 4.1 µs under O2 and KSV = 305 M(-1) in THF; KSV = 0.0077%(-1) in polystyrene film). The oxygen sensitive mechanism of 1(Dy) is discussed based on the photophysical properties of the corresponding gadolinium(iii) complex, [{((MeMe)ArO)3tacn}Gd(III)(THF)].

A gadolinium(iii) complex that shows room-temperature phosphorescence in the crystalline state.

This paper presents a gadolinium(iii) complex that shows blue phosphorescence in the crystalline state at room temperature under air atmosphere; color of the crystals can be changed to pale-green from blue by doping of 1-naphthol.

A highly luminescent and highly oxygen-sensitive Tb(III) complex with a tris-aryloxide functionalised 1,4,7-triazacyclononane ligand.

This communication presents a new terbium(III) complex that shows the highest luminescence quantum yield among the oxygen-sensitive lanthanide complexes (Φ = 0.91 under N2, Φ = 0.054 under air).