The Overlooked Dual Phosphorescence of Lappert's Diamino Stannylene Sn[N(SiMe3)2]2

The diamino stannylene Sn[N(SiMe₃)₂]₂ shows rich photophysics and photochemistry: unprecedented dual green/orange phosphorescence with long excited state lifetimes, excimer formation, and unimolecular bond homolysis. Photolytic Sn─N bond homolysis occurs only in the long-lived excited monomer but not in the excimer.

Abstract

The first stable heavy carbene homologues, the heavy tetrylenes, were reported in 1973 by Lappert and coworkers. These tetrylenes were extensively investigated with respect to ground state reactivity, such as small molecule activation, insertion into σ-bonds, coordination chemistry, materials chemistry, or catalysis. Their photophysical properties remained essentially unexplored. We report that the bright yellow-colored diamino stannylene Sn[N(SiMe₃)₂]₂ shows thermally activated dual orange/green phosphorescence with microsecond lifetime in fluid solution at room temperature, which has been overlooked for more than 50 years. These unique electronic and photophysical properties are studied in detail by temperature-dependent time-resolved emission and absorption spectroscopy and are corroborated by (time-dependent) density functional theory (DFT) calculations. The mechanism of photochemical radical formation has been disclosed, involving unprecedented stannylene excimers with second-order Jahn–Teller distorted structures. The present study provides new insights toward a rational design of tetrel(II) complexes with long-lived emissive excited states, with Sn[N(SiMe₃)₂]₂ being the prototype.

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