Emission from electronically excited species forms the basis for an important class of light sources-lasers. So far, commercially available solution-processed blue-emitting laser materials are based on organic compounds or semiconductor nanocrystals that have significant limitations: either low solubility, low chemical-and/or photo-stability and/or uncompetitive prices. Here we report a novel and competitive alternative to these existing laser materials that is based on boron hydrides, inorganic cluster compounds with a rich and diverse chemistry. We demonstrate that solutions of the borane anti-B 18 H 22 show, under pulsed excitation, blue laser emission at 406 nm with an efficiency (ratio of output/input energies) of 9.5%, and a photostability superior to many of the commercially available state-of-the-art blue laser dyes. This demonstration opens the doors for the development of a whole new class of laser materials based on a previously untapped resource for laser technology-the boranes.

The tuning of the photophysical properties of the highly fluorescent boron hydride cluster anti-B18H22 (1), by straightforward chemical substitution to produce 4,4'-(HS)2-anti-B18H20 (2), facilitates intersystem crossing from excited singlet states to a triplet manifold. This subsequently enhances O2((1)Δg) singlet oxygen production from a quantum yield of ΦΔ ∼ 0.008 in 1 to 0.59 in 2. This paper describes the synthesis and full structural characterization of the new compound 4,4'-(HS)2-anti-B18H20 (2) and uses UV-vis spectroscopy coupled with density functional theory (DFT) and ab initio computational studies to delineate and explain its photophysical properties.

Treatment of the laser borane anti-B18H22 (compound 1) with iodine in ethanol gives the monoiodinated derivative 7-I-anti-B18H21 (compound 2) in 67% yield, or, by reaction with iodine or ICl in the presence of AlCl3 in dichloromethane, the diiodinated derivative 4,4′-I2-anti-B18H20 (compound 3) in 85% yield. On excitation with 360 nm light, both compounds 2 and 3 give strong green phosphorescent emissions (λmax = 525 nm, ΦL = 0.41 and λmax = 545 nm, ΦL = 0.71 respectively) that are quenched by dioxygen to produce O2(1Δg) singlet oxygen with quantum yields of ΦΔ = 0.52 and 0.36 respectively. Similarly strong emissions can be stimulated via the nonlinear process of two-photon absorption when exciting with 720 or 800 nm light. The high quantum yields of singlet-oxygen production, coupled with the option of two-photon excitation, make compounds 2 and 3 promising O2(1Δg) photosensitizers. The molecular structures of compounds 2 and 3 were determined by single-crystal X-ray crystallographic studies as well as multinuclear NMR spectroscopy and mass spectrometry. Time-resolved UV–vis spectroscopy was used to delineate their photophysical properties, and the electronic-structure properties of the emitting species were determined by means of multiconfigurational quantum-chemistry computations.

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