Expanding Luminescence Horizons in Macropolyhedral Heteroboranes

Luminescence is observed in three novel macropolyhedral nineteen‐ and eighteen‐vertex chalcogenaboranes: Se 2 B 17 H 17 ( 1 ), SeB 17 H 19 ( 3 ) and SeB 18 H 20 ( 4 ). This led us to the recognition that previously published macropolyhedral heteroborane species might also exhibit luminescence. Thus, the known nineteen‐ and eighteen‐vertex dithiaboranes S 2 B 17 H 17 ( 2 ), n ‐S 2 B 16 H 16 ( 5 ) and i ‐S 2 B 16 H 16 ( 6 ) were synthesised and also found to exhibit a range of luminescent properties. These macropolyhedral species are very different from the previously unique fluorescent binary borane B 18 H 22 in terms of their structural architectures, by the presence of borane cluster hetero atoms, and, as in the cases of 5 and 6 , that their synthetic origins are not derived simply through the modification of B 18 H 22 itself. They consequently greatly expand the possibilities of finding new luminescent inorganic borane species.