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.