Metal-free organic emitters that display solution-phase room temperature phosphorescence (sRTP) remain exceedingly rare. Here, we investigate the structural and photophysical properties that support sRTP by comparing a recently reported sRTP compound (BTaz-Th-PXZ) to two novel analogous materials, replacing the donor group by either acridine or phenothiazine. The emissive triplet excited state remains fixed in all three cases, while the emissive charge-transfer singlet states (and the calculated paired charge-transfer T2 state) vary with the donor unit. While all three materials show dominant RTP in film, in solution different singlet-triplet and triplet-triplet energy gaps give rise to triplet-triplet annihilation followed by weak sRTP for the new compounds, compared to dominant sRTP throughout for the original PXZ material. Engineering both the sRTP state and higher charge-transfer states therefore emerges as a crucial element in designing emitters capable of sRTP.