Phosphorescence Tuning through Heavy Atom Placement in Unsymmetrical Difluoroboron β-Diketonate Materials

Difluoroboron β-diketonates (BF₂bdks) show both fluorescence (F) and room-temperature phosphorescence (RTP) when confined to a rigid matrix, such as poly(lactic acid). These materials have been utilized as optical oxygen sensors (e.g., in tumors, wounds, and cells). Spectral features include charge transfer (CT) from the major aromatic donor to the dioxaborine acceptor. A series of naphthyl–phenyl dyes (BF₂nbm) (1–6) were prepared to test heavy-atom placement effects. The BF₂nbm dye (1) was substituted with Br on naphthyl (2), phenyl (3), or both rings (4) to tailor the fluorescence/phosphorescence ratio and RTP lifetime—important features for designing O₂ sensing dyes by means of the heavy atom effect. Computational studies identify the naphthyl ring as the major donor. Thus, Br substitution on the naphthyl ring produced greater effects on the optical properties, such as increased RTP intensity and decreased RTP lifetime compared to phenyl substitution. However, for electron-donating piperidyl-phenyl dyes (5), the phenyl aromatic is the major donor. As a result, Br substitution on the naphthyl ring (6) did not alter the optical properties significantly. Experimental data and computational modeling show the importance of Br position. The S₁ and T₁ states are described by two singly occupied MOs (SOMOs). When both of these SOMOs have substantial amplitude on the heavy atom, passage from S₁ to T₁ and emission from T₁ to S₀ are both favored. This shortens the excited-state lifetimes and enhances phosphorescence.