Does Twisted π-Conjugation Framework Always Induce Efficient Intersystem Crossing? A Case Study with Benzo[ b]- and [ a]Phenanthrene-Fused BODIPY Derivatives and Identification of a Dark State

The photophysical properties, especially the intersystem crossing (ISC) of two heavy-atom-free BODIPY derivatives with twisted π-conjugated frameworks (benzo[b]-fused BODIPY, BDP-B; and [a]phenanthrene-fused BODIPY, BDP-P), are studied with steady-state and time-resolved optical and electron paramagnetic resonance (TREPR) spectroscopic methods as well as with ADC(2) theoretical investigations. Interestingly, BDP-B has a planar π-conjugation framework, but it displays weaker UV-vis absorption (ε = 3.8 × 10⁴ M^-1 cm^-1 at 569 nm) and fluorescence (Φ_F < 0.1%), a short-lived singlet-excited state (fluorescence lifetime, τ_F = 0.2 ns), and a long-lived triplet state (τ_T = 132.3 μs). In comparison, the more twisted BDP-P shows stronger UV-vis absorption (ε = 9.8 × 10⁴ M^-1 cm^-1 at 640 nm) and fluorescence (Φ_F = 70%), longer singlet-excited-state lifetime (τ_F = 6.4 ns), and shorter triplet-state lifetime (τ_T = 18.9 μs). In contrast to helicenes (Φ_T = ca. 90%), the ISC of BDP-P and BDP-B is nonefficient (Φ_T < 23%). The electron spin selectivity of the ISC of the derivatives is different, manifested by the phase pattern of the TREPR spectra as AAEAEE and EEEAAA for BDP-B and BDP-P, respectively. The spatially confined T₁ state wave function of the twisted molecule keeps the T₁ state energy high (1.44-1.61 eV). A dark S₁ state was identified for BDP-B. This work demonstrated that the twisted π-conjugated framework does not necessarily induce efficient ISC and we found a dark singlet state for BODIPY, which is rare.