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 (ΦF < 0.1%), a short-lived singlet-excited state (fluorescence lifetime, τF = 0.2 ns), and a long-lived triplet state (τT = 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 (ΦF = 70%), longer singlet-excited-state lifetime (τF = 6.4 ns), and shorter triplet-state lifetime (τT = 18.9 µs). In contrast to helicenes (ΦT = ca. 90%), the ISC of BDP-P and BDP-B is nonefficient (ΦT < 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.

Spiro Rhodamine-Perylene Compact Electron Donor-Acceptor Dyads: Conformation Restriction, Charge Separation, and Spin-Orbit Charge Transfer Intersystem Crossing.

Spiro rhodamine (Rho)-perylene (Pery) electron donor-acceptor dyads were prepared to study the spin-orbit charge transfer intersystem crossing (SOCT-ISC) in these rigid and sterically congested molecular systems. The electron-donor Rho (lactam form) moiety is attached via the N-C bond to the electron acceptor at either 1- or 3-position of the Pery moiety (Rho-Pery-1 and Rho-Pery-3). Severe torsion of the Pery moiety in Rho-Pery-1 was observed. The fluorescence of the two dyads is significantly quenched in polar solvents, and the singlet oxygen quantum yields (ΦΔ) are strongly dependent on solvent polarity (4-36%). Femtosecond transient absorption spectra demonstrate that charge separation (CS) takes 0.51 ps in Rho-Pery-1 and 5.75 ps in Rho-Pery-3, and the charge recombination (CR)-induced ISC is slow (>3 ns). Nanosecond transient absorption spectra indicate that the formation of triplet states via SOCT-ISC takes 24-75 ns for Rho-Pery-1 and 6-15 ns for Rho-Pery-3, and the distorted π-framework of the Pery moiety results in a shorter triplet lifetime of 19.9 vs 291 µs for the planar analogue. Time-resolved electron paramagnetic resonance spectroscopy confirms the SOCT-ISC mechanism.

The effect of one-atom substitution on the photophysical properties and electron spin polarization: Intersystem crossing of compact orthogonal perylene/phenoxazine electron donor/acceptor dyad.

A perylene (Pery)-phenoxazine (PXZ) compact orthogonal electron donor/acceptor dyad was prepared to study the relationship between the molecular structures and the spin-orbit charge transfer intersystem crossing (SOCT-ISC), as well as the electron spin selectivity of the ISC process. The geometry of Pery-PXZ (80.0°) is different from the previously reported perylene-phenothiazine dyad (Pery-PTZ, 91.5°), although there is only one atom variation for the two dyads. Pery-PXZ shows a high singlet oxygen quantum yield (84%). Femtosecond transient absorption spectra indicate that the charge separation (CS, faster than 120 fs) is faster than the Pery-PTZ analog (CS, 250 fs) and charge recombination (CR, i.e., SOCT-ISC, 5.98 ns) of Pery-PXZ is slower than the Pery-PTZ analog (CR, 0.9 ns). The intrinsic triplet state lifetime of Pery-PXZ is 242 µs vs the lifetime of 181 µs for the Pery-PTZ analog. Moreover, the triplet state lifetime of Pery-PXZ in the solid polymer matrix is extended to 4.45 ms, which indicates that the triplet state of Pery-PXZ in fluid solution is deactivated not only by the triplet-triplet annihilation effect but also by other factors such as vibration coupled relaxation. Interestingly, with pulsed laser excited time-resolved electron paramagnetic resonance spectroscopy, the electron spin polarization (ESP) pattern of the triplet state of the current dyad is opposite to that of Pery-PTZ. These results demonstrated the rich electron spin chemistry of the ISC of compact electron donor/acceptor dyads, e.g., the ESP is dependent on not only the molecular geometry but also the structure of the electron donor (or acceptor).

N

To study the effect of a stable radical on the photophysical properties of a phosphorescent Pt(II) coordination framework and the intramolecular magnetic interaction between radical ligands in the N^N Pt(II) bisacetylide complexes, we prepared a series of N^N Pt(II) bis(acetylide) complexes with oxoverdazyl radical acetylide ligands. The linker between the Pt(II) center and the spin carrier was systematically varied, to probe the effect on the sign and magnitude of the spin exchange interactions between the radical ligands and photophysical properties. The complexes were studied with steady-state and femtosecond/nanosecond transient absorption spectroscopy, continuous-wave electron paramagnetic resonance (EPR) spectroscopy, and density functional theory (DFT) computations. The transient absorption spectral studies show that the doublet excited state of the radicals are short-lived (τD ≈ 2 ps) and nonfluorescent. Moreover, the intrinsic long-lived triplet excited state (τT = 1.2 µs) of the Pt(II) coordination center was efficiently quenched by the radical (τT = 6.9 ps for one representative radical Pt(II) complex). The intramolecular magnetic interaction between the radical ligands through the diamagnetic Pt(II) atom was studied with temperature-dependent EPR spectroscopy; antiferromagnetic exchange interaction (-J S1S2, J = -5.4 ± 0.1 cm-1) for the complex with the shortest radical-radical distance through bridge fragments was observed. DFT computations give similar results for the sign and magnitude of the J values. For complexes with larger inter-radical distance, however, very weak coupling between the radical ligands was observed (|J| < 0.7 cm-1). Our results are useful for the study of the effect of a radical on the photophysical properties of the phosphorescent transition-metal complexes.

Balance between Triplet States in Photoexcited Orthogonal BODIPY Dimers.

The intersystem crossing (ISC) and the triplet states in two representative BODIPY orthogonal dimers were studied with time-resolved electron paramagnetic resonance (TREPR) spectroscopy. The electron spin polarization (ESP) of the triplet state of the dimers, accessed with spin-orbit charge-transfer ISC, is different from that of the monomer (spin-orbit coupling-induced ISC). The TREPR spectra show that the triplet state initially formed by charge recombination is localized on either of two subunits, with different preference and ESP patterns. On the basis of the relative orientation of the respective zero field splitting principal axes, the Tx state on one subunit and the Tz state on another subunit in the dimer are overpopulated. The balance between the two triplet states is confirmed by the temperature dependency of the population ratio. No quintet state was detected with TREPR down to 20 K; thus, the recently proposed singlet fission ISC mechanism is excluded.