Ultrafast Intramolecular Charge Transfer with N-(4-Cyanophenyl)carbazole. Evidence for a LE Precursor and Dual LE plus ICT Fluorescence

The photophysics of N-(4-cyanophenyl)carbazole (NP4CN) was investigated by using absorption and fluorescence spectra, picosecond fluorescence decays, and femtosecond transient absorption. In the nonpolar n-hexane as well as in the polar solvent acetonitrile (MeCN), a locally excited (LE) state is detected, as a precursor for the intramolecular charge transfer (ICT) state. A LE -> ICT reaction time tau(2) at 22 degrees C of 0.95 ps in ethyl cyanide (EtCN) and 0.32 ps in MeCN is determined from the decay of the LE excited state absorption (ESA) maximum around 620 nm. In the ESA spectrum of NP4CN in n-hexane at a pump-probe delay time of 100 ps, an important contribution of the LE band remains alongside the 1CT band, in contrast to what is observed in EtCN and MeCN. This shows that a LE reversible arrow ICT equilibrium is established in this solvent and the ICT reaction time of 0.5 ps is equal to the reciprocal of the sum of the forward and backward ICT rate constants 1/(k(a) + k(d)). In the photostationary S-o -> S-n absorption spectrum of NP4CN in n-hexane and MeCN, an additional CT absorption band appears, absent in the sum of the spectra of its electron donor (D) and acceptor (A) subgroups carbazole and benzonitrile. This CT band is located at an energy of similar to 4000 cm(-1) lower than for N-phenylcarbazole (NPC), due to the larger electron affinity of the benzonitrile moiety of NP4CN than the phenyl subunit of NPC. The fluorescence spectrum of NP4CN in n-hexane at 25 degrees C mainly consists of a structured LE emission, with a small ICT admixture, indicating that a LE -> ICT reaction just starts to occur under these conditions. In di-n-pentyl ether (DPeE) and di-n-butyl ether (DBE), a LE emission is found upon cooling at the high-energy edge of the ICT fluorescence band, caused by the onset of dielectric solvent relaxation. This is not the case in more polar solvents, such as diethyl ether (DEE) and MeCN, in which a structureless ICT emission band fully overlaps the strongly quenched LE fluorescence. For the series of D/A molecules NPC, N-(4-fluorophenyl)carbazole (NP4F), N-[4-(trifluoromethyl)phenyl]-carbazole (NP4CF), and NP4CN, with increasing electron affinity of their phenyl subgroup, an ICT emission in n-hexane 25 degrees C only is present for NP4CN, whereas in MeCN an ICT fluorescence is observed with NP4CF and NP4CN. The ICT fluorescence appears when for the energies E(ICT) of the ICT state and E(S-1) of the lowest excited singlet state the condition E(ICT) <= E(S-1) holds. E(ICT) is calculated from the difference E(D/D+) - E(A(-)/A) of the redox potentials of the D and A subgroups of the N-phenylcarbazoles. From solvatochromic measurements with NP4CN an ICT dipole moment mu e(ICT) = 19 D is obtained, somewhat larger than the literature values of 10-16 D, because of a different Onsager radius p. The carbazole/phenyl twist angle theta = 45 degrees of NP4CN in the S-o ground state, determined from X-ray crystal analysis, has become smaller for its ICT state, in analogy with similar conclusions for related N-phenylcarbazoles and other D/A molecules in the literature.