Excitation-dependent electron exchange energy and electron transfer dynamics in a series of covalently tethered N,N-bis(4'-tert-butylbiphenyl-4-yl)aniline - [C] fullerene dyads via varying π-conjugated spacers.

Femtosecond time-resolved fluorescence and transient absorption studies are reported for three newly synthesized covalently linked N,N-bis(4'-tert-butylbiphenyl-4-yl)aniline (BBA) and pyrrolidinofullerenes (C60)-based donor-π conjugated bridge-acceptor dyads (D-B-A) as functions of the bridge length (7.1, 9.5 and 11.2 Å for Dyad-1, Dyad-2 and Dyad-3), dielectric constants of the medium and pump wavelengths. In polar solvent, ultrafast fluorescence quenching (kEET ≥ 2 × 1012 s-1) of the BBA moiety upon excitation of the BBA moiety (320 nm) is observed in the dyads and is assigned to a mechanism involving electron exchange energy transfer (EET) from 1BBA* to C60 followed by electron transfer from BBA to 1C60*. Cohesive rise and decay dynamics of conjugated BBA˙+-C60˙- anion pairs confirm the involvement of a distance independent adiabatic charge-separation (CS) process (kCS ≥ 2.2 × 1011 s-1) with near unity quantum efficiency (φCS ≥ 99.7%) and a distance-dependent non-adiabatic charge-recombination (CR) process [kCR ∼ (1010-108) s-1]. In contrast, excitation of the C60 moiety (λex = 430 to 700 nm) illustrates photoinduced electron transfer from BBA to 1C60*, involving non-adiabatic (diabatic) and distance-dependent CS (kCS in the range of 0.59-1.78 × 1011 s-1) with 98.86-99.6% (Dyad-3-Dyad-1) quantum efficiency and a CR process with kCR values [kCR ∼ (1010-108) s-1] up to three orders greater than kCS of the respective dyads. Both the processes, CS and CR, upon C60 excitation and the CR process upon BBA excitation show distance dependent rate constants with exponential factor β ≤ 0.5 Å-1, and electron transfer is concluded to occur through a covalently linked conjugated π bridge. Global and target analysis of fsTA data reveal the occurrence of two closely lying CS states, thermally hot (CShot) and thermally relaxed (CSeq) states, and two CR processes with two orders of different rate constants. Careful analysis of the kinetic and thermodynamic data allowed us to estimate the total reorganization energy and electronic coupling matrix (V), which decrease exponentially with distance. These novel features of the distance independent adiabatic CS process and the distance-dependent diabatic CR process upon donor excitation are due to extending the π-conjugation between BBA and C60. The demonstrated results may provide a benchmark in the design of light-harvesting molecular devices where ultrafast CS processes and long-lived CS states are essential requirements.