Oligothiophene-Ring-Strapped Perylene Bisimides: Functionalizable Coaxial Donor-Acceptor Macrocycles.

Aesthetic designs from nature enable new knowledge to be gained and, at the same time, inspire scientific models. In this context, multicomponent macrocycles embody the advantage of precisely positioning the structural units to achieve efficient communication between them. However, the construction of a functionalizable macrocycle for ultrafast charge separation and stabilization has not been attempted. Herein, we report the synthesis, crystal structure, and transient absorption of a new functionalizable macrocycle consisting of an oligothiophene-ring-strapped perylene bisimide. Transient absorption results point to a sequential improvement in charge separation and stabilization from the macrocycle to the corresponding linear dimer and 2D polymer due to the unique design. Our macrocycle design with a supportive spatial arrangement of the donor and acceptor units will inspire the development of more complex synthetic systems with exciting electron-transfer and charge-separation features.

Probing ultrafast hot charge carrier migration in MoS2 embedded CdS nanorods.

Efficient utilization of hot charge carriers is of utmost benefit for a semiconductor-based optoelectronic device. Herein, a one-dimensional (1D)/two-dimensional (2D) heterojunction was fabricated in the form of CdS/MoS2 nanorod/nanosheet composite and migration of hot charge carriers was being investigated with the help of transient absorption (TA) spectroscopy. The band alignment was such that both the electrons and holes in the CdS region tend to migrate into the MoS2 region following photoexcitation. The composite system is composed of optical signatures of both CdS and MoS2, with the dominance of CdS nanorods. In addition, the TA signal of MoS2 is substantially enhanced in the heterosystem at the cost of the diminished CdS signal, confirming the migration of charge carrier population from CdS to MoS2. This migration phenomenon was dominated by the hot carrier transfer. The hot carriers in the high energy states of CdS are preferentially migrated into the MoS2 states rather than being cooled to the band edge. The hot carrier transfer time for a 400 nm pump excitation was calculated to be 0.21 ps. This is much faster than the band edge electron transfer process, occurring at 2.0 ps time scale. We found that these migration processes are very much dependent on the applied pump photon energy. Higher energy pump photons are more efficient in the hot carrier transfer process and place these hot carriers in the higher energy states of MoS2, further extending charge carrier separation. This detailed spectroscopic investigation would help in the fabrication of better 1D/2D heterojunctions and advance the optoelectronic field.