Ultrafast dynamics of mCP and Br-mCP: Insights from transient absorption spectroscopy

Heavy atom activated organic room-temperature phosphorescence (RTP) has attracted considerable interest due to its high phosphorescence quantum yield and prolonged lifetime. This research provides a detailed analysis of the transient absorption spectroscopy of 1,3-Bis(N-carbazolyl)benzene (mCP) and 9,9'-(5-Bromo-1,3-phenylene)bis(9H-carbazole) (Br-mCP) in toluene solution. In the femtosecond transient absorption (fs-TA) spectroscopy of mCP, the excited state absorption (ESA) signal decreases at 630 nm while the triplet-triplet absorption (TTA) signal increases at 420 nm. Meanwhile, the isosbestic point observed at 455 nm indicates an intersystem crossing (ISC) lifetime of 15.4 ns. Moving on to the nanosecond transient absorption (ns-TA) spectroscopy, the TTA signal reaches its peak at 27.3 ns before decreasing, with the triplet lifetime of mCP measured at 2.8 μs. Br-mCP exhibits a similar dynamic evolution to mCP, but with a quicker ISC process (9.4 ns) and a longer triplet lifetime (3.9 μs). The quicker ISC process in Br-mCP is ascribed to the presence of heavy atom in the molecular structure, leading to an enhanced spin-orbit coupling constant (ξ(S1, T3)Br-mCP = 1.371 cm−1 > ξ(S1, T4)mCP = 0.060 cm−1). The prolonged triplet lifetime of Br-mCP (3.9 μs > 2.8 μs) results from its lower reorganization energy, effectively reducing non-radiative vibrational energy losses within the molecule. This work significantly enhances our understanding of RTP materials incorporating heavy atoms. •The photodynamic processes of mCP and Br-mCP molecules were investigated using transient absorption spectroscopy.•The influence of the heavy-atom effect on intersystem crossing and the triplet state lifetime of the molecule was examined.•The reduction of reorganization energy can effectively mitigate the non-radiative energy loss of the molecule.