Modulating Resonance Energy Transfer with Supramolecular Control in a Layered Hybrid Perovskite and Chromium Photosensitizer Assembly

Recently, the low-dimensional organic-inorganic halide perovskites (OIHP) have been exploited heavily for their favorable exciton dynamics, broad-band emission, remarkable stability, and tunable band-edge excited-state energy compared to their 3D counterparts for potential optoelectronic applications. Low-dimensional perovskites are generally good candidates for utilization as room-temperature photoluminescence (PL) materials. Further, doping divalent transition metals like Mn²⁺ into OIHP is expected to introduce a ⁴T₁-⁶A₁-based low-energy luminescence emission around 600 nm; an optical property that is favorable for biomedical optoelectronics. Doping Mn²⁺ in the perovskite lattice is also expected to induce the generation of cytotoxic singlet oxygen species (¹O₂), a ROS that is being exploited for various therapeutic applications. To integrate these optical and therapeutic properties of a 2D (PEA)₂PbBr₄ (Pb PeV; PEA = phenylethylammonium cation) perovskite alloyed with Mn²⁺ ions (Mn:PbPeV) and the option for a photoinduced energy transfer process involving a Cr(III)-based ¹O₂ generating photosensitizer (CrPS), we designed a unique purpose-built nanoassembly (Mn:PbPeV@PCD) using the encapsulation properties of a water-soluble polymer derived from β-cyclodextrin (PCD). Here the PCD is observed to modulate the classical internal energy transfer of Pb²⁺ exciton to alloyed Mn²⁺ orange emission, resulting in the emergence of a new blue emission. The addition of CrPS into the Mn:PbPeV@PCD to generate the CrPS@Mn:PbPeV@PCD assembly results in restoring perovskite luminescence followed by the external energy transfer to CrPS. We have elucidated the mechanism of these cascade energy transfer processes between multiple components using steady-state and time-resolved luminescence techniques. Efficient ROS generation and its potential to induce an oxidation reaction of a biomolecule are realized using guanine as the target molecule. Further photoinduced cleavage studies with biomolecules confirmed the efficacy of the nanoassembly in inducing the cleavage of guanine-rich DNA. The study opens up a new direction in the field of perovskite for biomedical applications.