Unraveling an Ultrafast Electron Transport Mechanism in a Photocatalytic "Micromachine" for Their Potential Light Harvesting Applications.

Following the seminal discovery of Richard Feynman, several micromachines have been made that are capable of several applications, such as solar energy harvesting, remediation of environmental pollution, etc. Here we have synthesized a nanohybrid combining TiO2 nanoparticle and light harvesting robust organic molecule RK1 (2-cyano-3-(4-(7-(5-(4-(diphenylamino)phenyl)-4-octylthiophen-2-yl)benzo[c][1,2,5] thiadiazol-4-yl)phenyl) acrylic acid) as a model micromachine having solar light harvesting ability potential for application in photocatalysis, preparation of solar active devices, etc. Detailed structural characterization, including High Resolution Transmission Electronic Microscopy (HRTEM) and Fourier-transform infrared spectroscopy (FTIR), has been performed on the nanohybrid. We have studied the excited-state ultrafast dynamics of the efficient push-pull dye RK1 in solution, on mesoporous semiconductor nanoparticles, and in insulator nanoparticles by streak camera (resolution of the order of 500 fs). The dynamics of such photosensitizers in polar solvents have been reported, and it has been observed that completely different dynamics occur when they are attached to the surface of the semiconductor/insulator nanosurface. A femtosecond-resolved fast electron transfer has been reported when photosensitizer RK1 has been attached to the surface of the semiconductor nanoparticle, which in turn plays a crucial role in the development of an efficient light harvesting material. The generation of reactive oxygen species as a result of femtosecond-resolved photoinduced electron injection in the aqueous medium is also investigated in order to explore the possibility of redox-active micromachines, which are found to be crucial for efficient and enhanced photocatalysis.