| dc.description.abstract | Enzymes utilize several non-covalent interactions to perform catalytic reactions within small cavities. Coordination driven self-assembly has been found to be the simplest approach for constructing artificial enzyme analogues. The ability of the cages to efficiently catalyze reactions depends on the nature of cavities. Barrel-like metallacages with cylindrical architectures, and two open apertures have been found to act as ideal nanoreactors.1 The metal-ligand bond dynamicity often makes such cages stimuli-responsive, and the hosts may migrate to another architecture in the presence of different signals, for example, guest stimulus. Although guest-driven transformations are known in the literature, there is a dearth of applications in that field.
My thesis presents guest-induced structural transformations of Pd(II) cages and explores their application. In the first part, I will discuss the synthesis of a molecular barrel that reversibly shuttles between a Pd6 and a multiple-fullerene encapsulated homologous Pd8 architecture in the presence and absence of fullerene (C60/C70) guests, respectively.2 Fullerenes are well-known photosensitizers; however they are ineffective in common organic solvents like acetonitrile due to insolubility. The encapsulation of multiple C70 molecules within acetonitrile-soluble barrels enables their photosensitizing properties to be utilized in such a solvent. In this regard, I will discuss oxidative transformations using a C70-complex under visible light.3 Next, I will demonstrate how such complexes can be utilized for carrying out ozonolysis-mimicking, ROS-mediated olefin oxidations under innocuous red light and ambient conditions.4
The last part of my presentation deals with guest-mediated transformations between isomeric forms of a water-soluble Pd6 host. I will demonstrate how the guest shape controls the geometry of the host. Furthermore, I will discuss how enzyme-like structural modulations of the cage assist the selective photo-dimerization of anthracene derivatives within its hydrophobic pocket in aqueous media.5
References:
1. R. Banerjee, D. Chakraborty and P. S. Mukherjee, J. Am. Chem. Soc., 2023, 145, 7692.
2. R. Banerjee, S. Bhattacharyya and P. S. Mukherjee, JACS Au, 2023, 3, 1998.
3. R. Banerjee, D. Chakraborty, W.-T. Jhang, Y.-T. Chan and P. S. Mukherjee, Angew. Chem. Int. Ed., 2023, 62, e202305338.
4. R. Banerjee, M. Roy, M. Aggarwal, S. Maji, D. Adhikari and P. S. Mukherjee, Chem. Sci., 2025, 16, 12885.
5. R. Banerjee, P. Bhandari, N. Hickey and P. S. Mukherjee, J. Am. Chem. Soc., 2025, 147, 23049. | en_US |
