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Excimer Formation in Carboxylic Acid-Functionalized Perylene Diimides Attached to Silicon Dioxide Nanoparticles

Gorman, Jeffrey, Pandya, Raj, Allardice, Jesse R., Price, Michael B., Schmidt, Timothy W., Friend, Richard H., Rao, Akshay, Davis, Nathaniel J. L. K.
Journal of physical chemistry 2019 v.123 no.6 pp. 3433-3440
carboxylic acids, chemical structure, dyes, energy transfer, harvesting, ligands, light harvesting complex, nanocrystals, nanoparticles, phenols, silica
The creation of artificial light-harvesting complexes involves the ordered arrangement of chromophores in space. To guarantee efficient energy-transfer processes, organic dyes must be brought into close proximity, often leading to aggregation and the formation of excimer states. In recent years, the attachment of ligand-based chromophores to nanoparticles has also generated interest in relation to improved solar harvesting and spin-dependent electronic interactions such as singlet fission and upconversion. We explore the covalent attachment of two novel perylene-diimide (PDI) carboxylic acid ligands to silicon dioxide nanoparticles. This allows us to study electronic interactions between the ligands when attached to nanoparticles because these cannot couple to the wide band gap silicon dioxide. One of the synthesized PDI ligands has sterically hindering phenols in the bay position and undergoes minimal optical changes upon attachment, but the other forms an excimer state with a red-shifted and long-lived florescence. As such, molecular structure changes offer a method to tune weak and strong interactions between ligand layers on nanocrystal surfaces.