Here, we demonstrate the simultaneous utilization of both the hot carriers (electrons and holes) in the photocatalytic transformation of benzylamine to N‐benzylidenebenzylamine and the scope of reaction has also been successfully demonstrated with catalytic oxidation of 4‐methoxybenzylamine. The wavelength‐dependent excitation of AuNP allows us to tune the potential energy of charge carriers relative to the redox potential of the reactants which leads to energetically favorable product formation on the nanoparticle surface. We capture the formation of reaction intermediates and products by using in situ Raman spectroscopy, complemented by NMR spectroscopy and GC‐MS. Based on the experimental substantiations, a plausible reaction mechanism has been proposed.

Here, we demonstrate the simultaneous utilization of both the hot carriers (electrons and holes) in the photocatalytic transformation of benzylamine to N‐benzylidenebenzylamine and the scope of reaction has also been successfully demonstrated with catalytic oxidation of 4‐methoxybenzylamine. The wavelength‐dependent excitation of AuNP allows us to tune the potential energy of charge carriers relative to the redox potential of the reactants which leads to energetically favorable product formation on the nanoparticle surface. We capture the formation of reaction intermediates and products by using in situ Raman spectroscopy, complemented by NMR spectroscopy and GC‐MS. Based on the experimental substantiations, a plausible reaction mechanism has been proposed.

Unravelling how various physical parameters influence the strength of plasmon−exciton coupling is crucial for the successful realization of the exciting potential applications of plexcitonic nanostructures. Here, in this paper, using single-particlelevel spectroscopy, we demonstrate how nanostructures' shapes and morphologies affect the plasmon−exciton interaction. We studied cyanine dye J-aggregate hybrids of four nanostructures of different shapes and morphologies: nanorod, concave nanocube, nanostar, and truncated trigonal bipyramid. The localized surface plasmon resonances of each of these particles are chosen to be identical and at the same time resonant with the J-band of our cyanine dye to make sure that any indirect effect of particle size and shape through plasmon frequency does not arise. Working with these different shapes allows us to observe the effect of variation in the plasmon local density of states, plasmon damping, exciton number densities at hot-spots, and how the interplay of these factors finally affect plasmon−exciton coupling at the nanoscale. We find that the shape and morphology of a plasmonic nanoparticle influence not only the Rabi splitting energies and the transparency dip depth but also the plexciton dynamics.

Using visible photoexcitation of gold nanospheres we successfully demonstrate the simultaneous harvesting of plasmon-induced multiple hot holes in the complete oxidative scission of the C=C bond in styrene at room temperature to selectively form benzaldehyde and formaldehyde, which is a reaction that requires activation of multiple substrates. Our results reveal that, while extraction of hot holes becomes efficient for interband excitation, harvesting of multiple hot holes from the excited Au nanospheres becomes prevalent only beyond a threshold light intensity. We show that the alkene oxidation proceeded via a sequence of two consecutive elementary steps; namely, a binding step and a cyclic oxometallate transition state as the ratedetermining step. This demonstration of plasmon-excitation-mediated harvesting of multiple hot holes without the use of an extra hole transport media opens exciting possibilities, notably for difficult catalytic transformations involving multielectron oxidation processes.

Using visible photoexcitation of gold nanospheres we successfully demonstrate the simultaneous harvesting of plasmon-induced multiple hot holes in the complete oxidative scission of the C=C bond in styrene at room temperature to selectively form benzaldehyde and formaldehyde, which is a reaction that requires activation of multiple substrates. Our results reveal that, while extraction of hot holes becomes efficient for interband excitation, harvesting of multiple hot holes from the excited Au nanospheres becomes prevalent only beyond a threshold light intensity. We show that the alkene oxidation proceeded via a sequence of two consecutive elementary steps; namely, a binding step and a cyclic oxometallate transition state as the ratedetermining step. This demonstration of plasmon-excitation-mediated harvesting of multiple hot holes without the use of an extra hole transport media opens exciting possibilities, notably for difficult catalytic transformations involving multielectron oxidation processes.