The asymmetric and symmetric stretches of azido- (N3) and cyano- (CN), infrared reporters have shown interesting vibrational coupling properties in larger peptide and nucleoside systems using two-dimensional infrared (2D IR) spectroscopy. In much smaller molecular scaffolds, cross peaks were observed between the two vibrational reporters in the off-diagonal region of 2D IR spectrum. The time evolution of these signals indicates that both vibrational coupling and vibrational energy transfer between the IR reporters is present. By utilizing different scaffolds, the distance is varied between these reporters and the corresponding transfer rate as well as the degree of vibrational coupling. A relationship between the rate of vibrational energy transfer and distance between the N3 and CN moieties was established. A quantitative model will be put forth to describe the distance dependence of the energy transfer mechanism compared to the vibrational coupling.

2D IR vibrational energy transfer between azido- and cyano- reporters in different molecular scaffolds

255th National Meeting (2018)

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