Wavelength-Resolved Photoinduced Spin Polarization in a Broad Optical Range for a Porphyrin-Quinone System

Abstract

Photochemically induced dynamic nuclear polarization (photo-CIDNP) in liquid-state donor-acceptor systems is typically studied at a limited number of excitation wavelengths, leaving its spectral dependence incompletely characterized. Understanding the wavelength dependence of photo-CIDNP is important both for elucidating the underlying spin-chemical mechanisms and for optimizing hyperpolarization strategies in chemically and biologically relevant molecular systems. Here, we investigate wavelength-resolved photo-CIDNP in a tetraphenylporphyrin-1,4-benzoquinone donor-acceptor system over the 350-800 nm spectral range. Photon-flux-normalized CIDNP amplitudes were measured using both a tunable laser system and a broadband xenon lamp equipped with interchangeable 10 nm interference filters. The CIDNP response exhibits a non-monotonic dependence on excitation wavelength. Pronounced hyperpolarization is observed near 350 nm and in the 500-550 nm region, whereas excitation within the strongly absorbing 400-450 nm range results in a substantially reduced CIDNP response. Comparison with the UV-Vis absorption spectrum demonstrates that photo-CIDNP efficiency is not governed solely by optical absorption and reflects wavelength-dependent photophysical processes. After normalization to the excitation photon flux, lamp- and laser-based measurements yield consistent CIDNP results, validating broadband filtered excitation as a reliable and experimentally accessible approach for wavelength-resolved photo-CIDNP studies. These results establish excitation wavelength as an independent control parameter for liquid-state photo-CIDNP and provide a framework for systematic investigations of wavelength-dependent spin hyperpolarization.