Determining the key vibrations for spin relaxation in ruffled Cu(ii) porphyrins via resonance Raman spectroscopy.

Pinpointing vibrational mode contributions to electron spin relaxation ( T 1 ) constitutes a key goal for developing molecular quantum bits (qubits) with long room-temperature coherence times. However, there remains no consensus to date as to the energy and symmetry of the relevant modes that drive relaxation. Here, we analyze a series of three geometrically-tunable S = ½ Cu(ii) porphyrins with varying degrees of ruffling distortion in the ground state. Theoretical calculations predict that increased distortion should activate low-energy ruffling modes (∼50 cm -1 ) for spin-phonon coupling, thereby causing faster spin relaxation in distorted porphyrins. However, experimental T 1 times do not follow the degree of ruffling, with the highly distorted copper tetraisopropylporphyrin (CuTiPP) even displaying room-temperature coherence. Local mode fitting indicates that the true vibrations dominating T 1 lie in the energy regime of bond stretches (∼200-300 cm -1 ), which are comparatively insensitive to the degree of ruffling. We employ resonance Raman (rR) spectroscopy to determine vibrational modes possessing both the correct energy and symmetry to drive spin-phonon coupling. The rR spectra uncover a set of mixed symmetric stretch vibrations from 200-250 cm -1 that explain the trends in temperature-dependent T 1 . These results indicate that molecular spin-phonon coupling models systematically overestimate the contribution of ultra-low-energy distortion modes to T 1 , pointing out a key deficiency of existing theory. Furthermore, this work highlights the untapped power of rR spectroscopy as a tool for building spin dynamics structure-property relationships in molecular quantum information science.