Determining the key vibrations for spin relaxation in ruffled Cu() porphyrins 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 = 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 spinphonon 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 (200300 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 spinphonon coupling. The rR spectra uncover a set of mixed symmetric stretch vibrations from 200250 cm 1 that explain the trends in temperature-dependent T 1 . These results indicate that molecular spinphonon 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 structureproperty relationships in molecular quantum information science. By using resonance Raman spectroscopy and temperature-dependent pulse EPR spectroscopy, we show that bond stretching vibrational modes > 200 cm 1 drive spin relaxation in planar and ruffled copper porphyrins.