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Two-dimensional infrared (2D IR) spectroscopy, infrared pump–infrared probe spectroscopy, and density functional theory calculations were used to study vibrational relaxation by ring and carbonyl stretching modes in a series of methylated xanthine derivatives in acetonitrile and deuterium oxide (heavy water). Isotropic signals from the excited symmetric and asymmetric carbonyl stretch modes decay biexponentially in both solvents. Coherent energy transfer between the symmetric and asymmetric carbonyl stretching modes gives rise to a quantum beat in the time-dependent anisotropy signals. The damping time of the coherent oscillation agrees with the fast decay component of the carbonyl bleach recovery signals, indicating that this time constant reflects intramolecular vibrational redistribution (IVR) to other solute modes. Despite their similar frequencies, the excited ring modes decay monoexponentially with a time constant that matches the slow decay component of the carbonyl modes. The slow decay times, which are faster in heavy water than in acetonitrile, approximately match the ones observed in previous UV pump–IR probe measurements on the same compounds. The slow component is assigned to intermolecular energy transfer to solvent bath modes from low-frequency solute modes, which are populated by IVR and are anharmonically coupled to the carbonyl and ring stretch modes. 2D IR measurements indicate that the carbonyl stretching modes are weakly coupled to the delocalized ring modes, resulting in slow exchange that cannot explain the common solvent-dependence. IVR is suggested to occur at different rates for the carbonyl vs ring modes due to differences in mode-specific couplings and not to differences in the density of accessible states.

Eumelanin is a brown-black biological pigment with sunscreen and radical scavenging functions important to numerous organisms. Eumelanin is also a promising redox-active material for energy conversion and storage, but the chemical structures present in this heterogeneous pigment remain unknown, limiting understanding of the properties of its light-responsive subunits. Here, we introduce an ultrafast vibrational fingerprinting approach for probing the structure and interactions of chromophores in heterogeneous materials like eumelanin. Specifically, transient vibrational spectra in the double-bond stretching region are recorded for subsets of electronic chromophores photoselected by an ultrafast excitation pulse tuned through the UV-visible spectrum. All subsets show a common vibrational fingerprint, indicating that the diverse electronic absorbers in eumelanin, regardless of transition energy, contain the same distribution of IR-active functional groups. Aggregation of chromophores diverse in oxidation state is the key structural property underlying the universal, ultrafast deactivation behavior of eumelanin in response to photoexcitation with any wavelength.

Redox is emerging as an alternative modality for bio‐device communication. In contrast to the more familiar ionic electrical modality: (i) redox involves the flow of electrons through oxidation–reduction reactions; (ii) the aqueous medium is an “insulator” to this electron flow since free electrons do not normally exist in water; and (iii) redox states are intrinsically digital (oxidized and reduced). By exploiting these unique features, a catechol‐based molecular memory film is reported. This memory is fabricated by electrochemically grafting catechol to a chitosan–agarose polysaccharide network to generate a redox‐active but non‐conducting matrix. The redox state of the grafted catechol moieties serves as the 2‐state memory. It is shown that these redox states: can be repeatedly switched by diffusible mediators (electron shuttles); can be easily read electrically or optically; are stable for at least 2 h in the absence of energy; are sensitive to biologically relevant oxidizing and reducing contexts; and can be switched enzymatically. This catechol‐based molecular memory film is a simple circuit element for redox linked bioelectronics.

Bulky side chains promote a molecular packing and intermolecular coupling that effect high-efficiency singlet fission in amorphous solids of pentacene derivatives.

Triplet population dynamics of solution cast films of isolated polymorphs of 6,13‐bis(triisopropylsilylethynyl) pentacene (TIPS‐Pn) provide quantitative experimental evidence that triplet excitation energy transfer is the dominant mechanism for correlated triplet pair (CTP) separation during singlet fission. Variations in CTP separation rates are compared for polymorphs of TIPS‐Pn with their triplet diffusion characteristics that are controlled by their crystal structures. Since triplet energy transfer is a spin‐forbidden process requiring direct wavefunction overlap, simple calculations of electron and hole transfer integrals are used to predict how molecular packing arrangements would influence triplet transfer rates. The transfer integrals reveal how differences in the packing arrangements affect electronic interactions between pairs of TIPS‐Pn molecules, which are correlated with the relative rates of CTP separation in the polymorphs. These findings suggest that relatively simple computations in conjunction with measurements of molecular packing structures may be used as screening tools to predict a priori whether new types of singlet fission sensitizers have the potential to undergo fast separation of CTP states to form multiplied triplets.