In general, the formation and dissociation of solute-solvent complexes have been too rapid to measure without disturbing the thermal equilibrium. We were able to do so with the use of two-dimensional infrared vibrational echo spectroscopy, an ultrafast vibrational analog of two-dimensional nuclear magnetic resonance spectroscopy. The equilibrium dynamics of phenol complexation to benzene in a benzene-carbon tetrachloride solvent mixture were measured in real time by the appearance of off-diagonal peaks in the two-dimensional vibrational echo spectrum of the phenol hydroxyl stretch. The dissociation time constant tau(d) for the phenol-benzene complex was 8 picoseconds. Adding two electron-donating methyl groups to the benzene nearly tripled the value of tau(d) and stabilized the complex, whereas bromobenzene, with an electron-withdrawing bromo group, formed a slightly weaker complex with a slightly lower tau(d). The spectroscopic method holds promise for studying a wide variety of other fast chemical exchange processes.

Ultrafast infrared transient absorption measurements of the complete hydroxyl OD stretching mode spectrum of HOD in water, from 100 fs to tens of picoseconds, observe hydrogen bond breaking and monitor the equilibration of the hydrogen bond network in water. In addition, the vibrational lifetime, the time constant for hydrogen bond breaking, and the rate of orientational relaxation are determined. The reactant and photoproduct spectra of the hydrogen bond breaking process are identified by decomposing the transient spectra into two components, the initial spectrum associated with vibrational excited states (reactants) and the long-time spectrum associated with broken hydrogen bonds (photoproducts). By properly taking into account the perturbation of the reactant spectrum decay by the growth of the photoproduct spectrum, it is found that the vibrational relaxation (1.45 ps) and orientational relaxation (1.53 ps) are wavelength independent and, therefore, independent of the degree of hydrogen bonding. Energy deposited into water by vibrational relaxation does not immediately break a hydrogen bond by predissociation nor produce a thermally equilibrated hydrogen bond distribution at an elevated temperature. Following deposition of energy by vibrational relaxation, the hydrogen bond breaking time is 800 fs, and there is a transient period of several picoseconds during which the hydrogen bond distribution is not in thermal equilibrium.

Rechargeable aqueous zinc-ion batteries are promising candidates for large-scale energy storage but are plagued by the lack of cathode materials with both excellent rate capability and adequate cycle life span. We overcome this barrier by designing a novel hierarchically porous structure of Zn-vanadium oxide material. This Zn0.3V2O5·1.5H2O cathode delivers a high specific capacity of 426 mA·h g−1 at 0.2 A g−1 and exhibits an unprecedented superlong-term cyclic stability with a capacity retention of 96% over 20,000 cycles at 10 A g−1. Its electrochemical mechanism is elucidated. The lattice contraction induced by zinc intercalation and the expansion caused by hydronium intercalation cancel each other and allow the lattice to remain constant during charge/discharge, favoring cyclic stability. The hierarchically porous structure provides abundant contact with electrolyte, shortens ion diffusion path, and provides cushion for relieving strain generated during electrochemical processes, facilitating both fast kinetics and long-term stability.

Organic materials with long‐lived, color‐tunable phosphorescence are potentially useful for optical recording, anti‐counterfeiting, and bioimaging. Herein, we develop a series of novel host–guest organic phosphors allowing dynamic color tuning from the cyan (502 nm) to orange red (608 nm). Guest materials are employed to tune the phosphorescent color, while the host materials interact with the guest to activate the phosphorescence emission. These organic phosphors have an ultra‐long lifetime of 0.7 s and a maximum phosphorescence efficiency of 18.2 %. Although color‐tunable inks have already been developed using visible dyes, solution‐processed security inks that are temperature dependent and display time‐resolved printed images are unprecedented. This strategy can provide a crucial step towards the next‐generation of security technologies for information handling.