The hexachlorocerate(III) anion, [CeCl], was found to be a potent photoreductant in acetonitrile solution with an estimated excited-state reduction potential of -3.45 V versus CpFe. Despite a short lifetime of 22.1(1) ns, the anion exhibited a photoluminescence quantum yield of 0.61(4) and fast quenching kinetics toward organohalogens allowing for its application in the photocatalytic reduction of aryl chloride substrates.

Interfacial interactions can play an important role in the glass transition temperature (Tg) and relaxation dynamics of ultra-thin glass polymer films. We have recently shown that similar to the polymeric systems in ultra-thin molecular glass films of N, N′-Bis(3-methylphenyl)-N, N′-diphenylbenzidine (TPD), the Tg is reduced and dynamics are enhanced. Furthermore, in molecular glass systems, as the film thickness is reduced below ∼30 nm, the dynamics at the two interfaces correlate such that the range of the gradients in the dynamics induced by the free surface narrows compared to thicker films. These observations indicate that the dynamics of the glassy thin films are strongly correlated and cannot be explained by a simple two-layer model consisting of a bulk and a thin interfacial layer with a constant thickness and constant range of dynamical gradients. Here, we investigate the effect of film/substrate interactions on the film dynamics by varying the TPD/substrate interfacial interactions. We show that thin TPD films with thicknesses below ∼60 nm show a smaller extent of Tg reduction and enhanced dynamics when supported on a near-neutral substrate (wetting) compared to a weakly interacting (dewetting) substrate. However, the ∼30 nm length scale, where the activation energy significantly reduces from its bulk value as measured by the onset of the glass transition remains unchanged. Coarse-grained molecular dynamics simulation also shows a narrowing in the range of relaxation times once the thickness is sufficiently reduced for the two interfaces to dynamically correlate, consistent with previous work. These results suggest that the length-scale for the correlated dynamics is independent of interfacial interactions and the polymeric nature of the film and may originate from the bulk glass properties.

Stable glasses (SGs) are formed through surface-mediated equilibration (SME) during physical vapor deposition (PVD). Unlike intermolecular interactions, the role of intramolecular degrees of freedom in this process remain unexplored. Here, using experiments and coarse-grained molecular dynamics simulations, we demonstrate that varying dihedral rotation barriers of even a single bond, in otherwise isomeric molecules, can strongly influence the structure and stability of PVD glasses. These effects arise from variations in the degree of surface mobility, mobility gradients, and mobility anisotropy, at a given deposition temperature (Tdep) At high Tdep, flexible molecules have access to more configurations, which enhances the rate of SME, forming isotropic SGs. At low Tdep, stability is achieved by out of equilibrium aging of the surface layer. Here, the poor packing of rigid molecules enhances the rate of surface-mediated aging (SMA), producing stable glasses with layered structures in a broad range of Tdep. In contrast, the dynamics of flexible molecules couple more efficiently to the glass layers underneath, resulting in reduced mobility and weaker mobility gradients, producing unstable glasses. Independent of stability, the flattened shape of flexible molecules can also promote in-plane orientation orderat low Tdep. These results indicate that small changes in intramolecular relaxation barriers can be used as an approach to independently tune the structure and mobility profiles of the surface layer and thus the stability and structure of PVD glasses.

Stable glasses are formed during physical vapor deposition (PVD), through the surface-mediated equilibration process. Understanding surface relaxation dynamics is important in understanding the details of this process. Direct measurements of the surface relaxation times in molecular glass systems are challenging. As such, surface diffusion measurements have been used in the past as a proxy for the surface relaxation process. In this study, we show that the absence of enhanced surface diffusion is not a reliable predictor of reduced ability to produce stable glasses. To demonstrate, we have prepared stable glasses (SGs) from two structurally similar organic molecules, 1,3-bis­(1-naphthyl)-5-(2-naphthyl)­benzene (TNB) and 9-(3,5-di­(naphthalen-1-yl)­phenyl)­anthracene (α,α-A), with similar density increase and improved kinetic stability as compared to their liquid-quenched (LQ) counterparts. The surface diffusion values of these glasses were measured both in the LQ and SG states below their glass transition temperatures (T gs) using gold nanorod probes. While TNB shows enhanced surface diffusion in both SG and LQ states, no significant surface T g diffusion is observed on the surface of α,α-A within our experimental time scales. However, isothermal dewetting experiments on ultrathin films of both molecules below Tg indicate the existence of enhanced dynamics in ultrathin films for both molecules, indirectly showing the existence of an enhanced mobile surface layer. Both films produce stable glasses, which is another indication for the existence of the mobile surface layer. Our results suggest that lateral surface diffusion may not be a good proxy for enhanced surface relaxation dynamics required to produce stable glasses, and thus, other types of measurements to directly probe the surface relaxation times may be necessary.

When aged below the glass transition temperature, Tg, the density of a glass cannot exceed that of the metastable supercooled liquid (SCL) state, unless crystals are nucleated. The only exception is when another polyamorphic SCL state exists, with a density higher than that of the ordinary SCL. Experimentally, such polyamorphic states and their corresponding liquid–liquid phase transitions have only been observed in network-forming systems or those with polymorphic crystalline states. In otherwise simple liquids, such phase transitions have not been observed, either in aged or vapor-deposited stable glasses, even near the Kauzmann temperature. Here, we report that the density of thin vapor-deposited films of N,N′-bis(3-methylphenyl)-N,N′-diphenylbenzidine (TPD) can exceed their corresponding SCL density by as much as 3.5% and can even exceed the crystal density under certain deposition conditions. We identify a previously unidentified high-density supercooled liquid (HD-SCL) phase with a liquid–liquid phase transition temperature (TLL) ∼35 K below the nominal glass transition temperature of the ordinary SCL. The HD-SCL state is observed in glasses deposited in the thickness range of 25 to 55 nm, where thin films of the ordinary SCL have exceptionally enhanced surface mobility with large mobility gradients. The enhanced mobility enables vapor-deposited thin films to overcome kinetic barriers for relaxation and access the HD-SCL state. The HD-SCL state is only thermodynamically favored in thin films and transforms rapidly to the ordinary SCL when the vapor deposition is continued to form films with thicknesses more than 60 nm.