Effective thermal management is critical for the operation of many modern technologies, such as electronic circuits, smart clothing, and building environment control systems. By leveraging the static infrared-reflecting design of the space blanket and drawing inspiration from the dynamic color-changing ability of squid skin, we have developed a composite material with tunable thermoregulatory properties. Our material demonstrates an on/off switching ratio of ~25 for the transmittance, regulates a heat flux of ~36 W/m 2 with an estimated mechanical power input of ~3 W/m 2 , and features a dynamic environmental setpoint temperature window of ~8 °C. Moreover, the composite can manage one fourth of the metabolic heat flux expected for a sedentary individual and can also modulate localized changes in a wearer’s body temperature by nearly 10-fold. Due to such functionality and associated figures of merit, our material may substantially reduce building energy consumption upon widespread deployment and adoption.

The molecule–substrate interaction plays a key role in charge injection organic-based devices. Charge transfer at molecule–metal interfaces strongly affects the overall physical and magnetic properties of the system, and ultimately the device performance. Here, we report theoretical and experimental evidence of a pronounced charge transfer involving nickel tetraphenyl porphyrin molecules adsorbed on Cu(100). The exceptional charge transfer leads to filling of the higher unoccupied orbitals up to LUMO+3. As a consequence of this strong interaction with the substrate, the porphyrin’s macrocycle sits very close to the surface, forcing the phenyl ligands to bend upwards. Due to this adsorption configuration, scanning tunneling microscopy cannot reliably probe the states related to the macrocycle. We demonstrate that photoemission tomography can instead access the Ni-TPP macrocycle electronic states and determine the reordering and filling of the LUMOs upon adsorption, thereby confirming the remarkable charge transfer predicted by density functional theory calculations.

We study the structural evolution of Sr 3 Ir 2 O 7 as a function of pressure using x-ray diffraction. At a pressure of 54 GPa at room temperature, we observe a first-order structural phase transition, associated with a change from tetragonal to monoclinic symmetry and accompanied by a 4% volume collapse. Rietveld refinement of the high-pressure phase reveals a novel modification of the Ruddlesden-Popper structure, which adopts an altered stacking sequence of the perovskite bilayers. As the positions of the oxygen atoms could not be reliably refined from the data, we use density functional theory (local-density approximation+U +spin orbit) to optimize the crystal structure and to elucidate the electronic and magnetic properties of Sr 3 Ir 2 O 7 at high pressure. In the low-pressure tetragonal phase, we find that the in-plane rotation of the IrO 6 octahedra increases with pressure. The calculations further indicate that a bandwidth-driven insulator-metal transition occurs at ∼20 GPa, along with a quenching of the magnetic moment. In the high-pressure monoclinic phase, structural optimization resulted in complex tilting and rotation of the oxygen octahedra and strongly overlapping t 2g and e g bands. The t 2g bandwidth renders both the spin-orbit coupling and electronic correlations ineffectual in opening an electronic gap, resulting in a robust metallic state for the high-pressure phase of Sr 3 Ir 2 O 7 .

Stable hydrocarbon surface species in the carbon dioxide hydrogenation reaction on Ir(111) were identified by means of infrared-visible sum-frequency generation vibrational spectroscopy and X-ray photoelectron spectroscopy under near-ambient pressure conditions (0.1 mbar). By introducing gas phase binary and ternary mixtures of CO2, CO, and H2 into the reaction chamber, stable ethylidyne and ethynyl species were found at the metal surface above 425 K, in remarkable analogy with that observed during the ethylene decomposition process yielding graphene. In addition, upon increasing temperature (up to 600 K depending on the reaction conditions), vibrational and electronic spectroscopic fingerprints appeared that could be attributed to the nucleation of aromatic hydrocarbons at the edge of metastable graphenic clusters interacting with the metal surface.

We report the formation of dimethyl sulfoxide (DMSO) molecular complexes on Au(111) enabled by native gold adatoms unusually linking the molecules via a bonding of ionic nature, yielding a mutual stabilization between molecules and adatom(s). DMSO is a widely used polar, aprotic solvent whose interaction with metal surfaces is not fully understood. By combining X-ray photoelectron spectroscopy, low temperature scanning tunneling microscopy, and density functional theory (DFT) calculations, we show that DMSO molecules form complexes made by up to four molecules arranged with adjacent oxygen terminations. DFT calculations reveal that most of the observed structures are accurately reproduced if, and only if, the negatively charged oxygen terminations are linked by one or two positively charged Au adatoms. A similar behavior was previously observed only in nonstoichiometric organic salt layers, fabricated using linkage alkali atoms and strongly electronegative molecules. These findings suggest a motif for anchoring organic adlayers of polar molecules on metal substrates and also provide nanoscale insight into the interaction of DMSO with gold.

Long-lived excitons formed upon visible light absorption play an essential role in photovoltaics, photocatalysis, and even in high-density information storage. Here, we describe a self-assembled two-dimensional metal-organic crystal, composed of graphene-supported macrocycles, each hosting a single FeN4 center, where a single carbon monoxide molecule can adsorb. In this heme-like biomimetic model system, excitons are generated by visible laser light upon a spin transition associated with the layer 2D crystallinity, and are simultaneously detected via the carbon monoxide ligand stretching mode at room temperature and near-ambient pressure. The proposed mechanism is supported by the results of infrared and time-resolved pump-probe spectroscopies, and by ab initio theoretical methods, opening a path towards the handling of exciton dynamics on 2D biomimetic crystals.

The adsorption of CO on Pt nanoclusters grown in a regular array on a template provided by the graphene/Ir(111) Moiré was investigated by means of infrared-visible sum frequency generation vibronic spectroscopy, scanning tunneling microscopy, X-ray photoelectron spectroscopy from ultrahigh vacuum to near-ambient pressure, and ab initio simulations. Both terminally and bridge bonded CO species populate nonequivalent sites of the clusters, spanning from first to second-layer terraces to borders and edges, depending on the particle size and morphology and on the adsorption conditions. By combining experimental information and the results of the simulations, we observe a significant restructuring of the clusters. Additionally, above room temperature and at 0.1 mbar, Pt clusters catalyze the spillover of CO to the underlying graphene/Ir(111) interface.

Wrinkled surfaces and materials are found throughout the natural world in various plants and animals and are known to improve the performance of emerging optical and electrical technologies. Despite much progress, the reversible post-fabrication tuning of wrinkle sizes and geometries across multiple length scales has remained relatively challenging for some materials, and the development of comprehensive structure−function relationships for optically active wrinkled surfaces has often proven difficult. Herein, by drawing inspiration from natural cephalopod skin and leveraging methodologies established for artificial adaptive infrared platforms, we engineer systems with hierarchically reconfigurable wrinkled surface morphologies and dynamically tunable visible-to-infrared spectroscopic properties. Specifically, we demonstrate architectures for which mechanical actuation changes the surface morphological characteristics; modulates the reflectance, transmittance, and absorptance across a broad spectral window; controls the specular-to-diffuse reflectance ratios; and alters the visible and thermal appearances. Moreover, we demonstrate the incorporation of these architectures into analogous electrically actuated appearance-changing devices that feature competitive figures of merit, such as reasonable maximum areal strains, rapid response times, and good stabilities upon repeated actuation. Overall, our findings constitute another step forward in the continued development of cephalopod-inspired light-and heat-manipulating systems and may facilitate advanced applications in the areas of sensing, electronics, optics, soft robotics, and thermal management.