When fabricating macroscopic devices exploiting the properties of organic chromophores, the corresponding molecules need to be condensed into a solid material. Since optical absorption properties are often strongly affected by interchromophore interactions, solids with a well‐defined structure carry substantial advantages over amorphous materials. Here, the metal–organic framework (MOF)‐based approach is presented. By appropriate functionalization, most organic chromophores can be converted to function as linkers, which can coordinate to metal or metal‐oxo centers so as to yield stable, crystalline frameworks. Photoexcitations in such chromophore‐based MOFs are surveyed, with a special emphasis on light‐switchable MOFs from photochromic molecules. The conventional powder form of MOFs obtained using solvothermal approaches carries certain disadvantages for optical applications, such as limited efficiency resulting from absorption and light scattering caused by the (micrometer‐sized) powder particles. How these problems can be avoided by using MOF thin films is demonstrated.

Metal-organic frameworks offer tremendous potential for efficient separation of molecular mixtures. Different pore sizes and suitable functionalizations of the framework allow for an adjustment of the static selectivity. Here we report membranes which offer dynamic control of the selectivity by remote signals, thus enabling a continuous adjustment of the permeate flux. This is realized by assembling linkers containing photoresponsive azobenzene-side-groups into monolithic, crystalline membranes of metal-organic frameworks. The azobenzene moieties can be switched from the trans to the cis configuration and vice versa by irradiation with ultraviolet or visible light, resulting in a substantial modification of the membrane permeability and separation factor. The precise control of the cis:trans azobenzene ratio, for example, by controlled irradiation times or by simultaneous irradiation with ultraviolet and visible light, enables the continuous tuning of the separation. For hydrogen:carbon-dioxide, the separation factor of this smart membrane can be steplessly adjusted between 3 and 8.

Thin SiO2 films were grown on a Ru(0001) single crystal and studied by photoelectron spectroscopy, infrared spectroscopy and scanning probe microscopy. The experimental results in combination with density functional theory calculations provide compelling evidence for the formation of crystalline, double-layer sheet silica weakly bound to a metal substrate.