Switchable metal-organic frameworks change their structure in time and selectively open their pores adsorbing guest molecules, leading to highly selective separation, pressure amplification, sensing and actuation applications. The three-dimensional engineering of metal-organic frameworks has reached a high level of maturity, but spatiotemporal evolution opens a new perspective towards engineering materials in the 4 th dimension (time) by t-axis design, in essence exploiting the deliberate tuning of activation barriers. This work demonstrates the first example in which an explicit temporal engineering of a switchable metal-organic frameworkdeliberately tuned by variation of cobalt content. We present a spectrum of advanced analytical methods for analyzing the switching kinetics stimulated by vapor adsorption using in situ time resolved techniques ranging from ensemble adsorption and advanced synchrotron X-ray diffraction experiments to individual crystal analysis. A novel analysis technique based on microscopic observation of individual crystals in a microfluidic channel reveals the lowest limit for adsorption switching reported so far. The time constants for the bulk ensembles range from 2 -300 s. Differences in spatiotemporal response of crystal ensembles originate from a delay (induction) time that varies statistically and widens characteristically with increasing cobalt content reflecting increasing activation barriers.

Crystalline coordination polymers with high electrical conductivities and charge carrier mobilities might open new opportunities for electronic devices. However, current solvent-based synthesis methods hinder compatibility with microfabrication standards. Here, we describe a solvent-free chemical vapor deposition method to prepare high-quality films of the two-dimensional conjugated coordination polymer Cu-BHT (BHT = benzenehexanothiolate). This approach involves the conversion of a metal oxide precursor into Cu-BHT nanofilms with a controllable thickness (20–85 nm) and low roughness (<10 nm) through exposure to the vaporized organic linker. Moreover, the restricted metal ion mobility during the vapor–solid reaction enables high-resolution patterning via both bottom-up lithography, including the fabrication of micron-sized Hall bar and electrode patterns to accurately evaluate the conductivity and mobility values of the Cu-BHT films.

The explicit formulas for atomic coordinates of multiwalled coaxial and cylindrical scroll nanotubes with ordered structure are developed on the basis of a common oblique lattice. According to this approach, a nanotube is formed by transfer of its bulk analogue structure onto a cylindrical surface (with a circular or spiral cross section) and the chirality indexes of the tube are expressed in the number of unit cells. The monoclinic polytypic modifications of ordered coaxial and scroll nanotubes are also discussed and geometrical conditions of their formation are analysed. It is shown that tube radii of ordered multiwalled coaxial nanotubes are multiples of the layer thickness, and the initial turn radius of the orthogonal scroll nanotube is a multiple of the same parameter or its half.

A quantitative theory of diffraction by right- and left-handed coaxial nanotubes with an ordered structure is developed. Their reciprocal lattices, including pseudo-orthogonal nodes, are studied. The explicit formulas that govern relations between direct and reciprocal lattices of a nanotube are achieved and a simple descriptive tool for diffraction pattern indexing is proposed.

A new scandium metal−organic framework (Sc-MOF) with the composition of [Sc(OH)(OBA)], denoted as Sc-CAU-21, was prepared under solvothermal reaction conditions using 4,4′-oxidibenzoic acid (H 2 OBA) as the ligand. Single-crystal structure determination revealed the presence of the new inorganic building unit (IBU) {Sc 8 (μ-OH) 8 (O 2 C) 16 }. It is composed of cisconnected ScO 6 polyhedra forming an eight-membered ring through bridging μ-OH groups. The connection of the IBUs leads to a 3D framework, containing 1D pores with a diameter between 4.2 and 5.6 Å. Pore access is limited by the size of the IBU, and in contrast to the isoreticular aluminum compound Al-CAU-21 [Al(OH)(OBA)], which is nonporous toward nitrogen at 77 K, Sc-CAU-21 exhibits a specific surface area of 610 m 2 g −1 . The title compound is thermally stable in air up to 350 °C and can be employed as a host for photoluminescent ions. Sc-CAU-21 exhibits a ligand-based blue emission, and (co)substituting Sc 3+ ions with Ln 3+ ions (Eu 3+ , Tb 3+ , and Dy 3+ ) allows the tuning of the emitting color of the phosphor from red to green. Single-phase white-light emission with CIE color coordinates close to the ideal for white-light emission was also achieved. The luminescence property was utilized in combination with powder X-ray diffraction to study in situ the crystallization process of Sc-CAU-21:Tb and Sc-CAU-21:Eu. Both studies indicate a two-step crystallization process, with a crystalline intermediate, prior to the formation of Sc-CAU-21:Ln.