A zeolitic imidazolate framework with conformational variety

We show via structural considerations and DFT calculations that for a zeolitic imidazolate framework (ZIF) with sodalite (SOD) topology, [Zn(dcim)2]-SOD (dcim = 4,5-dichloroimidazolate), structural models of an infinite number of hypothetical conformational polymorphs with distinct linker orientations can be generated, which can be interconverted most likely only via reconstructive structural transitions. The relative total energies suggest that some of those polymorphs might be synthetically accessible. Efforts in that direction led to the synthesis of new trigonal 1 and previously known cubic 2 with improved crystallinity. According to structural analyses based on powder X-ray diffraction (PXRD) methods supported by NMR spectroscopy, 1 is the most stable of the theoretically predicted SOD-type framework conformers (isostructural to ZIF-7), whereas 2, at variance with a recent proposal, is a SOD-type material with a high degree of orientational disorder of the dcim linker units. The statistics of the linker orientations in 2 is close to that in 1, indicating that the disorder in 2 is not random. Rather, crystals of 2 are likely twins consisting of nanoscopic domains of trigonal 1 that are deformed to a cubic metric, with linker disorder located in the domain interfaces. As structural differences appear to be more related to characteristics of real as opposed to ideal crystal structures, we propose to not consider 1 and 2 as true conformational polymorphs. Systematic investigations of solvent mixtures led to the discovery of intermediate materials of 1 and 2. The PXRD patterns and SEM images indicate that they belong to a complete series of structural intermediates. Differences in the Ar adsorption/desorption behaviours reveal that 1, in contrast to 2, is a flexible ZIF framework.DFG/Priority Program/141

Patterning of Nanoparticle‐Based Aerogels and Xerogels by Inkjet Printing

Nanoparticle-based voluminous 3D networks with low densities are a unique class of materials and are commonly known as aerogels. Due to the high surface-to-volume ratio, aerogels and xerogels might be suitable materials for applications in different fields, e.g. photocatalysis, catalysis, or sensing. One major difficulty in the handling of nanoparticle-based aerogels and xerogels is the defined patterning of these structures on different substrates and surfaces. The automated manufacturing of nanoparticle-based aerogel- or xerogel-coated electrodes can easily be realized via inkjet printing. The main focus of this work is the implementation of the standard nanoparticle-based gelation process in a commercial inkjet printing system. By simultaneously printing semiconductor nanoparticles and a destabilization agent, a 3D network on a conducting and transparent surface is obtained. First spectroelectrochemical measurements are recorded to investigate the charge–carrier mobility within these 3D semiconductor-based xerogel networks

A zeolitic imidazolate framework with conformational variety: conformational polymorphs versus frameworks with static conformational disorder

We show via structural considerations and DFT calculations that for a zeolitic imidazolate framework (ZIF) with sodalite (SOD) topology, [Zn(dcim)2]-SOD (dcim = 4,5-dichloroimidazolate), structural models of an infinite number of hypothetical conformational polymorphs with distinct linker orientations can be generated, which can be interconverted most likely only via reconstructive structural transitions. The relative total energies suggest that some of those polymorphs might be synthetically accessible. Efforts in that direction led to the synthesis of new trigonal 1 and previously known cubic 2 with improved crystallinity. According to structural analyses based on powder X-ray diffraction (PXRD) methods supported by NMR spectroscopy, 1 is the most stable of the theoretically predicted SOD-type framework conformers (isostructural to ZIF-7), whereas 2, at variance with a recent proposal, is a SOD-type material with a high degree of orientational disorder of the dcim linker units. The statistics of the linker orientations in 2 is close to that in 1, indicating that the disorder in 2 is not random. Rather, crystals of 2 are likely twins consisting of nanoscopic domains of trigonal 1 that are deformed to a cubic metric, with linker disorder located in the domain interfaces. As structural differences appear to be more related to characteristics of real as opposed to ideal crystal structures, we propose to not consider 1 and 2 as true conformational polymorphs. Systematic investigations of solvent mixtures led to the discovery of intermediate materials of 1 and 2. The PXRD patterns and SEM images indicate that they belong to a complete series of structural intermediates. Differences in the Ar adsorption/desorption behaviours reveal that 1, in contrast to 2, is a flexible ZIF framework

Solvent-assisted linker exchange as a tool for the design of mixed-linker MIL-140D structured MOFs for highly selective detection of gaseous H2S

A MIL-140D-sdc framework has been used as a highly stable backbone for the introduction of 4,4′-azobenzene dicarboxylic acid (H2abdc) via solvent-assisted ligand exchange (SALE). The implemented azo groups can serve as coordination sites for copper ions. These can exchange ligands with different gases, but show a high selectivity against H2S, which makes this material promising for potential sensor applications

Direct grafting-from of PEDOT from a photoreactive Zr-based MOF – a novel route to electrically conductive composite materials

The postsynthetic potential of the two-dimensional metal–organic framework Zr-bzpdc-MOF which is based on the photoreactive molecule benzophenone-4,4′-dicarboxylic acid (H2bzpdc) is used here to selectively functionalize the MOF surface. We report the direct radical-induced oxidative grafting-from polymerization of the precursor EDOT on Zr-bzpdc-MOF, leading to an electrically conductive composite material and opening the road to a variety of applications

The International Linear Collider: Report to Snowmass 2021

The International Linear Collider (ILC) is on the table now as a new global energy-frontier accelerator laboratory taking data in the 2030s. The ILC addresses key questions for our current understanding of particle physics. It is based on a proven accelerator technology. Its experiments will challenge the Standard Model of particle physics and will provide a new window to look beyond it. This document brings the story of the ILC up to date, emphasizing its strong physics motivation, its readiness for construction, and the opportunity it presents to the US and the global particle physics community

The International Linear Collider: Report to Snowmass 2021

International audienceThe International Linear Collider (ILC) is on the table now as a new global energy-frontier accelerator laboratory taking data in the 2030s. The ILC addresses key questions for our current understanding of particle physics. It is based on a proven accelerator technology. Its experiments will challenge the Standard Model of particle physics and will provide a new window to look beyond it. This document brings the story of the ILC up to date, emphasizing its strong physics motivation, its readiness for construction, and the opportunity it presents to the US and the global particle physics community

The International Linear Collider: Report to Snowmass 2021

The International Linear Collider (ILC) is on the table now as a new global energy-frontier accelerator laboratory taking data in the 2030s. The ILC addresses key questions for our current understanding of particle physics. It is based on a proven accelerator technology. Its experiments will challenge the Standard Model of particle physics and will provide a new window to look beyond it. This document brings the story of the ILC up to date, emphasizing its strong physics motivation, its readiness for construction, and the opportunity it presents to the US and the global particle physics community