Molecular Rotors in Porous Organic Frameworks

Porous organic frameworks perform a variety of functions, owing to their extremely large surface areas, but the dynamics of the structural elements have never been explored. Our discovery of ultra‐fast molecular rotors (10⁶ Hz at 225 K) in their architectures allows us to look at them from a new perspective. The constructive elements are robust struts and rapid rotors, resulting in a dynamic material whose motion can be frozen or released at will. The rotational motion can be actively regulated in response to guests. As the temperature is increased, the rotors spin ever faster, approaching free‐rotational diffusion at 550 K. The unusual combination of remarkable nanoporosity with fast dynamics is intriguing for engineering oscillating dipoles and producing responsive materials with switchable ferroelectricity, and for applications spanning from sensors to actuators, which capture and release chemicals on command.     

Dynamics of alkoxy-oligothiophene ground and excited states in nanochannels

Two oligothiophenes, 4,4'-dipentoxy-2,2'-dithiophene and 4,4"-dipentoxy-2,2':5',2":5",2' '-tetrathiophene, have been included in the nanochannels of the autoassembling host TPP (tris-o-phenylenedioxycyclotriphosphazene). The effect of the confinement on the structure and properties of the two dyes, as conformational arrangements, dynamics, and photophysical behavior, was addressed by the combination of high spinning speed solid-state NMR and time-resolved EPR spectroscopy. We compared the conformations of the dyes in their ground and photoexcited triplet states and described in detail the dynamics of the supramolecular adducts from 4 K to room temperature. Above 200 K surprisingly fast spinning rates of the dithiophene core were discovered, while the side chains show far slower reorientation motion, being in bulky gauche-rich conformations. These lateral plugs keep the planar core as appended in the space like a nanoscale gyroscope, allowing a reorientation in the motion regime of liquids and a long triplet lifetime at unusually high temperature. The nuclear magnetic properties of the guest dyes are also largely affected by the aromatic rings of the neighboring host, imparting an impressive magnetic susceptibility effect (2 ppm proton shift). The high mobility is due to the formation of a nanocage in a channel where aliphatic and aromatic functions isolate the thiophene moieties. Instead, two conformers of the tetrathiophene twisted on the central bond are stabilized by interaction with the host. They interconvert fast enough to be averaged in the NMR time scale.     

Dipolar Rotors Orderly Aligned in Mesoporous Fluorinated Organosilica Architectures

New mesoporous covalent frameworks, based on hybrid fluorinated organosilicas, were prepared to realize a periodic architecture of fast molecular rotors containing dynamic dipoles in their structure. The mobile elements, designed on the basis of fluorinated p‐divinylbenzene moieties, were integrated into the robust covalent structure through siloxane bonds, and showed not only the rapid dynamics of the aromatic rings (ca. 10⁸ Hz at 325 K), as detected by solid‐state NMR spectroscopy, but also a dielectric response typical of a fast dipole reorientation under the stimuli of an applied electric field. Furthermore, the mesochannels are open and accessible to diffusing in gas molecules, and rotor mobility could be individually regulated by I₂ vapors. The iodine enters the channels of the periodic structure and reacts with the pivotal double bonds of the divinyl‐fluoro‐phenylene rotors, affecting their motion and the dielectric properties.     

Microporous Molecular Materials from Dipeptides Containing Non‐proteinogenic Residues

Dipeptides with two hydrophobic side chains have proved to be an exceptional source of microporous organic materials, but since previous structures were limited to the incorporation of only proteinogenic residues, their full potential as adsorbents has remained unexplored. Single‐crystal XRD data for ten new compounds with non‐proteinogenic L ‐2‐aminobutanoic acid and/or L ‐2‐amino‐pentanoic acid are presented. The gas‐phase accessibility of their crystal pores, with cross‐sections of 2.3 to 5.1 Å, was monitored by CO₂ and CH₄ adsorption isotherms. Included CO₂ was also detected spectroscopically by 2D MAS NMR. An extensive conformational analysis reveals that the use of linear rather than branched side chains (such as L ‐valine and L ‐isoleucine) affords peptides with a greater degree of conformational freedom and yields more‐flexible channel surfaces that may easily adapt to a series of potential guest molecules.     

Ordered mesoporous Co3O4 as highly active catalyst for low temperature CO-oxidation

Cubic ordered mesoporous Co(3)O(4), prepared via the nanocasting pathway using KIT-6 as hard template, was found to be an excellent catalyst for low temperature CO oxidation, with the activity clearly depending on surface area and pore systems of the catalysts.     

Nanoporosity of an organo-clay shown by hyperpolarized xenon and 2D NMR spectroscopy

Interlayer nanoporosity of hectorite pillared by tetraethylammonium ions is explored by hyperpolarized xenon NMR and relevant gases such as carbon dioxide revealing the adsorption capacity of the open galleries.