Hydrocarbon‐pool chemistry is important in methanol to olefins (MTO) conversion on acidic zeolite catalysts. The hydrocarbon‐pool (HP) species, such as methylbenzenes and cyclic carbocations, confined in zeolite channels during the reaction are essential in determining the reaction pathway. Herein, we experimentally demonstrate the formation of supramolecular reaction centers composed of organic hydrocarbon species and the inorganic zeolite framework in H‐ZSM‐5 zeolite by advanced 13C–27Al double‐resonance solid‐state NMR spectroscopy. Methylbenzenes and cyclic carbocations located near Brønsted acid/base sites form the supramolecular reaction centers in the zeolite channel. The internuclear spatial interaction/proximity between the 13C nuclei (associated with HP species) and the 27Al nuclei (associated with Brønsted acid/base sites) determines the reactivity of the HP species. The closer the HP species are to the zeolite framework Al, the higher their reactivity in the MTO reaction. 相似文献
Metal–organic frameworks (MOFs) are an extremely important class of porous materials with many applications. The metal centers in many important MOFs are zinc cations. However, their Zn environments have not been characterized directly by 67Zn solid‐state NMR (SSNMR) spectroscopy. This is because 67Zn (I=5/2) is unreceptive with many unfavorable NMR characteristics, leading to very low sensitivity. In this work, we report, for the first time, a 67Zn natural abundance SSNMR spectroscopic study of several representative zeolitic imidazolate frameworks (ZIFs) and MOFs at an ultrahigh magnetic field of 21.1 T. Our work demonstrates that 67Zn magic‐angle spinning (MAS) NMR spectra are highly sensitive to the local Zn environment and can differentiate non‐equivalent Zn sites. The 67Zn NMR parameters can be predicted by theoretical calculations. Through the study of MOF‐5 desolvation, we show that with the aid of computational modeling, 67Zn NMR spectroscopy can provide valuable structural information on the MOF systems with structures that are not well described. Using ZIF‐8 as an example, we further demonstrate that 67Zn NMR spectroscopy is highly sensitive to the guest molecules present inside the cavities. Our work also shows that a combination of 67Zn NMR data and molecular dynamics simulation can reveal detailed information on the distribution and the dynamics of the guest species. The present work establishes 67Zn SSNMR spectroscopy as a new tool complementary to X‐ray diffraction for solving outstanding structural problems and for determining the structures of many new MOFs yet to come. 相似文献
The photochemical behavior of bicyclo[2.1.1]hexyl derivatives was investigated by irradiation with a 450 W medium‐pressure mercury lamp in acetonitrile solution. The irradiation of methyl bicyclo[2.1.1]hexane‐5‐carbonylbenzoate ( 1a ) led to both Norrish type II cyclization and cleavage products with a molar ratio of 1:2.2, whereas the irradiation of methyl 5‐methylbicyclo[2.1.1]hexane‐5‐carbonylbenzoate ( 1b ) afforded the only Norrish/Yang photocyclization compound as the sole product. Such results were illustrated by several geometric parameters for Norrish/Yang photoreaction as ?1, ?4 and β obtained from the crystal structures. Furthermore, asymmetric photochemical studies using ionic chiral auxiliary technique were also conducted in the solid state. 相似文献
A new class of chiral macrocyclic arene composed of three chiral 2,6‐dihydroxyltriptycene subunits bridged by methylene groups was designed and synthesized. Structural studies showed that the macrocyclic molecule adopts a hex‐nut‐like structure with a helical chiral cavity and highly fixed conformation. Efficient resolution was achieved through the introduction of chiral auxiliaries to give a couple of enantiopure macrocycles, which exhibited high enantioselectivity towards three pairs of chiral compounds containing a trimethylamino group. 相似文献
Endowed with chiral channels and pores, chiral metal–organic frameworks (MOFs) are highly useful; however, their synthesis remains a challenge given that most chiral building blocks are expensive. Although MOFs with induced chirality have been reported to avoid this shortcoming, no study providing evidence for the ee value of such MOFs has yet been reported. We herein describe the first study on the efficiency of chiral induction in MOFs using inexpensive achiral building blocks and fully recoverable chiral dopants to control the handedness of racemic MOFs. This method yielded chirality‐enriched MOFs with accessible pores. The ability of the materials to form host–guest complexes was probed with enantiomers of varying size and coordination and in solvents with varying polarity. Furthermore, mixed‐matrix membranes (MMMs) composed of chirality‐enriched MOF particles dispersed in a polymer matrix demonstrated a new route for chiral separation. 相似文献
Synthesis of fully conjugated cyclophanes containing large‐size polycyclic aromatics is challenging. Now, three benzidine‐linked, hexa‐peri‐hexabenzocoronene (superbenzene)‐based ortho‐, para‐, and meta‐cyclophanes are synthesized through intermolecular Yamamoto coupling reaction of structurally pre‐organized precursors. Subsequent oxidative dehydrogenation gave the corresponding quinoidal benzidine‐linked cyclophanes. Their geometries were confirmed by X‐ray crystallographic analysis and their electronic properties were investigated by electronic absorption, cyclic voltammetry, and DFT calculations. The quinoidal benzidine‐linked cyclophanes show thermally populated paramagnetic activity with a relatively large singlet‐triplet energy gap. Two enantiomers for the ortho‐cyclophanes ( 1‐NH and 1‐N ) were isolated and their chiral figure‐of‐eight macrocyclic structures were identified. The cage‐like cyclophanes 2‐NH and 3‐NH with concave surface can selectively encapsulate fullerene C70. 相似文献
A changeable character : Differences in the dynamics of occluded moieties within the large pores (see graphic) of aluminium 1,3,5‐benzene tricarboxylate framework solid MIL‐110 are a function of the synthesis pH. Host–guest proton‐transfer processes lead to a reversible change in the character of the framework from cationic to neutral, depending on the nature of the extra‐framework moieties.
The excited‐state proton transfer and geminate recombination of 6‐hydroxyquinoline (6HQ) encaged in catalytic Na+‐exchanged faujasite zeolites X (NaX) and Y (NaY) have been explored by measuring steady‐state and picosecond time‐resolved spectra. The pathways and rate constants of proton transfer of excited 6HQ are determined by the microscopic environment of zeolitic hosts surrounding the guest molecules. The excited‐state proton transfer of a 6HQ molecule encapsulated in a zeolitic nanocavity is initiated by deprotonation of the enolic group to form an anionic intermediate and completed by subsequent protonation of the imino group to form a zwitterionic tautomer. Geminate recombination occurs to compete with proton transfer at each tautomerization step of excited‐state 6HQ because of the confined environment of dehydrated zeolitic supercages. Consequently, excited‐state equilibria among three prototropic species of 6HQ are established in microporous catalytic faujasite zeolites. Kinetic differences in NaX and NaY are attributed to dissimilarities in acidity/basicity. 相似文献
A solid‐state fluorescent host system was created by self‐assembly of a 21‐helical columnar organic fluorophore composed of (1R,2S)‐2‐amino‐1,2‐diphenylethanol and fluorescent 1‐pyrenecarboxylic acid. This host system has a characteristic 21‐helical columnar hydrogen‐ and ionic‐bonded network. Channel‐like cavities are formed by self‐assembly of this column, and various guest molecules can be included by tuning the packing of this column. Moreover, the solid‐state fluorescence of this host system can change according to the included guest molecules. This occurs because of the change in the relative arrangement of the pyrene rings as they adjust to the tuning of the packing of the shared 21‐helical column, according to the size of the included guest molecules. Therefore, this host system can recognize slight differences in molecular size and shape. 相似文献
The enhancement of the binding between halide anions and a Lewis acidic uranyl–salophen receptor has been achieved by the introduction of pendant electron‐deficient arene units into the receptor skeleton. The association and the occurrence of the elusive anion–π interaction with halide anions (as tetrabutylammonium salts) have been demonstrated in solution and in the solid state, providing unambiguous evidence on the interplay of the concerted interactions responsible for the anion binding. 相似文献
A peptidomimetic compound undergoes a reversible single‐crystal‐to‐single‐crystal transformation upon guest release/uptake with the transformation involving a drastic conformational change. The extensive and reversible alteration in the solid state is connected to the formation of an unprecedented “CH–π zipper” which can reversibly open and close (through the formation of CH–π interactions), thus allowing for guest sensing. 相似文献