Dense Energetic Nitraminofurazanes

3,3′‐Diamino‐4,4′‐bifurazane ( 1 ), 3,3′‐diaminoazo‐4,4′‐furazane ( 2 ), and 3,3′‐diaminoazoxy‐4,4′‐furazane ( 3 ) were nitrated in 100 % HNO₃ to give corresponding 3,3′‐dinitramino‐4,4′‐bifurazane ( 4 ), 3,3′‐dinitramino‐4,4′‐azofurazane ( 5 ) and 3,3′‐dinitramino‐4,4′‐azoxyfurazane ( 6 ), respectively. The neutral compounds show very imposing explosive performance but possess lower thermal stability and higher sensitivity than hexogen (RDX). More than 40 nitrogen‐rich compounds and metal salts were prepared. Most compounds were characterized by low‐temperature X‐ray diffraction, all of them by infrared and Raman spectroscopy, multinuclear NMR spectroscopy, elemental analysis, and by differential scanning calorimetry (DSC). Calculated energetic performances using the EXPLO5 code based on calculated (CBS‐4M) heats of formation and X‐ray densities support the high energetic performances of the nitraminofurazanes as energetic materials. The sensitivities towards impact, friction, and electrostatic discharge were also explored. Additionally the general toxicity of the anions against vibrio fischeri, representative for an aquatic microorganism, was determined.     

Preparation and characterization of inclusion complexes of beta-cyclodextrin with ionic liquid

The solubilities of beta-cyclodextrin (beta-CD), ionic liquid (IL) 1-butyl-3-methylimidazolium hexafluorophosphate (bmimPF6), and their mixture in water were determined, and the conductivity of these aqueous solutions was measured. It was demonstrated that beta-CD and bmimPF6 could enhance the solubility of each other, and the solubility curves of each were linear with gradients of about 1. The conductivity decreased remarkably with increasing beta-CD concentration, and a discernible break in the conductivity curve could be observed when beta-CD and bmimPF6 were equimolar in the solution. The solubility and conductivity results indicated that inclusion complexes (ICs) of 1:1 stoichiometry were formed. The inclusion compounds were further characterized by using powder X-ray diffraction (XRD) analysis, 13C CP/MAS (cross-polarization magic-angle spinning) NMR and 1H NMR spectroscopy, and thermogravimetric analysis (TGA). The results showed that the ICs were a fine crystalline powder. The host-guest system exhibited a channel-type structure and each glucose unit of beta-CD was in a similar environment. The decomposition temperature of the ICs was lower than that of bmimPF6 and beta-CD individually.     

A versatile tripodal host with cylindrical conformation: solvatomorphism, inclusion behavior, and separation of guests

Tripodal host 2,4,6-tris(1-phenyl-1H-tetrazolylsulfanylmethyl)mesitylene (TPTM) has been synthesized through a facile procedure. As expected, it adopts an all-syn cylindrical configuration, thereby delimiting an inner cavity. To explore the solvatomorphism and inclusion behavior of TPTM, a series of organic and inorganic species were employed as guests to afford 17 inclusion compounds (1, 2, 3 a-3 f, 4 a-4 i) that can be classified into four distinct forms (forms I-IV), under similar conditions. These compounds were characterized by single-crystal and powder X-ray diffraction, and (1)H NMR studies. In compound 1 with form I, one foot of a TPTM molecule inserts into the cavity of an opposite TPTM molecule to form a dimeric "hand-shake" motif with one acetonitrile molecule occupying the void. Compound 2 with form II contains three types of capsule-shaped dimers, each of which holds a CH(2)Cl(2) molecule as the guest. In compounds 3 a-3 f with form III, each pair of TPTM molecules interdigitates to form a capsule-shaped dimeric unit accommodating a guest molecule in the endo-cavity. In compounds 4 a-4 i with form IV, each TPTM molecule makes contact with three nearby TPTM molecules in a "self-including" manner to generate a graphite-like organic layer, and through further superposition to form open hexagonal channels. From the experimental and theoretical results, the intrinsic properties of guest molecules, such as size, shape, and self-interaction, can be regarded as the main factors leading to these solvatomorphism phenomena and the subtle inclusion behavior of TPTM. Thermogravimetric analyses show that the encapsulated guest molecules in these compounds can be evacuated at relatively high temperatures, and this demonstrates the outstanding inclusion capability of TPTM. In addition, for compound 4 a with benzene molecules in the channels, reversible exchange of toluene and separation of xylene isomers on single crystals have been observed.     

Supramolecular dye inclusion single crystals created from 2,3,6-trimethyl-β-cyclodextrin and porphyrins

In Nature, chromophoric groups play various roles, such as oxygen carriers, electron donors, light sensitizers, which are achieved in many cases by control of their aggregation modes in proteins. Host-guest chemistry between cyclodextrins and porphyrins has attracted great interest from supramolecular chemists because of their unique structures and functions that mimic those of proteins with chromophoric prosthetic groups. To mimic Nature's contrivances, the host-guest systems between cyclodextrins and porphyrins have frequently been studied. It is really surprising, however, that to date no detailed structural information of these complexes has been obtained from single-crystal analysis. In 2011, we reported the first successful isolation of a dye inclusion single crystal (DISC) between 2,3,6-trimethyl-β-cyclodextrin (TMβCD) and 5,10,15,20-tetrapyridylporphyrin (TPyP), and analyzed its X-ray crystal structure. The crystal structure revealed not only the real complex mode but also the attractive orientation of TPyP in the DISC. Herein, we present new strategies to prepare DISCs of TMβCD for several porphyrins and provide crystal structures, details of the complex modes, and optical properties. We believe that the present study has various important implications not only for the basic crystal analysis of inclusion complexes but also for potential applications that use these single crystals.     

Distribution of Butane in the Host Water Cage of Structure II Clathrate Hydrates

To understand host–guest interactions of hydrocarbon clathrate hydrates, we investigated the crystal structure of simple and binary clathrate hydrates including butane (n‐C₄H₁₀ or iso‐C₄H₁₀) as the guest. Powder X‐ray diffraction (PXRD) analysis using the information on the conformation of C₄H₁₀ molecules obtained by molecular dynamics (MD) simulations was performed. It was shown that the guest n‐C₄H₁₀ molecule tends to change to the gauche conformation within host water cages. Any distortion of the large 5¹²6⁴ cage and empty 5¹² cage for the simple iso‐C₄H₁₀ hydrate was not detected, and it was revealed that dynamic disorder of iso‐C₄H₁₀ and gauche‐nC₄H₁₀ were spherically extended within the large 5¹²6⁴ cages. It was indicated that structural isomers of hydrocarbon molecules with different van der Waals diameters are enclathrated within water cages in the same way owing to conformational change and dynamic disorder of the molecules. Furthermore, these results show that the method reported herein is applicable to structure analysis of other host–guest materials including guest molecules that could change molecular conformations.     

Supramolecular assemblies of sulfonatocalixarenes with phenanthroline: factors governing capsule formation versus bilayer arrangements

Four crystalline complexes were prepared by the inclusion complexation of the 1,10-phenanthrolinium ion (Phen) with p-sulfonatothiacalix[4]arene (TCAS) (2 from a solution at pH 1-2 and 4 from 1 M HCl) and with p-sulfonatocalix[5]arene (C5AS) (3 from a solution at pH 1-2 and 5 from 1 M HCl) upon varying the acidity of the solution. By combining the results obtained for complexes 2-5 with those for our previously reported complex (1), p-sulfonatocalix[4]arene (C4AS) complexed to Phen, it was revealed that p-sulfonatocalixarenes (CASs) form "bis-molecular" capsules (1, 2, and 3) around Phen at pH 1-2, whereas complexes 4 and 5 display distinct host-guest inclusion behavior at higher acid concentrations. The degree of compactness of the capsules increases with the enlargement of the calixarene cavity, which is affected significantly by both the penetration depth of Phen and the structure of the Phen dimer. Furthermore, the complexation behavior of TCAS/C5AS with Phen in 1 M DCl was investigated by using NMR spectroscopy, and was discussed in comparison with the previously reported results obtained from solutions at pH 2.0.