Cucurbit[10]uril

Melamine diamine 1 is able to displace CB[5] from the CB[10].CB[5] complex resulting in CB[10].12 and precipitated CB[5].1. We were able to isolate free CB[10] by treatment of CB[10].1 with acetic anhydride followed by washing with MeOH, DMSO, and water. The spacious cavity of CB[10] is able to complex large guests, including a cationic calix[4]arene derivative in its 1,3-alternate form (CB[10].1,3-alt-3). The addition of adamantane carboxylic acid (4) to CB[10].3 triggers a conformational change during the formation of termolecular complex CB[10].cone-3.4.     

Fe-catalyzed three-component dicarbofunctionalization of unactivated alkenes with alkyl halides and Grignard reagents

A highly chemoselective iron-catalyzed three-component dicarbofunctionalization of unactivated olefins with alkyl halides (iodides and bromides) and sp²-hybridized Grignard reagents is reported. The reaction operates under fast turnover frequency and tolerates a diverse range of sp²-hybridized nucleophiles (electron-rich and electron-deficient (hetero)aryl and alkenyl Grignard reagents), alkyl halides (tertiary alkyl iodides/bromides and perfluorinated bromides), and unactivated olefins bearing diverse functional groups including tethered alkenes, ethers, protected alcohols, aldehydes, and amines to yield the desired 1,2-alkylarylated products with high regiocontrol. Further, we demonstrate that this protocol is amenable for the synthesis of new (hetero)carbocycles including tetrahydrofurans and pyrrolidines via a three-component radical cascade cyclization/arylation that forges three new C–C bonds.

A highly selective iron-catalyzed three-component dicarbofunctionalization of unactivated alkenes with alkyl halides and sp²-hybridized Grignard reagents is reported.     

The inverted cucurbit[n]uril family

We report the isolation, characterization, and recognition behavior of iCB[6] and iCB[7], which are diastereomers of CB[6] and CB[7], respectively, containing a single inverted glycoluril unit. Product resubmission experiments establish that these inverted CB[n] are intermediates in the mechanism of CB[n] formation. As a consequence of the inverted glycoluril ring, these inverted cucurbiturils possess a permanent dipole moment, are slightly smaller than their diastereomers, show distinctive selectivity in their recognition behavior, and report directly on the contents of their hydrophobic cavity.     

New structures in the bi­pyridine–copper(II) nitrate–methanol system: [(bpy)2Cu(NO3)]NO3·CH3OH and [(bpy)2Cu(NO3)]NO3

Reaction of 2,2′‐bi­pyridine (bpy) and copper(II) nitrate in methanol results in two complexes, namely light‐blue bis(2,2′‐bi­pyridine)­nitrato­copper(II) nitrate methanol solvate, [Cu(NO₃)(C₁₀H₈N₂)₂]NO₃·CH₃OH, (I), which is unstable in air, and the product of its decomposition, catena‐poly­[[[bis(2,2′‐bi­pyridine)copper(II)]‐μ‐nitrato‐O:O′] nitrate], {[Cu(NO₃)(C₁₀H₈N₂)₂]NO₃}_n, (II). The crystal structures of both compounds were determined from one crystal at room temperature. Later, the structure of (I) was redetermined at low temperature. In (I) and (II), the Cu atom is coordinated by two bpy and one or two nitrate ions, respectively. The second nitrate ion in (I), along with the methanol solvent mol­ecule, is found in the outer coordination sphere, not bonded to Cu. The nitrate in (I) is chelating, while in (II), it bridges (bpy)₂Cu complexes, forming a one‐dimensional chain structure. The Cu cation in (II) lies on a twofold axis and the uncoordinated NO₃^? ion is located close to a twofold axis and is therefore disordered. Compound (I) converts into (II) upon loss of solvent.     

Cucurbit[7]uril⋅Guest Pair with an Attomolar Dissociation Constant

Host?guest complexes between cucurbit[7] (CB[7]) or CB[8] and diamantane diammonium ion guests 3 or 6 were studied by ¹H NMR spectroscopy and X‐ray crystallography. ¹H NMR competition experiments revealed that CB[7]? 6 is among the tightest monovalent non‐covalent complexes ever reported in water with K_a=7.2×10¹⁷ M ^?1 in pure D₂O and 1.9×10¹⁵ M ^?1 in D₂O buffered with NaO₂CCD₃ (50 mM ). The crystal structure of CB[7]? 6 allowed us to identify some of the structural features responsible for the ultratight binding, including the distance between the NMe₃⁺ groups of 6 (7.78 Å), which allows it to establish 14 optimal ion‐dipole interactions with CB[7], the complementarity of the convex van der Waals surface contours of 6 with the corresponding concave surfaces of CB[7], desolvation of the C?O portals within the CB[7]? 6 complex, and the co‐linearity of the C₇ axis of CB[7] with the N⁺???N⁺ line in 6 . This work further blurs the lines of distinction between natural and synthetic receptors.     

Pb(3)F(5)NO(3), a cationic layered material for anion-exchange

Our research involves the development of new cationic materials for anion-based applications. We report the solvothermal synthesis and characterization of Pb(3)F(5)NO(3), a new layered lead fluoride material that, unlike the majority of layered and open-framework materials, is cationic in charge. The structure consists of polyhedral lead centers connected by doubly and triply bridging fluoride groups. We quantitatively exchanged the interlamellar nitrate groups of Pb(3)F(5)NO(3) for dichromate, under ambient aqueous conditions. Nuclear magnetic resonance and UV-vis spectroscopy show the reaction proceeds to 61.0% completion in several days. The material is also stable to 450 degrees C, which is vastly superior to organic resins that are still the standard for anion-exchange. The presence of extraframework anions also opens up other potentially unique anion-based properties, such as new catalytic reactions, anion intercalation, or growth of anionic clusters within the void spaces of the cationic material.     

Stability and performance analysis of a block elimination solver for bordered linear systems

A new block elimination method for bordered systems is proposedand its numerical properties are analysed. In the case wherethe leading principal block is ill-conditioned or singular andthe method becomes unstable a perturbation approach is usedto enhance the stability. Results of experiments performed onthe SGI Power Challenge 8000 and on the Cray J-9x illustratethe performance of the new algorithm and compare it with thecurrent best approach. It is shown that the new method worksfaster while preserving stability.