Cycloelimination of Imidazolidin‐2‐ylidene N‐Heterocyclic Carbenes: Mechanism and Insights into the Synthesis of Stable “NHC‐CDI” Amidinates

We report the discovery that 1,3‐bis(aryl)imidazolidin‐2‐ylidenes, one of the most widely studied classes of N‐heterocyclic carbenes (NHCs), undergo quantitative conversion to zwitterionic “NHC‐CDI” amidinates upon heating to ≈100 °C in solution. The mechanism of this novel NHC decomposition process is studied in detail. These studies enabled the rational synthesis of a new class of bench stable amidinates from a panel of NHCs and carbodiimides. We expect these constructs to find utility in a variety of applications.     

Properties and applications of precision oligomer materials; where organic and polymer chemistry join forces

Precise oligomeric materials constitute a growing area of research with implications for various applications as well as fundamental studies. Notably, this field of science which can be termed macro-organic chemistry, draws inspiration from both traditional polymer chemistry and organic synthesis, combining the molecular precision of organic chemistry with the materials properties of macromolecules. Discrete oligomers enable access to unprecedented materials properties, for example, in self-assembled structures, crystallization, or optical properties. The degree of control over oligomer structures resembles many biological systems and enables the design of materials with tailored properties and the development of fundamental structure–property relationships. This Review highlights recent developments in macro-organic chemistry from synthetic concepts to materials properties, with a focus on self-assembly and molecular recognition. Finally, an outlook for future research directions is provided.     

Influence of Amide Connectivity on the Hydrogen-Bond-Directed Self-Assembly of [n.n]Paracyclophanes

Reported here is the synthesis and self-assembly characterization of [n.n]paracyclophanes ( [n.n]pCps , n=2, 3) equipped with anilide hydrogen bonding units. These molecules differ from previous self-assembling [n.n]paracyclophanes ( [n.n]pCps ) in the connectivity of their amide hydrogen bonding units (C-centered/carboxamide vs. N-centered/anilide). This subtle change results in a ≈30-fold increase in the elongation constant for the [2.2]pCp -4,7,12,15-tetraanilide ( [2.2]pCpNTA ) compared to previously reported [2.2]pCp -4,7,12,15-tetracarboxamide ( [2.2]pCpTA ), and a ≈300-fold increase in the elongation constant for the [3.3]pCp -5,8,14,17-tetraanilide ( [3.3]pCpNTA ) compared to previously reported [3.3]pCp -5,8,14,17-tetracarboxamide ( [3.3]pCpTA ). The [n.n]pCpNTA monomers also represent the reversal of a previously reported trend in solution-phase assembly strength when comparing [2.2]pCpTA and [3.3]pCpTA monomers. The origins of the assembly differences are geometric changes in the association between [n.n]pCpNTA monomers—revealed by computations and X-ray crystallography—resulting in a more favorable slipped stacking of the intermolecular π-surfaces ( [n.n]pCpNTA vs. [n.n]pCpTA ), and a more complementary H-bonding geometry ( [3.3]pCpNTA vs. [2.2]pCpNTA ).     

Embedding Banach spaces into the space of bounded functions with countable support

We prove that a WLD subspace of the space consisting of all bounded, countably supported functions on a set Γ embeds isomorphically into if and only if it does not contain isometric copies of . Moreover, a subspace of is constructed that has an unconditional basis, does not embed into , and whose every weakly compact subset is separable (in particular, it cannot contain any isomorphic copies of ).     

Aircraft selection modeling: a multi-step heuristic to enumerate airlift alternatives

Annals of Operations Research - We consider the use of the new C-130J-30 aircraft for long distance (strategic) cargo movement. Currently, only large aircraft, the C-5 and the C-17, are identified...