Cryptands with 1,3,5-Tris(1′,3′-dioxan-2′-yl)-benzene Units: Synthesis and Structural Investigations

Various cryptands based on 1,3-dioxane decorated 1,3,5-trisubstituted-benzene building blocks, connected by different chains (exhibiting ester, ether, or triazol groups) to several units with <i>C₃</i> symmetry, are reported. The structure of the compounds was investigated by single crystal X-ray diffraction, NMR, and MS. The role of the 1,3-dioxane units was targeted to ensure the preorganization of the substrate for the macrocyclization reactions on one side, and for easier NMR assignment of the structure of the cryptands on the other side

π‑Conjugated Discrete Oligomers Containing Planar and Nonplanar Aromatic Motifs

A new family of π-conjugated oligomers featuring a nonplanar polycyclic aromatic hydrocarbon, corannulene, and a planar aromatic unit, thiophene, is synthesized through an iterative metal-catalyzed coupling protocol. The two structural motifs are connected through an acetylene linkage. In the shorter oligomers, a thiophene unit is attached to one or two corannulenes. In the higher analogues, two, three, and four thiophene units are placed in an alternating fashion with three, four, and five corannulene units, respectively. Photophysical studies reveal extended π-effects that initially increase and then attenuate as a function of the oligomer length. Notably, longer oligomers are found to be highly active for nonlinear absorption and emission properties. The oligomer with three corannulene and two thiophene units exhibits a two-photon absorption cross section of 600 GM and two-photon-excited intense green luminescence. This work, therefore, introduces the concept of combining planar and nonplanar aromatic motifs in the design of π-conjugated discrete oligomers, establishes synthetic feasibility of such hybrid materials, reports on their photophysical properties that is anticipated to have significant implications for future research targets, and features the discovery that corannulene derivatives can exhibit excellent nonlinear optical activity when extended through π-bridges

Synthesis, structure, electrochemical behaviour and electrochemical investigations on the assembling with pyrene of a novel C₃ cryptand

<div><p>The synthesis and the structure of a new cryptand with 1,3,5-triphenylbenzene caps and pyridine rings in the chains are reported. The formation of a host–guest assembly between the investigated cryptand and pyrene was predicted by molecular modelling and confirmed by the electrochemical investigations by cyclic voltammetry using graphite electrodes.</p></div