The fluorescent “molecular squid”, a strained nanocarbon receptor derived from calixarene, binds neutral and cationic guests in solution. In the solid state, it forms stable inclusion complexes and shows porosity toward gases and vapors.
Efficient energy and electron transfer in photoexcited dye assemblies is of fundamental importance in both biological and artificial light‐harvesting systems. Efficient transfer according to the Förster mechanism is now reported in multi‐chromophore cassettes consisting of four BODIPY units rigidly linked to a pseudo‐tetrahedral acceptor dye. This central chromophore was obtained by fusing porphyrin and perylenediimide motifs and displays strong absorption extending into the near infrared.
A simple reagent, N‐bromosuccinimide, is the oxidant of choice in the stereospecific synthesis of azacoronene propellers. This new family of chiral chromophores features small electronic bandgaps, rich redox chemistry, and large chiroptical responses.
This review summarizes recent advances in the chemistry of curved aromatic molecules. By focusing on the key accomplishments of the last decade, we provide a general overview of synthetic methods capable of efficient induction of internal strain in π‐conjugated frameworks. The review is structured according to the topology change involved in the strain‐inducing reaction step (cyclizations, eliminations, ring expansions and contractions), and highlights the striking diversity of structures achievable with modern synthetic methodology.
Chrysaorenes and their macrocyclic precursors do not usually swarm on your floor. However, to prepare yourself for the encounter, you may wish to read the paper nevertheless.
Deep, fluorescent aromatic bowls, resembling carbon nanotube endcaps, are prepared by Ni(0)-mediated coupling of simple heterocyclic precursors. This one-step synthesis, capable of introducing an unprecedented amount of internal strain, relies on accurate timing of transmetalation and reductive elimination steps.
Chrysaorole,* which is a jellyfish‐shaped strained heteroaromatic molecule, was obtained from a carbazole‐based macrocyclic precursor by using a new “fold‐in” strategy.*after Chrysaora, a genus of jellyfish. Χρυσάωρ“golden armament” .
The image shows the host–guest interaction between the figure‐eight dication of di‐p‐benzihexaphyrin and a dichloroacetate anion. For details see Section 6.5 of this review.
The two complementary worlds of π aromaticity meet in one molecule. Di‐p‐benzihexaphyrin contains two phenylene rings, which, when oriented face‐to‐face, define an antiaromatic macrocycle with an orientable (Hückel) π system. With a 90° twist of one phenylene ring, the molecule transforms into a remarkable edge‐to‐face conformer with a Möbius topology. The different colors of the two forms show the effect of topology switching on the π conjugation. .
The two inner protons of 22-hydroxybenziporphyrin, a phenol-containing porphyrin analogue, act as a switch of antiaromaticity. This unusual example of keto-phenol tautomerization, which interchanges - and annulenoid conjugation pathways, has been investigated by means of NMR spectroscopy and computational methods. .