Triindenotriphenylenes: Spin-Frustrated Triskelion Triradicals with Excellent Ambient Stability.

A triskelion-shaped triradical triindeno[1,2-a:1',2'-g:1'',2''-m]triphenylen-7-yl (1) and its internally fused derivative obtained by oxidative cyclization (2) were prepared in a straightforward synthetic sequence. Both compounds were confirmed to be triradicals and to possess intramolecular antiferromagnetic exchange interactions between spins, displaying a spin-frustrated doublet ground state with doublet-quartet energy gaps of -0.14 kcal/mol for 1 and -0.06 kcal/mol for 2. Despite their open-shell character, they were sufficiently stable to be handled under ambient conditions on a timescale of days. Both compounds could be reversibly reduced to mono-, di-, and trianions and oxidized to 1+ and 22+, with strong NIR absorptions (1800 to over 3200 nm) observed for all open-shell ions.

Dinor[7]helicene and Beyond: Divergent Synthesis of Chiral Diradicaloids with Variable Open-Shell Character.

Diradicaloid helicenes constructed formally by non-benzenoid double π-extension of phenanthrene were synthesized by a common strategy involving double electrophilic benzannulation. Steric effects in the second benzannulation step led to considerable structural diversity among the products, yielding a symmetrical dinor[7]helicene 1 and two isomeric unsymmetrical double helicenes 2 and 3, containing a nor[5]helicene and [4]helicene fragment, respectively, in addition to a common nor[6]helicene motif. Geometries, configurational dynamics, and electronic structure of these helicenes were analyzed using solid-state structures, spectroscopic methods, and computational analyses. The open-shell character of the singlet states of these helicenes increases in the order 3<1<2, with strongly varying diradicaloid indexes and singlet-triplet gaps. Compounds 1-3 displayed narrow optical gaps of 0.79-1.25 eV, resulting in significant absorption in the near infrared (NIR) region. They also exhibit reversible redox chemistry, each of them yielding stable radical cations, radical anions, and dianions, in some cases possessing intense NIR absorptions extending beyond 2500 nm.

Recent Advances in Heterocyclic Nanographenes and Other Polycyclic Heteroaromatic Compounds.

This review surveys recent progress in the chemistry of polycyclic heteroaromatic molecules with a focus on structural diversity and synthetic methodology. The article covers literature published during the period of 2016-2020, providing an update to our first review of this topic (Chem. Rev. 2017, 117 (4), 3479-3716).

Selection from a pool of self-assembling lipid replicators.

Replication and compartmentalization are fundamental to living systems and may have played important roles in life's origins. Selection in compartmentalized autocatalytic systems might provide a way for evolution to occur and for life to arise from non-living systems. Herein we report selection in a system of self-reproducing lipids where a predominant species can emerge from a pool of competitors. The lipid replicators are metastable and their out-of-equilibrium population can be sustained by feeding the system with starting materials. Phase separation is crucial for selective surfactant formation as well as autocatalytic kinetics; indeed, no selection is observed when all reacting species are dissolved in the same phase. Selectivity is attributed to a kinetically controlled process where the rate of monomer formation determines which replicator building blocks are the fittest. This work reveals how kinetics of a phase-separated autocatalytic reaction may be used to control the population of out-of-equilibrium replicators in time.

A halogen-bonding foldamer molecular film for selective reagentless anion sensing in water.

We describe self-assembled monolayers of novel halogen-bonding and hydrogen-bonding foldamer receptors capable of selectively recruiting perrhenate, iodide and thiocyanate in water. Unprecedented anion sensing via impedance-derived capacitance spectroscopy enables subsequent sensitive and selective anion detection without the need for a redox probe. Importantly, the sensing of any anion should be possible using this novel electrochemical approach.

Anion Recognition in Water by Charge-Neutral Halogen and Chalcogen Bonding Foldamer Receptors.

A novel strategy for the recognition of anions in water using charge-neutral σ-hole halogen and chalcogen bonding acyclic hosts is demonstrated for the first time. Exploiting the intrinsic hydrophobicity of halogen and chalcogen bond donor atoms integrated into a foldamer structural molecular framework containing hydrophilic functionalities, a series of water-soluble receptors was constructed for an anion recognition investigation. Isothermal titration calorimetry (ITC) binding studies with a range of anions revealed the receptors to display very strong and selective binding of large, weakly hydrated anions such as I- and ReO4-. This is achieved through the formation of 2:1 host-guest stoichiometric complex assemblies, resulting in an encapsulated anion stabilized by cooperative, multidentate, convergent σ-hole donors, as shown by molecular dynamics simulations carried out in water. Importantly, the combination of multiple σ-hole-anion interactions and hydrophobic collapse results in I- affinities in water that exceed all known σ-hole receptors, including cationic systems (ß2 up to 1.68 × 1011 M-2). Furthermore, the anion binding affinities and selectivity trends of the first example of an all-chalcogen bonding anion receptor in pure water are compared with halogen bonding and hydrogen bonding receptor analogues. These results further advance and establish halogen and chalcogen bond donor functions as new tools for overcoming the challenging goal of anion recognition in pure water.

Neutral iodotriazole foldamers as tetradentate halogen bonding anion receptors.

Neutral tetradentate halogen bond donor foldamers were synthesised and exhibit enhanced anion affinities over their hydrogen bonding analogues, displaying iodide selectivity over lighter halide, carboxylate and dihydrogen phosphate anions. A foldamer with a chiral (S)-binaphthol motif was demonstrated to distinguish between enantiomers of chiral anions.