An olympicenyl radical, a spin 1/2 hydrocarbon radical with C 2v symmetry and uneven spin distribution, remains elusive despite the considerable theoretical research interest. Herein, we report syntheses of two air-stable olympicenyl radical derivatives, OR1 and OR2, with half-life times (τ1/2) in air-saturated solution of 7 days and 34 days. The high stability was ascribed to kinetic blocking of reactive sites with high spin densities. X-ray crystallographic analysis revealed unique 20-center–2-electron head-to-tail π-dimer structures with intermolecular distances shorter than the sum of van der Waals radius of carbon. The ground state of the π-dimers was found to be singlet, with singlet–triplet energy gaps estimated to be −2.34 kcal/mol and −3.28 kcal/mol for OR1 and OR2, respectively, by variable-temperature electron spin resonance (ESR) spectroscopy. The monomeric radical species were in equilibrium with the π-dimer in solution, and the optical and electrochemical properties of the monomers and π-dimers in solution were investigated by UV–vis–NIR spectroscopy and cyclic voltammetry, revealing a concentration-dependent nature. Theoretical calculations illustrated that upon formation of a π-dimer the local aromaticity of each monomer was enhanced, and spatial ring current between the monomers was present, which resulted in an increment of aromaticity of the interior of the π-dimer.

The semiconductor/electrolyte interface plays a crucial role in photoelectrochemical (PEC) water-splitting devices as it determines both thermodynamic and kinetic properties of the photoelectrode. Interfacial engineering is central for the device performance improvement. Taking the cheap and stable hematite (α-FeO) wormlike nanostructure photoanode as a model system, we design a facile sacrificial interlayer approach to suppress the crystal overgrowth and realize Ti doping into the crystal lattice of α-FeO in one annealing step as well as to avoid the consequent anodic shift of the photocurrent onset potential, ultimately achieving five times increase in its water oxidation photocurrent compared to the bare hematite by promoting the transport of charge carriers, including both separation of photogenerated charge carriers within the bulk semiconductor and transfer of holes across the semiconductor-electrolyte interface. Our research indicates that understanding the semiconductor/electrolyte interfacial engineering mechanism is pivotal for reconciling various strategies in a beneficial way, and this simple and cost-effective method can be generalized into other systems aiming for efficient and scalable solar energy conversion.

Singlet diradicaloids hold great potential as semiconductors for organic field‐effect transistors (OFETs). However, their relative low material and device stabilities impede the practical applications. Here, to achieve balanced stability and performance, two isomeric dibenzoheptazethrene derivatives with singlet diradical character were synthesized in a concise manner. Benefitting from the aromatic stabilization, both compounds display a small diradical character and large singlet–triplet gap, as corroborated by variable‐temperature electron paramagnetic resonance spectra, single‐crystal analysis, and theoretical calculations. OFET devices based on single crystals showed a high hole mobility of 0.15 cm2 V−1 s−1, which is the highest for zethrene‐based semiconductors. Both isomers exhibited remarkable material stability in air‐saturated solutions as well as excellent bias‐stress and storage stability in device under ambient air.

The hitherto elusive benzo [c]anthanthrenyl radical derivatives composed of seven fused six-membered rings are synthesized and isolated in the crystalline form, representing a laterally π-extended doublet open-shell graphene fragment compared to the phenalenyl and olympicenyl radical structures. X-ray crystallographic analysis revealed one-dimensional chain stacking with relatively close intermolecular contacts, which is an important precondition for achieving single-component conductors. The magnetic, optical, and redox properties are investigated in the solution phase. In combination with the good stability, such open-shell molecular systems have potentials as functional electronic materials.

The σ-dimer of a kinetically protected olympicenyl radical, which evaded the experimental detection, was revealed by conversion into biolympicenylidene with Econfiguration in a regioselective manner. The complicated stereochemistry and energetics of the σ-dimers derived from C 2v symmetry and uneven spin distribution of the olympicenyl radical were revealed by the theoretical calculations, and the energetic preference of π-dimer over σ-dimer by a minute gap was disclosed. The E-biolympicenylidene, a polycyclic ene structure previously considered as reactive intermediate in the phenalenyl radical system, exhibited exceptional stability, which allowed for a detailed investigation on its singlet diradical character and physical properties by means of X-ray crystallography, UV-vis-NIR absorption/emission spectroscopy and cyclic voltammetry, and assisted by theoretical calculations. The E-biolympicenylidene showed high resistance towards both thermal and photochemical ring-cyclization reactions, which was attributed to high activation energies for the rate-determining electrocyclization operated on both disrotatory and conrotatory mode, as well as a small spin density at the bonding sites for the radical-radical coupling process.