Open-shell species are central to spintronics and infrared optoelectronics, but remain challenging to stabilize in discrete molecular systems. Herein, we report that electron injection into pillar-shaped, radially π-conjugated [4]cyclonaphthodithiophene diimides ([4]C-NDTIs) triggers global aromaticity, yielding radical species with notable stability and optical properties.

The stabilization of 4π-electron systems remains a fundamental challenge in chemistry, stemming from their intrinsic antiaromaticity and thermodynamic instability as dictated by Hückel’s rule. A recent experimental study has demonstrated that rational molecular design using N-heterocyclic carbenes (NHCs) can surmount these limitations by inducing aromaticity. However, the issue of T1 aromaticity in such systems remains unresolved. Elucidating the substituent-modulated behavior of T1 (anti)aromaticity is crucial for deciphering the physicochemical properties of these systems.

Single-component organic photovoltaics (SC-OPVs) offer an innovative approach to the traditional bulk-heterojunction organic photovoltaics (BHJ-OPVs) by chemically bonding the donor and acceptor materials within a single molecule. This approach has the potential not only to reduce the manufacturing costs but also to stabilize the photoactive layer against common morphological degradation processes typically observed in BHJ-OPVs.

While triplet carbenes have been stabilized through spin delocalization, capturing triplet aluminyl anions─isoelectronic counterparts of carbenes─has remained an unsolved challenge in main-group chemistry. All previously reported aluminyl anions exhibit a singlet ground state, despite the use of diverse ligand frameworks. Herein, we report the first example of formally triplet aluminyl anions within bimetallic clusters, [((CH3)2C(CH2NPiPr2)2)2Al2Pd2]M2 (M = Li, Na, K).

Aryl and vinyl boron reagents are widely employed in modern organic synthesis. However, the direct coupling of nucleophilic vinyl boron reagents to construct conjugated 1,4-diarylbutadiene dianionic (DABDA) motifs in the absence of additives remains a significant challenge. Here, we report for the first time the direct coupling of various β-aryl vinyl boron reagents, initiated by the rare-earth metal monoalkyl complexes for the synthesis of a number of rare-earth metal complexes featuring inverse sandwich DABDA motifs.

The photoisomerism of azo switches using light in the near-IR region (NIR, 780-1400 nm) is highly preferable for the applications to biomedical and pharmacological fields. The common chemical modifications of azobenzene only enables the E ⇆ Z photoswitching wavelengths of azobenzene derivatives close to the red limit of near-infrared light.

In accordance with the constraints by Hückel’s and Baird’s rules, species generally exhibit aromaticity in one state (the lowest singlet state S0 or the lowest triplet state T1). Consequently, species with adaptive aromaticity (being aromatic in both the S0 and T1 states) are particularly rare. In this study, density functional theory (DFT) was employed to investigate adaptive aromaticity in 14e–, 16e– and 18e– metallabenzenes.

Anionic reagents with silicon-containing double bonds, M(R)Si═ERn (E = main group elements), have garnered significant interest owing to their unique metal-mediated reactivity and their potential in transferring the Si═E unit. Within this domain, the intriguing field of Si-metalated phosphasilenes remains uncharted.

Adaptive aromaticity has attracted substantial attention due to its unconventional two-state aromaticity in both the lowest singlet state (S0) and the lowest triplet state (T1) and its application to the singlet fission. Here we carry out a comprehensive investigation on a series of pyrrole derivatives by density functional theory (DFT) calculations and machine learning.