1,1'-Biolympicenyl: A Stable Non-Kekulé Diradical with a Small Singlet and Triplet Energy Gap.

Dimerization of delocalized polycyclic hydrocarbon radicals is a simple and versatile method to create diradicals with tailored electronic structures and accessible high-spin states. However, the synthesis is challenging, and the stability issue of the diradicals remains a concern. In this study, we present the synthesis of a stable non-Kekulé 1,1'-biolympicenyl diradical 1 using a protection-oxidation-protection strategy. Diradical 1 demonstrated exceptional stability, with a solution half-life time exceeding 3.5 years and a solid state thermal decomposition temperature above 300 °C. X-ray crystallographic analysis revealed its intersected molecular structure and tightly bound dimer configuration. A singlet ground state with a small singlet-triplet energy gap is consistently identified using electron paramagnetic resonance (EPR) and a superconducting quantum interference device (SQUID) in a rigid matrix, and the triplet state is thermally accessible at room temperature. The solution phase properties were systematically examined through EPR, absorption spectroscopy, and cyclic voltammetry, revealing a rotational motion in the slow-motion regime and multistage redox characteristics. This study presents an efficient synthetic and stabilization strategy for organic diradicals, enabling the development of various high-spin functional materials.

Highly Efficient Room-Temperature Light-Induced Synthesis of Polymer Dots: A Programming Control Paradigm of Polymer Nanostructurization from Single-Component Precursor.

Polymer dots (PDs) have raised considerable research interest due to their advantages of designable nanostructures, high biocompatibility, versatile photoluminescent properties, and recyclability as nanophase. However, there remains a lack of in situ, real-time, and noncontact methods for synthesizing PDs. Here we report a rational strategy to synthesize PDs through a well-designed single-component precursor (an asymmetrical donor-acceptor-donor' molecular structure) by photoirradiation at ambient temperature. In contrast to thermal processes that normally lack atomic economy, our method is mild and successive, based on an aggregation-promoted sulfonimidization triggered by photoinduced delocalized intrinsic radical cations for polymerization, followed by photooxidation for termination with structural shaping to form PDs. This synthetic approach excludes any external additives, rendering a conversion rate of the precursor exceeding 99%. The prepared PDs, as a single entity, can realize the integration of nanocore luminescence and precursor-transferred luminescence, showing 41.5% of the total absolute luminescence quantum efficiency, which is higher than most reported PD cases. Based on these photoluminescent properties, together with the superior biocompatibility, a unique membrane microenvironmental biodetection could be exemplified. This strategy with programming control of the single precursor can serve as a significant step toward polymer nanomanufacturing with remote control, high-efficiency, precision, and real-time operability.

Overcrowded Ethylene-Bridged Nanohoop Dimers: Regioselective Synthesis, Multiconfigurational Electronic States, and Global Hückel/Möbius Aromaticity.

The design and preparation of molecular systems with multiple geometric and electronic configurations are the cornerstones for multifunctional materials with stimuli-responsive behaviors. We describe here the regioselective and facile synthesis of two types of overcrowded ethylene-bridged nanohoop dimers, with folded and twisted geometric structures as well as closed-shell, diradical and dication electronic structures. The strained nanohoop structures have a profound effect on the overall molecular and electronic configurations, which resulted in the destabilized diradical state. X-ray crystallographic analysis revealed the folded molecular geometry for the neutral species and twisted geometry for the dication species. The unique molecular dynamics, optical properties, and dynamic redox properties were disclosed in the solution phase by spectroscopic and electrochemical methods. Furthermore, the global Hückel and Möbius aromaticity were revealed by a combination of experimental and theoretical approaches. Our studies shed light on the design of nanohoop-incorporated multiconfigurational materials with unique topologies and functions.

A Fluorescence-Phosphorescence-Phosphorescence Triple-Channel Emission Strategy for Full-Color Luminescence.

Organic luminogens constitute promising prototypes for various optoelectronic applications. Since gaining distinct color emissions normally requires the alternation of the conjugated backbone, big issues remain in material synthetic cost and skeleton compatibility while pursuing full-color luminescence. Upon a facile one-step coupling, three simple but smart perchalcogenated (O, S, and Se) arenes are synthesized. They exhibit strong luminescent tricolor primaries (i.e., blue, green, and red, respectively) in the solid state with a superior quantum yield up to >40% (5-10 times higher than that in corresponding solutions). The properties originate from a fluorescence-phosphorescence-phosphorescence triple-channel emission effect, which is regulated by S and Se heavy atoms-dependent intersystem crossing upon molecular packing, as well as Se-Se atom interaction-caused energy splittings. Consequently, full-color luminescence, including a typical white-light luminescence with a Commission Internationale de I'Eclairage coordinate of (0.30, 0.35), is realized by complementarily incorporating these tricolor luminescent materials in the film. Moreover, mechanochromic luminescent color conversions are also observed to achieve the fine-tuning of the luminescent tints. This strategy can be smart to address full-color luminescence on the same molecular skeleton, showing better material compatibility as an alternative to the traditional multiple-luminophore engineering.

Orthogonally Incorporating Dual-Fluorescence Control into Gated Photochromism for Multifunctional Molecular Switching.

Gated photochromism is of interest for the operation and control of modern high-tech optofunctional materials. For further advancing this topic towards the achievement of multifunctional molecular switching, however, it remains a great challenge to incorporate multiple fluorescence regulation into gated photochromism in one unimolecular system. Herein, it is reported that a dithienylethene derivative DTEN with a Schiff base connection can be facilely synthesized by one-step coupling, and it enabled distinct color and spectral changes upon different stimuli, including ultraviolet, visible light, Ni2+ , and Al3+ . Relying on hydrazine and hydroxy units in this molecule, compound DTEN exhibited novel Ni2+ -locked photochromic characteristics originating from complexation of the compound with Ni2+ in a 2:1 stoichiometry. On the other hand, a 1:1 complexation between compound DTEN and Al3+ could allow both of the initial and photostationary states of DTEN to display fluorescent enhancement and a redshift, realizing a dual-fluorescence "turn-on" sensing of Al3+ by light. On this basis, it is argued that the switching of the coordination mode between DTEN and Ni2+ or Al3+ brings up the possibility of tunable photoswitching by multiple stimuli, which offers a novel way for future development of multifunctional switching materials with different input and output signals, as exemplified by the construction of a delicate molecular circuit.

Induction of Metabolic Reprogramming in Kidney by Singlet Diradical Nanoparticles.

Polycyclic aromatic compounds with an open-shell singlet diradical ground state, namely singlet diradicals, have recently gained attention in the fields of organic electronics, photovoltaics, and spintronics owing to their unique electronic structures and properties. Notably, singlet diradicals exhibit tunable redox amphoterism, which makes them excellent redox-active materials for biomedical applications. However, the safety and therapeutic efficacy of singlet diradicals in biological systems have not yet been explored. Herein, the study presents a newly designed singlet diradical nanomaterial, diphenyl-substituted biolympicenylidene (BO-Ph), exhibiting low cytotoxicity in vitro, non-significant acute nephrotoxicity in vivo, and the ability to induce metabolic reprogramming in kidney organoids. Integrated transcriptome and metabolome analyses reveal that the metabolism of BO-Ph stimulates glutathione (GSH) synthesis and fatty acid degradation, increases the levels of intermediates in the tricarboxylic acid (TCA) and carnitine cycles, and eventually boosts oxidative phosphorylation (OXPHOS) under redox homeostasis. Benefits of BO-Ph-induce metabolic reprogramming in kidney organoids include enhancing cellular antioxidant capacity and promoting mitochondrial function. The results of this study can facilitate the application of singlet diradical materials in the treatment of clinical conditions induced by mitochondrial abnormalities in kidney.

Enhancing the Operability of Photoexcitation-Controlled Aggregation-Induced Emissive Molecules in the Organic Phase.

Controllable aggregation-induced emission luminogens (AIEgens) by photoexcitation can be conducted within a single solvent, thus opening new opportunities for preparing and processing smart materials. However, undesired side-reactions like photooxidation that can easily occur in the organic phase remain, limiting their applications. To enhance the operability of photoexcitation-controlled AIEgens (to specifically produce a phosphorescence characteristic) in the organic phase, in this work, we employ a typical prototype, hexathiobenzene, usually as the specific phosphorescent group, and investigate a series of physical and chemical factors, such as light intensity, dissolved oxygen content, and solvent polarity, to explore ways to control the photoexcitation-controllable AIEgens against the impurities from side-reactions. An organogel strategy was also developed to minimize interference factors and improve the practical application ability. We believe that the presented results provide new insights into the further development of the photoexcitation-based functional materials and the promotion of their practical usage.

A monomolecular platform with varying gated photochromism.

In the development of modern high-performance photoelectric materials, the gated photochromic materials have attracted wide attention. However, the integration of varying signal regulations into gated photochromism to construct efficient photochromic materials is still an urgent necessity. Herein, we designed and synthesized a new gated photoswitching DTEP based on a Schiff base with a diarylethene core. The photochromic properties of compound DTEP can be regulated to different degrees by multiple stimuli, including UV/visible light, Cu2+ and Ni2+. The compound DTEP showed different response abilities to Cu2+ and Ni2+, due to the diverse complexation modes between DTEP and Cu2+ as well as Ni2+. The photochromic properties of compound DTEP could be inhibited completely by the introduction of Cu2+ to form a 1 : 1 complexation, while the weak gated photochromism could be found from the DTEP-Ni2+ complex in a 1 : 2 stoichiometry. Relying on such varying degrees of gated photochromic properties, a new molecular logic circuit was constructed to undertake complicated logical operations.