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.
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.
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 photoexcitationbased functional materials and the promotion of their practical usage.
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.
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