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Although photochromic molecules have attracted widespread interest in various fields, solid-state photochromism remains a formidable challenge, owing to the substantial conformational constraints that hinder traditional molecular photoisomerization processes. Benefiting from the significant color change upon radical generation, chemical systems enabling a photoinduced radical (PIR) behavior through photoinduced electron transfer (PET) could be ideal candidates for solid-state photochromism within minimized need of conformational freedom. However, the transient nature of radicals causes a dilemma in this scheme. Herein, we present a general crystal engineering strategy for rapidly generated (7-s irradiation to saturation) and ultra-stable (lasting 12 weeks) PIRs in the solid state, based on the anti-parallel alignment of para-hydroxyphenyl groups of persulfurated arenes to form a strong non-covalent network for efficient PET and radical stabilization. Using this strategy, a PIR platform was constructed, with a superior photochromic behavior remaining in different solid forms (even in the fully-ground sample) due to their transcendent crystallization ability. On this basis, our compounds can be further processed into reusable papers for light-writing, accompanied by water fumigation for modulating the reversible process. This work provides new insights into addressing solid-state photochromism and can inspire a wide range of optical material design from the switchable radical perspective., (© 2024 Wiley‐VCH GmbH.)

Molecular emitters with multi-emissive properties are in high demand in numerous fields, while these properties basically depend on specific molecular conformation and packing. For amorphous systems, special molecular arrangement is unnecessary, but it remains challenging to achieve such luminescent behaviors. Herein, we present a general strategy that takes advantage of molecular rigidity and S 1 -T 1 energy gap balance for emitter design, which enables fluorescence-phosphorescence dual-emission properties in various solid forms, whether crystalline or amorphous. Subsequently, the amorphism of the emitters based polymethyl methacrylate films endowed an in situ regulation of the dual-emissive characteristics. With the ratiometric regulation of phosphorescence by external stimuli and stable fluorescence as internal reference, highly controllable luminescent color tuning (yellow to blue including white emission) was achieved. There properties together with a persistent luminous behavior is of benefit for an irreplaceable set of optical information combination, featuring an ultrahigh-security anti-counterfeiting ability. Our research introduces a concept of eliminating the crystal-form and molecular-conformational dependence of complex luminescent properties through emitter molecular design. This has profound implications for the development of functional materials., (© 2024 Wiley-VCH GmbH.)

Utilizing water molecules to regulate the luminescence properties of solid materials is highly challenging. Herein, we develop a strategy to produce water-triggered luminescence-switching cocrystals by coassembling hydrophilic donors with electron-deficient acceptors, where 1,2,4,5-Tetracyanobenzene (TCNB) was used as the electron acceptor and pyridyl benzimidazole derivatives were used as the electron donors enabling multiple hydrogen-bonds. Two cocrystals, namely 2PYTC and 4PYTC were obtained and showed heat-activated emission, and such emission could be quenched or weakened by adding water molecules. The cocrystal structure exhibited the donor molecule that can form multiple hydro bonds with water and acceptor molecules due to the many nitrogen atoms of them. The analyses of the photophysical data, powder X-ray diffraction, and other data confirmed the reversible fluorescence "on-off" effects were caused by eliminating and adding water molecules in the crystal lattice. The density functional theory calculations indicate that the vibration of the O-H bond of water molecules in the cocrystal can absorb the excitation energy and suppress fluorescence. Furthermore, the obtained cocrystals also showed temperature, humidity, and H + /NH 4 + responsive emission behavior, which allows their applications as thermal and humidity sensors, and multiple information encryptions. This research paves the way for preparing intelligent hydrophilic organic cocrystal luminescent materials., (© 2024 Wiley-VCH GmbH.)

It is challenging to achieve stable and efficient radical emissions under ambient conditions. Herein, we present a rational design strategy to protect photoinduced carbonyl free radical emission through electrostatic interaction and spin delocalization effects. The host-guest system is constructed from tricarbonyl-substituted benzene molecules and a series of imidazolium ionic liquids as the guest and host, respectively, whereby the carbonyl anion radical emission can be in situ generated under the light irradiation and further stabilized by electrostatic interaction. More importantly, the anion species and the alkyl chain length of imidazolium ionic liquids show a noticeable effect on luminescence efficiency, with the highest radical emission efficiency is as high as 53.3 % after optimizing the imidazole ionic liquid's structure, which is about four times higher than the polymer-protected radical system. Theoretical calculations confirm the synergistic effect of strong electrostatic interactions and that the spin delocalization effect significantly stabilizes the radical emission. Moreover, such a radical emission system also could be integrated with a fluorescent dye to induce multi-color or even white light emission with reversible temperature-responsive characteristics. The radical emission system can also be used to detect different amine compounds on the basis of the emission changes and photoactivation time., (© 2023 Wiley-VCH GmbH.)

Sapphyrin is a pentapyrrolic expanded porphyrin with a 22π aromatic character. Herein, we report the synthesis of a 20π antiaromatic sapphyrin isomer 1 by oxidative cyclization of a pentapyrrane precursor P 5 with a terminal β-linked pyrrole. The resulting isomer 1, containing a mis-linked bipyrrole unit in the skeleton, exhibits a reactivity for further oxidation due to the distinct antiaromatic electronic structure, affording a fused macrocycle 2, possessing a spiro-carbon-containing [5.6.5.6]-tetracyclic structure. Subsequent treatment with an acid afforded a weakly aromatic pyrrolone-appended N-confused corrole 3, and thermal fusion gave a [5.6.5.7]-tetracyclic-ring-embedded 14π aromatic triphyrin(2.1.1) analog 4. The cyclization at the mis-linked pyrrole moiety of P 5 played a crucial role in synthesizing the antiaromatic porphyrinoid susceptible to facile transformation to novel porphyrinoids with variable aromaticity., (© 2022 Wiley-VCH GmbH.)

The synthesis of an antiaromatic tetraoxa[8]circulene annulated with four perylene diimides (PDI), giving a dynamic non-planar π-conjugated system, is described. The molecule contains 32 aromatic rings surrounding one formally antiaromatic planarized cyclooctatetraene (COT). The intense absorption (ϵ=3.35×10 5  M -1  cm -1 in CH 2 Cl 2 ) and emission bands are assigned to internal charge-transfer transitions in the combined PDI-circulene π-system. The spectroscopic data is supported by density functional theory calculations, and nuclear independent chemical shift calculation indicate that the antiaromatic COT has increased aromaticity in the reduced state. Electrochemical studies show that the compound can reversibly reach the tetra- and octa-anionic states by reduction of the four PDI units, and the deca-anionic state by reduction of the central COT ring. The material functions effectively in bulk hetero junction solar cells as a non-fullerene acceptor, reaching a power conversion efficiency of 6.4 %., (© 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

How to utilize molecular vibration to tune triplet-involved emissions in multiple states is highly challenging. Here, star-shaped triphenylamine derivatives have been employed as model systems to understand how molecular vibration affects thermally activated delayed fluorescence (TADF) and room temperature phosphorescence (RTP) emissions in multiple states. Nonplanar, star-shaped conformations allow molecules to generate appropriate vibrations in the solution state, facilitating vibronic coupling between their T 1 and T 2 states to generate effective TADF. More importantly, a relatively dispersed state can allow the molecules to efficiently vibrate in the solid state, and a crystalline environment further promotes a more efficient TADF. Lastly, by suppressing molecular vibration to inhibit the TADF, ultra-long RTP was observed upon doping these molecules into polymers. These molecules can be used in information encryption and storage as well as bioimaging., (© 2022 Wiley-VCH GmbH.)

Controlling phase separation and transition plays a core role in establishing and maintaining the function of diverse self-assembled systems. However, it remains challenging to achieve wide-range continuous phase transition for dynamically producing a variety of assembled structures. Here, we developed a far-from-equilibrium system, upon the integration of photoexcitation-induced aggregation molecules and block copolymers, to establish an in situ phase-volume ratio photocontrol strategy. Thus, full-scale phase-diagram structures, from lamellar structure to gyroidal, cylindrical, and finally to a spherical one, can be accessed under different irradiation periods. Moreover, the phase transition was accompanied by considerable aggregation-induced phosphorescence and hydrophilicity/hydrophobicity change for building a functional surface. This strategy allows for a conceptual advance of accessing a wide range of distinct self-assembled structures and functions in real time., (© 2022 Wiley-VCH GmbH.)

Developing radical emission at ambient conditions is a challenging task since radical species are unstable in air. In the present work, we overcome this challenge by coassembling a series of tricarbonyl-substituted benzene molecules with polyvinyl alcohol (PVA). The strong hydrogen bonds between the guest dopants and the PVA host matrix protect the free radicals of carbonyl compounds after light irradiation, leading to strong solid state free radical emission. Changing temperature and peripheral functional groups of the tricarbonyl-substituted benzenes can influence the intensity of the radical emission. Quantum-chemical calculations predict that such free radical fluorescence originates from anti-Kasha D 2 →D 0 vertical emission by the anion radicals. The photoinduced radical emission by the tricarbonyl-substituted benzenes was successfully utilized for information encryption application., (© 2021 Wiley-VCH GmbH.)

An N-confused phlorin isomer bearing a dipyrrin moiety at the α-position of the confused pyrrole ring (1) was synthesized. Pd II and B III coordination at the peripheral prodigiosin-like moiety of 1 afforded the corresponding complexes 2 and 3. Reflux of 2 in triethylamine (TEA) converted the meso-phenyl into the Pd II -coordinating phenoxy group to afford 4. Under the same reaction conditions, TEA was linked to the α-position of the dipyrrin unit in 3 as an N,N-diethylaminovinyl group to afford 5. Furthermore, peripheral coordination of B III in 3 and 5 improved the planarity of the phlorin macrocycle and thus facilitated the coordination of Ag III at the inner cavity to afford 3-Ag and 5-Ag, respectively. These results provide an effective approach for developing unique porphyrinoids through peripheral coordination., (© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A hybrid thia-norhexaphyrin comprising a directly linked N-confused pyrrole and thiophene unit (1) revealed unique macrocycle transformations to afford multiply inner-annulated aromatic macrocycles. Oxidation with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone triggered a cleavage of the C-S bond of the thiophene unit, accompanied with skeletal rearrangement to afford unique π-conjugated products: a thiopyrrolo-pentaphyrin embedded with a pyrrolo[1,2]isothiazole (2), a sulfur-free pentaphyrin incorporating an indolizine moiety (3), and a thiopyranyltriphyrinoid containing a 2H-thiopyran unit (4). Furthermore, 2 underwent desulfurization reactions to afford a fused pentaphyrin containing a pyrrolizine moiety (5) under mild conditions. Using expanded porphyrin scaffolds, oxidative thiophene cleavage and desulfurization of the hitherto unknown N-confused core-modified macrocycles would be a practical approach for developing unique polypyrrolic aromatic macrocycles., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)