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In their Communication (e202202977), Zikai He et al. report on the circularly polarized room-temperature phosphorescence of a bidibenzo[ I b,d i ]furan scaffold with locked axial chirality. Bidibenzo[b,d]furan, Circularly-Polarized Luminescence, Locked Axial Chirality, Poly(Vinyl Alcohol), Room-Temperature Phosphorescence Keywords: Bidibenzo[b,d]furan; Circularly-Polarized Luminescence; Locked Axial Chirality; Poly(Vinyl Alcohol); Room-Temperature Phosphorescence EN Bidibenzo[b,d]furan Circularly-Polarized Luminescence Locked Axial Chirality Poly(Vinyl Alcohol) Room-Temperature Phosphorescence 1 1 1 07/20/22 20220725 NES 220725 B Organic Electronics b . [Extracted from the article]

The development of novel luminescent radicals, characterized by their unique doublet emission, endows a significant challenge. In this study, we reported the synthesis of a luminescent neutral radical, BCzAnM‐R, tailored by two carbazolyl groups and an anthryl group to achieve a nonalternant structure. It exhibited near‐infrared emission with a peak at 1020 nm in toluene. Interestingly, its corresponding cation, BCzAnM‐C, was synthesized through an unconventional SnCl2‐mediated reduction‐aromatization‐oxidation reaction in one‐pot and gram‐scale. The cation demonstrated remarkable stability for up to weeks in ambient conditions and facilitated the silica‐gel chromatography isolation as an organic salt with SnCl3− as the counter ion. The carbazolyl groups effectively modulate molecular structures, photophysical properties, and stabilities. Notably, BCzAnM‐R represents the first luminescent triarylmethyl radical with two carbazolyl groups directly attached to the central carbon. [ABSTRACT FROM AUTHOR]

Azobenzene derivatives are well-known for their photoisomerization. Due to E - Z isomerization, azobenzene derivatives are seldom fluorescent, which hinders their high-tech applications. Herein, we report two azobenzene derivatives, TPE-Azo-OH and TPE-Azo-2OH, with photoisomerization properties and solid-state fluorescence. Theoretical investigations revealed that the unusual fluorescence contributed from the S 2 (π, π*) by state-mixing in solid state. TPE-Azo-2OH exhibits even stronger fluorescence due to the suppression of photoisomerization by intramolecular hydrogen bond. Furthermore, upon reduction, these azobenzene derivatives exhibit fluorescence transformation from red to green. These new azobenzene derivatives with AIE attributes and stimuli-responsiveness are expected to provide a new platform for developing photo-responsive luminescent materials. • Azobenzene derivatives with AIE characteristics have been constructed. • The emission of the dark state is achieved through state mixing of the S 2 state. • Intramolecular hydrogen bonding enhances fluorescence emission. • Bond cleavage of the azo-group achieves emission color change. [ABSTRACT FROM AUTHOR]

Anti-Kasha's process in organic luminogens has attracted many attentions since its discovery. However, only limited examples of anti-Kasha's rule have been reported and anti-Kasha triplet energy transfer (ET) is even less-touched. Benefiting from anti-Kasha's rule, this work provided an efficient strategy to realize excitation wavelength dependent (Ex-De) afterglow in a host-guest system. The host has almost imperceptible RTP upon 365 nm excitation and guest is totally RTP inactive, while the doping host-guest system exhibits Ex-De afterglow with improved quantum yields. Anti-Kasha triplet ET process is realized from the higher excited triplet state T 2 of host to the lowest excited singlet state S 1 of the aggregated/unimolecular guest. ET efficiency in the doping system could be tuned by simply changing its processing methods to guide host and guest to adopt denser or looser intermolecular packing. The strategy of anti-Kasha triplet ET endows the host-guest doping system with multiple stimuli-responsive properties, including Ex-De afterglow, mechano-, and thermal-triggered afterglow behaviors. The corresponding applications of these properties are also realized in multiple information anti-counterfeiting and display., (© 2023. The Author(s).)

The development of smart-responsive materials, in particular those with non-invasive, rapid responsive phosphorescence, is highly desirable but has rarely been described. Herein, we designed and prepared a series of molecular rotors containing a triazine core and three bromobiphenyl units: o-Br-TRZ, m-Br-TRZ, and p-Br-TRZ. The bromine and triazine moieties serve as room temperature phosphorescence-active units, and the bromobiphenyl units serve as rotors to drive intramolecular rotation. When irradiated with strong ultraviolet photoirradiation, intramolecular rotations of o-Br-TRZ, m-Br-TRZ, and p-Br-TRZ increase, successively resulting in a photothermal effect via molecular motions. Impressively, the photothermal temperature attained by p-Br-TRZ is as high as 102 °C, and synchronously triggers its phosphorescence due to the ordered molecular arrangement after molecular motion. The thermal effect is expected to be important for triggering efficient phosphorescence, and the photon input for providing a precise and non-invasive stimulus. Such sequential photo-thermo-phosphorescence conversion is anticipated to unlock a new stimulus-responsive phosphorescence material without chemicals invasion., (© 2022. The Author(s).)

The development of solid-state intelligent materials, in particular those showing photoresponsive luminescence (PRL), is highly desirable for their cutting-edge applications in sensors, displays, data-storage, and anti-counterfeiting, but is challenging. Few PRL materials are constructed by tethering the classic photochromic systems with newly-emerged solid-state emitters. Selective solid-state photoreactions are demanded to precisely manipulate the luminescent behavior of these emitters, which require dramatic structural change and enough free space, thus limiting the scope of the PRL family. Here, a new PRL material, TPE-4N, that features sensitive and reversible fluorescence switching is reported. The interesting on-off luminescent property of TPE-4N can be facilely tuned through fast phototriggering and thermal annealing. Experimental and theoretical investigations reveal that subtle molecular conformation variation induces the corresponding PRL behavior. The crystalline and amorphous state endows an efficient and weak ISC process, respectively, to turn on and off the emission. The readily fabricated thin-film of TPE-4N exhibits non-destructive PRL behavior with high contrast (>10 2 ), good light transmittance (>72.3%), and great durability and reversibility under room light for months. Remarkably, a uniform thin-film with such fascinating PRL properties allows high-tech applications in invisible anti-counterfeiting and dynamic optical data storage with micro-resolution., (© 2020 Wiley-VCH GmbH.)

A novel dark through-bond energy transfer (DTBET) strategy is proposed and applied as the design strategy to develop ratiometric Hg 2+ sensors with high performance. Tetraphenylethene ( TPE ) derivatives with aggregation-induced emission (AIE) characteristics are selected as dark donors to eliminate emission leakage from the donors. The TBET mechanism has been adopted since it experiences less influence from spectral overlapping than Förster resonance energy transfer (FRET), making it more flexible for developing cassettes with large pseudo-Stokes shifts. In this work, energy transfer from the TPE derivatives (dark donor) to a rhodamine moiety (acceptor) was illustrated through photophysical spectroscopic studies and the energy transfer efficiency (ETE) was found to be up to 99%. In the solution state, no emission from the donors was observed and large pseudo-Stokes shifts were achieved (>280 nm), which are beneficial for biological imaging. Theoretical calculations were performed to gain a deeper mechanistic insight into the DTBET process and the structure-property relationship of the DTBET cassettes. Ratiometric Hg 2+ sensors were rationally constructed based on the DTBET mechanism by taking advantage of the intense emission of TPE aggregates. The Hg 2+ sensors exhibited well resolved emission peaks. >6000-fold ratiometric fluorescent enhancement is also achieved and the detection limit was found to be as low as 0.3 ppb. This newly proposed DTBET mechanism could be used to develop novel ratiometric sensors for various analytes and AIEgens with DTBET characteristics will have great potential in various areas including light harvesting materials, environmental science, chemical sensing, biological imaging and diagnostics.

Molecules with Möbius topology have drawn increasing attention from scientists in a variety of fields, such as organic chemistry, inorganic chemistry, and material science. However, synthetic difficulties and the lack of functionality impede their fundamental understanding and practical applications. Here, we report the facile synthesis of an aggregation-induced-emission (AIE)-active macrocycle (TPE-ET) and investigate its analogous triply and singly twisted Möbius topologies. Because of the twisted and flexible nature of the tetraphenylethene units, the macrocycle adjusts its conformations so as to accommodate different guest molecules in its crystals. Moreover, theoretical studies including topological and electronic calculations reveal the energetically favorable interconversion process between triply and singly twisted topologies., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)