A series of novel persistent room-temperature phosphorescence (pRTP) materials (PEPCz) obtained via a combination of chalcogen atoms (O, S, Se, and Te) and a carbazolyl moiety is reported. Single crystal structure analysis revealed that PEPCz had similar molecular conformations and almost identical crystal packing. Mechanistic study showed that the intramolecular electronic coupling between the chalcogen atoms and π-units was responsible for tunable pRTP. The PEPCz were used not only to realize graphic encryption, but also to fabricate pRTP sensors for H2O2 and TNT detection.
A series of novel ortho-terphenylene viologen derivatives (o-TPV 2+ ) with through-space conjugation (TSC) via the combination of ortho-terphenylene skeletons with viologen structure is reported. Their optoelectronic properties can be adjusted by N-arylation or N-alkylation reactions. Compared with other viologen derivatives, o-TPV 2+ not only exhibits strong photoluminescence but also retards the charge recombination process and stabilizes the diradical state without forming a quinoid structure due to the special TSC effect. Based on their special redox characteristics, o-TPV 2+ was applied to the photocatalytic oxidative coupling of benzylamine with 96% yield. In addition, pTA-o-TPV 2+ (tethered with p-toluic acid)-modified g-C 3 N 4 was used for visiblelight-driven hydrogen production for the first time, exceeding 15 times the rate over unmodified g-C 3 N 4 .
Although naphthalene diimide (NDI) and its derivatives have been widely used for organic Li-ion batteries (OLIBs), they are limited by a low lithium uptake capacity and ambiguous lithiation mechanism. Herein, we report two isometric thionated-NDI cathodes (cis-2S and trans-2S) obtained by replacing O with S in the imide groups which improves the battery performance compared with parent NDI (P-NDI). Remarkably, the position of S atoms plays an important role as the potential plateau of cis-2S was 100 mV higher than trans-2S, 256 mV higher than P-NDI, and the capacity of cis-2S was twice than that of trans-2S, four times as P-NDI after 400 cycles. The in situ Raman, X-ray photoelectron spectroscopy (XPS), and DFT calculations revealed that the lithiation process occurs on the less electronegative S atoms. For cis-2S, the electron density on the lithiation sites is lower than trans-2S because of a stronger electron inductive effect. This in turn enhances the redox potential and cycling stability of cis-2S. This contribution provides an additional molecular engineering strategy to develop novel organic cathode materials for high performance OLIBs.
Selenoviologens‐appendant metallacycles M1 (rhomboid) and M2 (hexagonal) were synthesized and utilized in electrochromism and photocatalysis, as reported in the Research Article (e202209054) by Gang He et al. The highly stable radical cations and long‐lived charge separation states of the selenoviologens (SeV2+) originate from the metallacyclic effect. Their properties were validated by femtosecond transient absorption (fs‐TA), demonstrating the vital role of the metallacycle in organic photocatalytic reactions.
A series of novel bismuth-bridged viologen analogues, bismoviologens (BiV 2+ ), synthesized through a combination of a bismuth atom and viologen skeleton is reported. Their optical and electrochemical properties were fine-tuned through the N-arylation or N-alkylation reactions. Bismolviologens not only showed good redox properties but also exhibited phosphorescence under ambient conditions (in air at room temperature). This phenomenon makes BiV 2+ the first examples of phosphorescent viologen analogues reported to date. On the basis of the excellent and unique redox and optical properties of BiV 2+ , their electrophosphorochromic devices were fabricated. Furthermore, BiV 2+ was used for the first time as both a photocatalyst and electron mediator in visible light-induced cross-dehydrogenative coupling reactions.
π‐Conjugated arylene diimide derivatives as a kind of well‐known organic dyes have been widely used as building blocks for constructing n‐type semiconductors. However, the large π‐framework faded their solid‐state emission, which hinders their application in organic light‐emitting diodes (OLEDs). Herein, two novel π‐conjugated donor–acceptor–donor (D‐A‐D) type compounds BPI‐PhPXZ and BPI‐PhDMAC, composed of twisted biphenyl‐diimide (BPI) acceptors and phenoxazine or acridine donors are synthesized. BPI‐PhPXZ and BPI‐PhDMAC show prominent aggregation‐induced emission (AIE) and thermally activated delayed fluorescence (TADF), and enjoy good thermal and electrochemical stabilities. Doped OLEDs fabricated with the two compounds have achieved high external quantum efficiencies (EQEs) of 18.1% and 16.2%, respectively. The results highlight the beneficial role of well‐designed BPI acceptor for the development of efficient D‐A‐D type TADF emitters with AIE properties.
Highly electron-accepting viologen derivative, o-carborane viologens (CbV2+), and their iron based-supramolecular polymer (FeSPs) with tunable optoelectronic properties are reported. Carborane viologens showed excellent electron redox properties with low reduction threshold...
Two coordinated metallacycles (rhomboid for M1, hexagonal for M2) with selenoviologens (SeV2+) pendants were synthesized via coordination‐driven hierarchical self‐assembly. M1/M2 with rigid and discrete metallacyclic cores showed tunable optoelectronic properties due to strong π–π stacking and push–pull electron structures. Femtosecond transient absorption (fs‐TA) revealed that the formation of macrocyclic structure can not only enhance the stability of radical cation, but also improve the efficiency of intramolecular charge transfer and produce a long‐lived charge separation state. The electrochromic performances of M1/M2‐based devices were exhibited to show decent radical stabilization. By using M1/M2 as the photocatalyst, the improved catalytic efficiency (>80 %) of visible‐light‐induced cross‐dehydrogenative coupling (CDC) reactions was achieved due to the highly stable radical cations and long‐lived charge separation states, which were also confirmed by fs‐TA.
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