Despite the great potential of heteroatom-containing polycyclic aromatic hydrocarbons in organic optoelectronics, there are very limited reports on heteroaromatics containing a B-N-B bond in the π-scaffold. Herein, stable 1,9-dibora-9a-azaphenalenyl (DBAP) derivatives, named BNB-embedded phenalenyls, are presented. The DBAP skeleton contains a three-center two-π-electron B-N-B moiety with 12 π-electrons and can be regarded as the isoelectronic structure of the phenalenyl cation. Chemical reduction of the phenyl derivative of DBAP by potassium generated the dianion containing 14 delocalized π-electrons, which can be regarded as the isoelectronic structure of the phenalenyl anion. The dianion is sandwiched and stabilized by two bulky [K([18]crown-6)] counterions according to its X-ray structure. However, its monoanion (an isoelectronic structure of the henalenyl radical) generated by mixing equal moles of neutral compound and dianion gave an unusual B-N-B-embedded benzo[cd]fluoranthene dianion, which again was confirmed by X-ray crystallographic analysis. The new dianion containing 20 π-electrons is highly aromatic and is further stabilized by [K([18]crown-6)] counterions. An aromaticity driven rearrangement mechanism was proposed for this unusual transformation. Based on X-ray structures and theoretical calculations, the B-N-B moiety in the neutral and anionic DBAP participates in the π-electron delocalization along the whole DBAP skeleton like their phenalenyl cation/radical/anion counterparts, but with more localized character. Therefore, our studies report the first synthesis and characterization of a B-N-B-embedded phenalenyl and its anionic species, which show unique electronic structure and unusual reactivity different from that of their all-carbon phenalenyl analogues.
We have prepared a turn-on fluorescent probe for biothiols based on bromoketo coumarin (KC-Br). The emission intensity of the coumarin chromophore is modulated by both the heavy atom effect and internal charge transfer (ICT) process. The probe KC-Br is intrinsically nonfluorescent; however, after being reacted with thiols, the bromide moiety is substituted by the -SH group, which elicits a significant fluorescence increase. We surmised the free -NH2 group would further react with carbonyl in the Cys/Hcy-substituted intermediate product yielding to Schiff base compound KC-Cys/KC-Hcy, but not in compound KC-GSH. The ICT effect has a stronger influence in compound KC-GSH than that in compound KC-Cys/KC-Hcy, resulting in compound KC-GSH having a stronger fluorescence. Thus, the probe has a good selectivity for GSH over other various biologically relevant species and even two other similar biothiols (Cys/Hcy) and could image glutathione (GSH) in living cells. We expect the design concept presented in this work would be widely used for the design of fluorescent probes for distinguishing among biothiols.
The porous structure composed of non-metal elements of covalent organic frameworks (COFs) contributes to a large surface area and multifunction, rendering COFs a brilliant material for energy storage. Unfortunately, the low conductivity of most COFs limits their application in batteries. Herein, we fabricate COF-derived nitrogen-doped porous carbon (NPC) using nitrogen-rich COF-JLU2 as precursors by a simple carbonization for potassium-ion batteries (PIBs) and aluminum (Al) batteries for the first time. The computational results suggest that NPC has an enhanced conductivity and optimized electron density distribution. NPC could overcome the low conductivity of COF and thus further optimize its electrochemical performance in PIBs and Al batteries. It displays an excellent stability even after 2500 cycles (as the anode for PIBs) and 30000 cycles (as the cathode for Al batteries) with a high Coulombic efficiency. This fascinating study may be extended in other COFs for energy storage applications.
We introduce a new FRET strategy to construct a ratiometric fluorescent H2S sensor. The ratio emission signal of the coumarin-naphthalimide dyad is modulated by the FRET process, which works in coordination with the ICT mechanism. The FRET process on/off is controlled through tuning the overlap level of the donor emission spectrum with the acceptor absorption via modulation of the acceptor fluorophore absorption wavelength. was applied to visualize both the intracellular exogenous and endogenous H2S through blue and green emission channels.
Synthesis of triangulene and its derivatives is challenging due to their intrinsic high spin nature. Herein, we report solution-phase synthesis and isolation of a nitrogen-doped triangulene (i.e., aza-triangulene) (NT) and its cation (NT + ) in single-crystal form. Notably, the cation NT + can be regarded as an isoelectronic structure of the corresponding all-carbon triangulene. Both NT and NT + show reasonable stability due to kinetic blocking by bulky and electron-withdrawing aryl substituents, and intramolecular donoracceptor interaction. Bond length analysis, magnetic measurements and theoretical calculations reveal that the neutral NT has a doublet ground state with a zwitterionic character, while the cation NT + exhibits a triplet ground state with a singlet-triplet energy gap of + 0.84 kcal mol À 1 . This study provides a rational strategy to access high-spin systems by heteroatom doping of pure π-conjugated polycyclic hydrocarbons.
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