Boron-nitrogen-doped π-conjugated systems have been regarded as a type of organic materials with exceptional electronic and optical properties, which makes them promising in optoelectronic devices. Due to the isoelectronic relationship...
A series of tetracoordinate boron-doped polycyclic aromatic hydrocarbons have been synthesized under mild conditions, featuring delayed fluorescence and aggregation-induced emission.
The incorporation of heteroatoms and/or heptagons as the defects into helicenes expands the variety of chiroptical materials with novel properties. However, it is still challenging to construct novel boron‐doped heptagon‐containing helicenes with high photoluminescence quantum yields (PLQYs) and narrow full‐width‐at‐half‐maximum (FWHM) values. We report an efficient and scalable synthesis of a quadruple helicene 4Cz‐NBN with two nitrogen‐boron‐nitrogen (NBN) units and a double helicene 4Cz‐NBN‐P1 bearing two NBN‐doped heptagons, the latter could be formed via a two‐fold Scholl reaction of the former. The helicenes 4Cz‐NBN and 4Cz‐NBN‐P1 exhibit excellent PLQYs up to 99 % and 65 % with narrow FWHM of 24 nm and 22 nm, respectively. The emission wavelengths are tunable via stepwise titration experiments of 4Cz‐NBN‐P1 toward fluoride, enabling distinguished circularly polarized luminescence (CPL) from green, orange (4Cz‐NBN‐P1‐F1) to yellow (trans/cis‐4Cz‐NBN‐P1‐F2) with near‐unity PLQYs and broader circular dichroism (CD) ranges. The five structures of the aforementioned four helicenes were confirmed by single crystal X‐ray diffraction analysis. This work provides a novel design strategy for construction of non‐benzenoid multiple helicenes exhibiting narrow emissions with superior PLQYs.
Modification of π-conjugated systems using a boron atom as the dopant has become a powerful approach to create new structures and new properties. Herein, we report a facile synthesis of replacing the carbon edges of [4]triangulene by three oxygen-boron-oxygen (OBO) units. The triangulenes are structurally similar to [4]triangulene and isoelectronic to the trianion of [4]triangulene. The structure of triangulene is confirmed by single-crystal X-ray diffraction analysis, revealing an off-plane core with three edgemodified OBO units. These triangulenes exhibit excellent thermal stability. These compounds have phosphorescence with lifetime longer than 1 s at 77 K. Both theoretical calculations and photophysical investigation of triangulenes indicate that this kind of molecules display a rare anti-Kasha fluorescence and phosphorescence emissions from multiple higher excited states.
The boron-doped polycyclic aromatic hydrocarbons (PAHs) have attracted ongoing attention in the field of optoelectronic materials due to their unique optical and redox properties. To investigate the effect of tetracoordinate boron in PAHs bearing N-heterocycles (indole and carbazole), a facile approach to four-coordinate boron-doped PAHs was developed, which does not require elevated temperature and pre-synthesized functionalized boron reactants. Five tetracoordinate boron-doped PAHs (NBNN-1 – NBNN-5) were synthesized with different functional groups. Two of them (NBNN-1 and NBNN-2) could further undergo oxidative coupling reactions to form fused off-plane tetracoordinate boron-doped PAHs NBNN-1f and NBNN-2f. Compared to the three-coordinate boron-doped counterparts, the UV/Vis absorption and fluorescent emission are significantly red-shift. Unlike the distinct impact of coordination number of boron on optoelectronic properties, the difference of functional groups on the boron atom has negligible impact on their optical and electrochemical properties. The compounds NBNN-1f and NBNN-2f show aggregation-induced emission.
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