A novel BN-fused coronene derivative 1,5,9-triaza-2,6,10-triphenylboracoronene (1) has been successfully synthesized in one step from 2,3,6,7,9,10-hexamethoxy-1,5,9-triamino-triphenylene. Compound 1 has been investigated using photophysical, electrochemical, and molecular simulation methods. Interestingly, three phenyl groups at B centers in compound 1 can be replaced by hydroxyl units stepwise through hydroxylation in wet organic solvents, leading to changes in the packing and physical properties.
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http://dx.doi.org/10.1021/ol503575t | DOI Listing |
Angew Chem Int Ed Engl
December 2024
Key Laboratory of Organic Optoelectronics and Molecular Engineering, Department of Chemistry, Tsinghua University, Beijing, 100084, P.R. China.
The in-depth research on the charge transport properties of BN-embedded polycyclic aromatic hydrocarbons (BN-PAHs) still lags far behind studies of their emitting properties. Herein, we report the successfully synthesis of novel ladder-type BN-PAHs (BCNL1 and BCNL2) featuring a highly ordered BCN acene unit, achieved via a nitrogen-directed tandem C-H borylation. Single-crystal X-ray diffraction analysis unambiguously revealed their unique and compact herringbone packing structures.
View Article and Find Full Text PDFOrg Lett
December 2024
Ningbo Key Laboratory of Biomedical Imaging Probe Materials and Technology, Laboratory of Advanced Theranostic Materials and Technology, Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences, Ningbo, Zhejiang 315201, China.
-directed 2-fold bromoboration reactions of diynes with BBr have been developed, allowing the access to novel internally BN-doped polycyclic aromatic hydrocarbons from readily available precursors under mild conditions. Computational investigations identified three potential reaction mechanisms, each involving either BBr or [BBr], with low activation barriers ( < 16 kcal/mol) for all pathways. The resulting brominated products can be further functionalized through various cross-coupling protocols, enabling the synthesis of highly luminescent emitters with quantum yield exceeding 90.
View Article and Find Full Text PDFJ Phys Chem A
September 2024
Department of Chemical Sciences and Centre for Advanced Functional Materials, Indian Institute of Science Education and Research (IISER), Kolkata, Mohanpur 741246, India.
The electronic structure of boron (B)-nitrogen (N)-substituted pyrene molecules is the center of attraction in designing an efficient intermolecular singlet fission (x-SF) material. Thermodynamic energy criteria required for x-SF are obtained by captodative substitution with B and N in pristine pyrene to increase the lowest singlet-triplet energy gap. We computed low-lying excited states of BN-embedded pyrene molecules by exactly solving the Pariser-Parr-Pople (PPP) model Hamiltonian and compared these results with the TDDFT and EOM-CCSD values.
View Article and Find Full Text PDFAdv Mater
August 2024
Beijing National Laboratory for Molecular Sciences, CAS Research/Education Center for Excellence in Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190, P. R. China.
In recent years, conjugated polymers have received widespread attention due to their characteristic advantages of light weight, favorable solution processability, and structural modifiability. Among various conjugated polymers, fluorinated ones have developed rapidly to achieve high-performance n-type or ambipolar polymeric semiconductors. The uniqueness of fluorinated conjugated polymers contains the high coplanarity of their structures, lower frontier molecular orbital energy levels, and strong nonbonding interactions.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
August 2024
School of Chemistry and Chemical Engineering, Shandong University, Jinan, 250100, China.
The replacement of a CC unit with an isoelectronic BN unit in aromatic systems can give rise to molecules and materials with fascinating properties. We report here the synthesis, characterization, and reactivity of a 1,4,2,3-diazadiborole species, 2, featuring an unprecedented 6π-aromatic BN-heterocyclic moiety that is isoelectronic to cyclopentadienide (Cp). Bearing an unsymmetrical B=B entity, 2 exhibits reactivity toward oxidants, protic reagents, electrophiles, and unsaturated substrates.
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