In:
Angewandte Chemie, Wiley, Vol. 136, No. 11 ( 2024-03-11)
Abstract:
Precisely introducing topological defects is an important strategy in nanographene crystal engineering because defects can tune π‐electronic structures and control molecular assemblies. The synergistic control of the synthesis and assembly of nanographenes by embedding the topological defects to afford two‐dimensional (2D) crystals on surfaces is still a great challenge. By in‐situ embedding ladder bipyrazinylene (LBPy) into acene, the narrowest nanographene with zigzag edges, we have achieved the precise preparation of 2D nonbenzenoid heteroacene crystals on Au(111). Through intramolecular electrocyclization of o ‐diisocyanides and Au adatom‐directed [2+2] cycloaddition, the nonbenzenoid heteroacene products are produced with high chemoselectivity, and lead to the molecular 2D assembly via LBPy‐derived interlocking hydrogen bonds. Using bond‐resolved scanning tunneling microscopy, we determined the atomic structures of the nonbenzenoid heteroacene product and diverse organometallic intermediates. The tunneling spectroscopy measurements revealed the electronic structure of the nonbenzenoid heteroacene, which is supported by density functional theory (DFT) calculations. The observed distinct organometallic intermediates during progression annealing combined with DFT calculations demonstrated that LBPy formation proceeds via electrocyclization of o ‐diisocyanides, trapping of heteroarynes by Au adatoms, and stepwise elimination of Au adatoms.
Type of Medium:
Online Resource
ISSN:
0044-8249
,
1521-3757
DOI:
10.1002/ange.v136.11
DOI:
10.1002/ange.202318142
Language:
English
Publisher:
Wiley
Publication Date:
2024
detail.hit.zdb_id:
506609-8
detail.hit.zdb_id:
1479266-7
