Control over on-surface reaction pathways is crucial but challenging for the precise construction of conjugated nanostructures at the atomic level. Herein we demonstrate a selective on-surface covalent coupling reaction that is templated by metal-organic coordinative bonding, and achieve a porous nitrogen-doped carbon nanoribbon structure. In contrast to the inhomogeneous polymorphic structures resulting from the debrominated aryl-aryl coupling reaction on Au(111), the incorporation of an Fe-terpyridine (tpy) coordination motif into the on-surface reaction controls the molecular conformation, guides the reaction pathway, and finally yields pure organic sexipyridine-p-phenylene nanoribbons. Emergent molecular conformers and reaction products in the reaction pathways are revealed by scanning tunneling microscopy, density functional theory calculations and X-ray photoelectron spectroscopy, demonstrating the template effect of Fe-tpy coordination on the on-surface covalent coupling. Our approach opens an avenue for the rational design and synthesis of functional conjugated nanomaterials with atomic precision.

The core/shell micro-/nanostructures with versatility, tunability, stability, dispersibility, and biocompatibility are widely applied in optics, biomedicine, catalysis, and energy. Organic micro-/nanocrystals have significant applications in miniaturized optoelectronics because of their controllable self-assembly behavior, tunable optical properties, and tailor-made molecular structure. Nevertheless, the advanced organic core/shell micro-/nanostructures, which possess multifunctionality, flexibility, and higher compatibility, are rarely demonstrated because of the dynamic nature of molecular self-assembly and the complex epitaxial relationship of material combination. Herein, we demonstrate the one-dimensional organic core/shell micro-/nanostructures with component interchange, which originates from the 4,4′-((1E,1′E)-(2,5-dimethoxy-1,4-phenylene)­bis­(ethene-2,1-diyl))­dipyridine (DPEpe) single-crystal microrods or the DPEpe-HCl single-crystal microrods after a reversible protonation or deprotonation process. Notably, the DPEpe/DPEpe-HCl core/shell microrods display vivid visualizations of tunable emission color via an efficient energy-transfer process during the stepwise formation of a shell layer. More significantly, these DPEpe/DPEpe-HCl and DPEpe-HCl/DPEpe core/shell microrods cooperatively demonstrate the multicolor optical waveguide properties continuously adjusted from green [CIE (0.326, 0.570)], to yellow [CIE (0.516, 0.465)], and to red [CIE (0.614, 0.374)]. Our investigation provides a new strategy to fabricate the organic core/shell micro-/nanostructures, which can eventually contribute to the advanced organic optoelectronics at the micro-/nanoscale.

Carbazole is a classic tricyclic aromatic compound that has been widely used in organic optoelectronics. Appropriate functionalization on its aromatic rings will significantly increase the possibilities for its application as an optoelectronic material. Position engineering of carbazole not only leads to its structural diversity, but also substantially enriches its functionality. Bicarbazoles have 15 isomers, most of which are well studied and have been applied in organic light‐emitting diodes (OLEDs). However, one isomer, 9,9′‐bicarbazole, is rarely investigated as an OLED material. Therefore, two 9,9′‐bicarbazole derivatives, 3,3′‐di(10H‐phenoxazin‐10‐yl)‐9,9′‐bicarbazole and 3,3′‐di(10H‐phenothiazin‐10‐yl)‐9,9′‐bicarbazole, have been designed and prepared for use as host materials for green and red OLEDs. These two compounds demonstrated good device performances, and it is believed that the 9,9′‐bicarbazole building block could be a novel platform for the design of efficient host materials for OLEDs.

Diazaspirocycle molecular platforms were used to construct hosts for efficient phosphorescent organic light-emitting diodes.

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