posted on 2024-02-02, 17:33authored byGuilin Hu, Jingyi He, Jing Chen, Yongjun Li
Graphdiyne
(GDY) multilayers show stacking-style-dependent physical
properties; thus, controlling the stacking style of nanostructures
is crucial for utilizing their electrical, optical, and transport
properties in electro-optical devices. Herein, we report the assemblies
of nanographdiynes decorated with substituents with different steric
hindrances to adjust the stacking style. We show that the π-stacked
aggregates were influenced by peripheral substituents and the substrate.
Steric hexaterphenyl-substituted nanoGDY scaffolds led to dimer structures
stacked in the AB-3 configuration with a twist angle of 26.01°
or the AB-1 configuration with an in-plane shift along one diyne link.
With the interval replacement of steric substituents with long C12
alkyl chains, nanoGDYs were stacked in the AB-2 configuration to decrease
the steric congestion, eventually leading to one-dimensional (1D)
nanofibrous aggregates. Self-assembly in the presence of substrates
can result in ABC-stacked nanoGDYs, which endowed us with the possibility
of using nanoGDY as the template for GDY growth in a homogeneous reaction.
High-resolution transmission electron microscopy (HRTEM), powder X-ray
diffraction (PXRD), X-ray photoelectron spectroscopy (XPS), Raman
spectroscopy, and near-infrared–ultraviolet–visible
(NIR–UV–vis) absorption spectroscopy indicate that the
crystalline GDY prepared in this way is a 1.18 eV bandgap semiconductor.