Pyrenes, as photoactive polycyclic aromatic hydrocarbons (PAHs), represent promising modules for the bottom-up assembly of functional nanostructures. Here, we introduce the synthesis of a family of pyrene derivatives peripherally functionalized with pyridin-4-ylethynyl termini and comprehensively characterize their self-assembly abilities on a smooth Ag(111) support by scanning tunneling microscopy. By deliberate selection of number and geometric positioning of the pyridyl-terminated substituents, two-dimensional arrays, one-dimensional coordination chains, and chiral, porous kagomé-type networks can be tailored. A comparison to phenyl-functionalized reference pyrenes, not supporting the self-assembly of ordered structures at low coverage, highlights the role of the pyridyl moieties for supramolecular crocheting and knitting. Furthermore, we demonstrate the selective spangling of pores in the two-dimensional pyrene assemblies by a distinct number of iodine atoms as guests by atomically resolved imaging and complementary X-ray photoelectron spectroscopy.

Intramolecular current-induced vibronic excitations are reported in highly ordered monolayers of quaterphenylene dicarbonitriles at an electronically patterned boron nitride on copper platform (BN/Cu(111)). A first level of spatially modulated conductance at the nanometer-scale is induced by the substrate. Moreover, a second level of conductance variations at the molecular level is found. Low temperature scanning tunneling microscopy studies in conjunction with molecular dynamics calculations reveal collective amplification of the molecule's interphenylene torsion angles in the monolayer. Librational modes influencing these torsion angles are identified as initial excitations during vibronic conductance. Density functional theory is used to map phenylene breathing modes and other vibrational excitations that are suggested to be at the origin of the submolecular features during vibronic conductance.

The controlled modification of electronic and photophysical properties of polycyclic aromatic hydrocarbons by chemical functionalization, adsorption on solid supports, and supramolecular organization is the key to optimize the application of these compounds in (opto)electronic devices. Here, we present a multimethod study comprehensively characterizing a family of pyridin-4-ylethynyl-functionalized pyrene derivatives in different environments. UV–vis measurements in toluene solutions revealed absorption at wavelengths consistent with density functional theory (DFT) calculations, while emission experiments showed a high fluorescence quantum yield. Scanning tunneling microscopy (STM) and spectroscopy (STS) measurements of the pyrene derivatives adsorbed on a Cu(111)-supported hexagonal boron nitride (hBN) decoupling layer provided access to spatially and energetically resolved molecular electronic states. We demonstrate that the pyrene electronic gap is reduced with an increasing number of substituents. Furthermore, we discuss the influence of template-induced gating and supramolecular organization on the energies of distinct molecular orbitals. The selection of the number and positioning of the pyridyl termini in tetrasubstituted, trans- and cis-like-disubstituted derivatives governed the self-assembly of the pyrenyl core on the nanostructured hBN support, affording dense-packed arrays and intricate porous networks featuring a kagome lattice.