We report on the fabrication of a boron-based two-dimensional (2D) material via electron irradiation-induced cross-linking of carborane self-assembled monolayers (SAMs) on crystalline silver substrates. The SAMs of 1,2-dicarba-closo-dodecarborane-9,12-dithiol (O9,12) were prepared on flat crystalline silver substrates and irradiated with low-energy electrons, resulting in a 2D nanomembrane. The mechanical stability and compact character of the carborane nanomembrane were improved by using 12-(1',12'-dicarba-closo-dodecarboran-1'-yl)-1,12-dicarba-closo-dodecarborane-1-thiol (1-HS-bis-pCB), a longer, rod-like SAM precursor with two para-carborane units linked linearly together. The self-assembly, cross-linking process, and transfer of the resulting membranes onto holey substrates were characterized with different complementary surface-sensitive techniques including X-ray photoelectron spectroscopy (XPS), ultraviolet photoelectron spectroscopy (UPS), and low-energy electron diffraction (LEED) as well as scanning tunneling and electron microscopies (STM, SEM) to provide insight on the structural changes within the cross-linked SAMs. The presented methodology has potential for the development of boron-based 2D materials for applications in electronic and optical devices.

• Klíčová slova
• carboranes, electron irradiation induced chemical synthesis, molecular self-assembly, nanomembranes, two-dimensional materials,
• Publikační typ
• časopisecké články MeSH

The chemistry and physics of macropolyhedral B18H22 clusters have attracted significant attention due to the interesting photophysical properties of anti-B18H22 (blue emission, laser properties) and related potential applications. We have focused our attention on the "forgotten" syn-B18H22 isomer, which has received very little attention since its discovery compared to its anti-B18H22 isomer, presumably because numerous studies have reported this isomer as nonluminescent. In our study, we show that in crystalline form, syn-B18H22 exhibits blue fluorescence and becomes phosphorescent when substituted at various positions on the cluster, associated with peculiar microstructural-dependent effects. This work is a combined theoretical and experimental investigation that includes the synthesis, separation, structural characterization, and first elucidation of the photophysical properties of three different monothiol-substituted cluster isomers, [1-HS-syn-B18H21] 1, [3-HS-syn-B18H21] 3, and [4-HS-syn-B18H21] 4, of which isomers 1 and 4 have been proved to exist in two different polymorphic forms. All of these newly substituted macropolyhedral cluster derivatives (1, 3, and 4) have been fully characterized by NMR spectroscopy, mass spectrometry, single-crystal X-ray diffraction, IR spectroscopy, and luminescence spectroscopy. This study also presents the first report on the mechanochromic shift in the luminescence of a borane cluster and generally enriches the area of rather rare boron-based luminescent materials. In addition, we present the first results proving that they are useful constituents of carbon-free self-assembled monolayers.

• Publikační typ
• časopisecké články MeSH