Macropolyhedral syn-B18H22, the “Forgotten” Isomer

0574399 - ÚACH 2024 RIV US eng J - Journal Article
Patel, Deepak Kumar - Sooraj, Bhuvanachandrannair Sreekala - Kirakci, Kaplan - Macháček, Jan - Kučeráková, Monika - Bould, Jonathan - Dušek, Michal - Frey, M. - Neumann, C. - Ghosh, S. - Turchanin, A. - Pradeep, T. - Baše, Tomáš
Macropolyhedral syn-B18H22, the “Forgotten” Isomer.
Journal of the American Chemical Society. Roč. 145, č. 32 (2023), s. 17975-17986. ISSN 0002-7863. E-ISSN 1520-5126
R&D Projects: GA MŠMT(CZ) LTAIN19152; GA MŠMT LM2023065
Research Infrastructure: e-INFRA CZ - 90140
Institutional support: RVO:61388980 ; RVO:68378271
Keywords : Boron * Crystal structure * Molecular structure * Supramolecular chemistry, * Thiols
OECD category: Inorganic and nuclear chemistry; Condensed matter physics (including formerly solid state physics, supercond.) (FZU-D)
Impact factor: 15, year: 2022
Method of publishing: Open access

The chemistry and physics of macropolyhedral B18H22 clusters have attracted significant attention dueto theinteresting photophysical properties of anti-B18H22 (blue emission, laser properties) and relatedpotential applications. We have focused our attention on the “forgotten” syn-B18H22 isomer, which has receivedvery little attention since its discovery compared to its anti-B18H22 isomer, presumably becausenumerous studies have reported this isomer as nonluminescent. In ourstudy, we show that in crystalline form, syn-B18H22 exhibits blue fluorescence and becomes phosphorescentwhen substituted at various positions on the cluster, associated withpeculiar microstructural-dependent effects. This work is a combinedtheoretical and experimental investigation that includes the synthesis,separation, structural characterization, and first elucidation ofthe photophysical properties of three different monothiol-substitutedcluster 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 fullycharacterized by NMR spectroscopy, mass spectrometry, single-crystalX-ray diffraction, IR spectroscopy, and luminescence spectroscopy.This study also presents the first report on the mechanochromic shiftin the luminescence of a borane cluster and generally enriches thearea of rather rare boron-based luminescent materials. In addition,we present the first results proving that they are useful constituentsof carbon-free self-assembled monolayers.
Permanent Link: https://hdl.handle.net/11104/0344863


Research data: CCDC