13C or Not 13C: selective synthesis of asymmetric carbon-13-labeled platinum(II) cis-acetylides.
|Archer, Stuart A., Keane, Theo, Delor, Milan, Meijer, Anthony J. H. M. and Weinstein, Julia A.
Asymmetric isotopic labeling of parallel and identical electron- or energy-transfer pathways in symmetrical molecular assemblies is an extremely challenging task owing to the inherent lack of isotopic selectivity in conventional synthetic methods. Yet, it would be a highly valuable tool in the study and control of complex light-matter interactions in molecular systems by exclusively and nonintrusively labeling one of otherwise identical reaction pathways, potentially directing charge and energy transport along a chosen path. Here we describe the first selective synthetic route to asymmetrically labeled organometallic compounds, on the example of charge-transfer platinum(II) cis-acetylide complexes. We demonstrate the selective 13C labeling of one of two acetylide groups. We further show that such isotopic labeling successfully decouples the two ν(C≡C) in the mid-IR region, permitting independent spectroscopic monitoring of two otherwise identical electron-transfer pathways, along the 12C≡12C and 13C≡13C coordinates. Quantum-mechanical mixing leads to intriguing complex features in the vibrational spectra of such species, which we successfully model by full-dimensional anharmonically corrected DFT calculations, despite the large size of these systems. The synthetic route developed and demonstrated herein should lead to a great diversity of asymmetric organometallic complexes inaccessible otherwise, opening up a plethora of opportunities to advance the fundamental understanding and control of light-matter interactions in molecular systems.
|Organometallic chemistry; Chemistry; Spectroscopy; Electron transfer
|American Chemical Society
|Digital Object Identifier (DOI)
|Web address (URL)
|09 Aug 2016
|Publication process dates
|16 Oct 2018, 12:10
Archived with thanks to Inorganic Chemistry
|University of Sheffield, Department of Chemistry, University of Sheffield, Sheffield S3 7HF, United Kingdom, Department of Chemistry, University of Sheffield, Sheffield S3 7HF, United Kingdom, Department of Chemistry, University of Sheffield, Sheffield S3 7HF, United Kingdom, Department of Chemistry, University of Sheffield, Sheffield S3 7HF, United Kingdom and Department of Chemistry, University of Sheffield, Sheffield S3 7HF, United Kingdom
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