Academic Journal
(13)C or Not (13)C: Selective Synthesis of Asymmetric Carbon-13-Labeled Platinum(II) cis-Acetylides.
| العنوان: | (13)C or Not (13)C: Selective Synthesis of Asymmetric Carbon-13-Labeled Platinum(II) cis-Acetylides. |
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| المؤلفون: | Archer, S.A., Keane, T., Delor, M., Meijer, A.J., Weinstein, J.A. |
| بيانات النشر: | American Chemical Society |
| سنة النشر: | 2016 |
| المجموعة: | White Rose Research Online (Universities of Leeds, Sheffield & York) |
| الوصف: | 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 (13)C 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 (12)C≡(12)C and (13)C≡(13)C 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. |
| نوع الوثيقة: | article in journal/newspaper |
| وصف الملف: | text |
| اللغة: | English |
| Relation: | https://eprints.whiterose.ac.uk/103879/3/12C13C-Acetylides_150716AJHMM.pdf; https://eprints.whiterose.ac.uk/103879/9/acs%252Einorgchem%252E6b01287.pdf; Archer, S.A., Keane, T. orcid.org/0000-0003-4975-0868 , Delor, M. et al. (2 more authors) (2016) (13)C or Not (13)C: Selective Synthesis of Asymmetric Carbon-13-Labeled Platinum(II) cis-Acetylides. Inorganic Chemistry, 55 (17). pp. 8251-8253. ISSN 0020-1669 |
| DOI: | 10.1021/acs.inorgchem.6b01287 |
| الاتاحة: | https://eprints.whiterose.ac.uk/103879/ https://eprints.whiterose.ac.uk/103879/3/12C13C-Acetylides_150716AJHMM.pdf https://eprints.whiterose.ac.uk/103879/9/acs%252Einorgchem%252E6b01287.pdf https://doi.org/10.1021/acs.inorgchem.6b01287 |
| Rights: | cc_by_4 |
| رقم الانضمام: | edsbas.E5942D9 |
| قاعدة البيانات: | BASE |
| DOI: | 10.1021/acs.inorgchem.6b01287 |
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