Charge and spin delocalization in mixed-valent vinylruthenium-triarylamine-conjugates with planarized triarylamines
We report on three new vinylruthenium-triarylamine (TA) conjugates with planarized TA substituents. The neutral, mono-, and dioxidized forms of the complexes were scrutinized by UV/vis/NIR, IR, and EPR spectroscopies as well as by quantum chemical calculations. By analyzing the intervalence charge-t...
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| Main Authors: | , , , , , |
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| Format: | Article (Journal) |
| Language: | English |
| Published: |
January 13, 2022
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| In: |
Organometallics
Year: 2022, Volume: 41, Issue: 5, Pages: 532-546 |
| ISSN: | 1520-6041 |
| DOI: | 10.1021/acs.organomet.1c00619 |
| Online Access: | Verlag, lizenzpflichtig, Volltext: https://doi.org/10.1021/acs.organomet.1c00619
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| Author Notes: | Stefanie Breimaier, Nina Fröhlich, Jan Herberger, Michael Linseis, Milan Kivala, and Rainer F. Winter |
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| 245 | 1 | 0 | |a Charge and spin delocalization in mixed-valent vinylruthenium-triarylamine-conjugates with planarized triarylamines |c Stefanie Breimaier, Nina Fröhlich, Jan Herberger, Michael Linseis, Milan Kivala, and Rainer F. Winter |
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| 520 | |a We report on three new vinylruthenium-triarylamine (TA) conjugates with planarized TA substituents. The neutral, mono-, and dioxidized forms of the complexes were scrutinized by UV/vis/NIR, IR, and EPR spectroscopies as well as by quantum chemical calculations. By analyzing the intervalence charge-transfer (IVCT) transitions of the mixed-valent radical cations, we obtain information on the extent of electronic coupling between the chemically different redox sites. Completely delocalized Ru-MeTA+ shows a vibrationally structured, non-solvatochromic IVCT band. Decreased blueshifts of the indicative Ru(CO) stretching vibration during the first oxidation and larger A(14N) EPR hyperfine splitting constants in concert with smaller g-values indicate enhanced TA contributions to the singly occupied molecular orbital of the other two complexes Ru-TOTA•+ and Ru-DOTA•+ and hence less symmetrical charge and spin density distributions. This is also reflected by the solvatochromism and the asymmetric shape of the IVCT band with a smaller bandwidth at the low-energy side. Temperature-dependent UV/vis/NIR spectroscopy of mixed-valent Ru-TOTA•+ and Ru-DOTA•+ revealed that the band skewing is due to the vibrational coupling of the IVCT transition to symmetrical vibrations, placing these radical cations near or at the class II/III borderline according to Robin and Day. | ||
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