Tuning valence tautomerism in a family of dinuclear cobalt complexes incorporating a conjugated bridging bis(dioxolene) ligand with weak communication

Fischer, Tristan E.; Janetzki, Jett T.; M. Zahir, F. Zahra; Gable, Robert W.; Starikova, Alyona A.; Boskovic, Colette

doi:10.1039/d3dt04162j

Cited by 2 publications

(1 citation statement)

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“…[104] There is also evidence that local binding sites critically determine relaxation pathways including reactive ones such as bond breaking and charge transfer leading for example to ionisation or valence tautomerism. [110][111] A further breakthrough for elucidation of such interactions was the development of 2-and multi-dimensional time-and spatially-resolved spectroscopy [112][113][114][115][116] because fs laser pulses with pulse duration well below 100 fs are typically spectrally broad due to Heisenberg's uncertainty principle. Such sophisticated experiments have not yet been tested on complicated systems with many degrees of freedom including the ones presented here.…”

Section: The Relevance Of Using Time Vs Frequency Domains To Interpre...mentioning

confidence: 99%

Gaining Insights into the Interplay between Optical and Magnetic Properties in Photoexcited Coordination Compounds

Braun,

Powell,

Unterreiner

2024

Chemistry A European J

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We describe early and recent advances in the fascinating field of combined magnetic and optical properties of inorganic coordination compounds and in particular of 3d‐4f single molecule magnets. We cover various applied techniques which allow for the correlation of results obtained in the frequency and time domain in order to highlight the specific properties of these compounds and the future challenges towards multidimensional spectroscopic tools. An important point is to understand the details of the interplay of magnetic and optical properties through performing time‐resolved studies in the presence of external fields especially magnetic ones. This will enable further exploration of this fundamental interactions i.e. the two components of electromagnetic radiation influencing optical properties.

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Section: The Relevance Of Using Time Vs Frequency Domains To Interpre...mentioning

confidence: 99%

Gaining Insights into the Interplay between Optical and Magnetic Properties in Photoexcited Coordination Compounds

Braun,

Powell,

Unterreiner

2024

Chemistry A European J

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Tuning Valence Tautomerism in Dinuclear Cobalt Complexes by Modulating Communication in the Bridging Ligand

Janetzki,

Gransbury,

Gable

et al. 2024

Eur J Inorg Chem

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The capability of bis(dioxolene) ligands to access multiple redox states makes them ideal candidates to tune the electronic properties of metal complexes, for example to achieve valence tautomerism (VT). In this study, a family of dinuclear cobalt complexes have been isolated with the bridging bis(dioxolene) thean− ligand in the cat2−‐cat2−, cat2−‐SQ●− and SQ●−‐SQ●− states (cat2− = catecholate, SQ●− = semiquinonate): [{CoIII(tpa)}2(theacat‐cat)](PF6)2 (1), [{CoIII(tpa)}2(theacat‐SQ)](PF6)3 (2), and [{CoIII(tpa)}2(theaSQ‐SQ)](PF6)4 (3) (theaH4 = 2,3,6,7‐tetrahydroxy‐9,10‐dimethyl‐9,10‐dihydro‐9,10‐ethanoanthracene, tpa = tris(2‐pyridylmethyl)amine). Multi‐technique analysis confirmed that 1, 2 and 3 adopt low spin (LS)‐CoIII containing {CoIII‐cat‐cat‐CoIII}, {CoIII‐cat‐SQ‐CoIII} and {CoIII‐SQ‐SQ‐CoIII} states, respectively. Compound 1 undergoes thermally‐induced {CoIII‐cat‐cat‐CoIII} ⇌ {CoIII‐cat‐SQ‐CoII} VT in the solid‐ and solution‐states above 300 K, involving high spin‐CoII. This interconversion is contrary to expectations, as tpa typically stabilizes low spin‐CoIII‐cat. Compound 2 is mixed‐valence class II‐III, indicating a localized electronic structure, with electron transfer faster than the EPR and solvent rearrangement timescales, but slower than the IR timescale. Compound 3 exhibits strong antiferromagnetic exchange. The overlap between the dioxolene π‐orbitals in thean− increases the accessibility of the cat2−‐SQ●− state, resulting in VT for 1. This study demonstrates that thean− can be isolated in multiple oxidation states in metal complexes, promising for applications in magnetic materials.

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Tuning valence tautomerism in a family of dinuclear cobalt complexes incorporating a conjugated bridging bis(dioxolene) ligand with weak communication

Abstract: Valence tautomerism (VT) involves the stimulated reversible intramolecular electron transfer between a redox-active metal and ligand. Dinuclear cobalt complexes bridged by bis(dioxolene) ligands can undergo thermally-induced VT with access to...

Cited by 2 publications

References 59 publications

Gaining Insights into the Interplay between Optical and Magnetic Properties in Photoexcited Coordination Compounds

Gaining Insights into the Interplay between Optical and Magnetic Properties in Photoexcited Coordination Compounds

Tuning Valence Tautomerism in Dinuclear Cobalt Complexes by Modulating Communication in the Bridging Ligand

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