Thermal and optical control of electronic states in a single layer of switchable paramagnetic molecules

Poneti, Giordano; Poggini, Lorenzo; Mannini, Matteo; Cortigiani, Brunetto; Sorace, Lorenzo; Otero, Edwige; Sainctavit, Philippe; Magnani, Agnese; Sessoli, Roberta; Dei, Andrea

doi:10.1039/c5sc00163c

Cited by 48 publications

(35 citation statements)

References 62 publications

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“…The molecules at the surface suffer less chemical pressure, and may possibly exhibit a lower transition temperature. Indeed, when probed by X-ray absorption spectroscopy with the total electron yield detection mode that is extremely sensitive to the surface layer, a much higher ratio of HS molecules was detected compared with that obtained by magnetometry in the reported VT cobalt-dioxolene complexes [38][39][40] . However, the preliminary experiments showed that 1•0.5EtOH was very sensitive to X-ray exposure and exhibited irreversible X-ray-induced damage that hindered further investigations of the surface effect using this technique.…”

Section: Resultsmentioning

confidence: 93%

Macroscopic Polarization Change via Electron Transfer in a Valence Tautomeric Cobalt Complex

Liu

Gao

et al. 2020

Nat Commun

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Polarization change induced by directional electron transfer attracts considerable attention owing to its fast switching rate and potential light control. Here, we investigate electronic pyroelectricity in the crystal of a mononuclear complex, [Co(phendiox)(rac-cth)] (ClO 4)•0.5EtOH (1•0.5EtOH, H 2 phendiox = 9, 10-dihydroxyphenanthrene, rac-cth = racemic 5, 5, 7, 12, 12, 14-hexamethyl-1, 4, 8, 11-tetraazacyclotetradecane), which undergoes a twostep valence tautomerism (VT). Correspondingly, pyroelectric current exhibits double peaks in the same temperature domain with the polarization change consistent with the change in dipole moments during the VT process. Time-resolved Infrared (IR) spectroscopy shows that the photo-induced metastable state can be generated within 150 ps at 190 K. Such state can be trapped for tens of minutes at 7 K, showing that photo-induced polarization change can be realized in this system. These results directly demonstrate that a change in the molecular dipole moments induced by intramolecular electron transfer can introduce a macroscopic polarization change in VT compounds.

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Section: Resultsmentioning

confidence: 93%

Macroscopic Polarization Change via Electron Transfer in a Valence Tautomeric Cobalt Complex

Liu

Gao

et al. 2020

Nat Commun

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“…Recently, more complex architectures, such as core–shell particles, multilayer films, hybrid plasmonic, and fluorescent SCO particles have been also synthesized attesting a certain degree of maturity of the field and providing scope for the development of multifunctional nanomaterials displaying synergistic effects. Let us mention also that conceptually related valence tautomeric and Jahn–Teller switch type molecule‐based nanomaterials have been also synthesized recently—raising similar fundamental questions and application ideas …”

Section: Introductionmentioning

confidence: 89%

Spin Crossover Nanomaterials: From Fundamental Concepts to Devices

et al. 2017

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Nanoscale spin crossover materials capable of undergoing reversible switching between two electronic configurations with markedly different physical properties are excellent candidates for various technological applications. In particular, they can serve as active materials for storing and processing information in photonic, mechanical, electronic, and spintronic devices as well as for transducing different forms of energy in sensors and actuators. In this progress report, a brief overview on the current state-of-the-art of experimental and theoretical studies of nanomaterials displaying spin transition is presented. Based on these results, a detailed analysis and discussions in terms of finite size effects and other phenomena inherent to the reduced size scale are provided. Finally, recent research devices using spin crossover complexes are highlighted, emphasizing both challenges and prospects.

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“…More recently, the control of the charge distribution of VT complexes assembled on flat gold surfaces has been attained by Poneti and co-workers. 34 In this case, the authors synthesised a series of catechol-based VT complexes with different charge distributions of the ls-Co(III)Cat and the hs-Co(II)SQ tautomers and assembled them on gold surfaces through the thiol moiety previously introduced in the catechol ligand. In contrast to the results reported by Shultz et al, these authors observed that the charge distribution of the complexes as well as their entropydriven interconversion equilibria were not affected by surface grafting and that the VT behaviour of the bulk phase was quantitatively reproduced on the surface.…”

Section: Nanostructured Surfaces and Interfacesmentioning

confidence: 99%

Switchable colloids, thin-films and interphases based on metal complexes with non-innocent ligands: the case of valence tautomerism and their applications

et al. 2016

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Thermal and optical control of electronic states in a single layer of switchable paramagnetic molecules

Abstract: Thermally and optically induced Valence Tautomeric interconversion has been observed for a monolayer of a cobalt–dioxolene complex on gold.

Cited by 48 publications

References 62 publications

Macroscopic Polarization Change via Electron Transfer in a Valence Tautomeric Cobalt Complex

Macroscopic Polarization Change via Electron Transfer in a Valence Tautomeric Cobalt Complex

Spin Crossover Nanomaterials: From Fundamental Concepts to Devices

Switchable colloids, thin-films and interphases based on metal complexes with non-innocent ligands: the case of valence tautomerism and their applications

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