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Switching of Electronic States of Cobalt Dioxolene Complexes Triggered by Spin-Crossover Process and Valence Tautomerism

  • Spin-crossover and valence tautomeric complexes are of tremendous interest in the field of molecular electronics, electronic storage devices and information processing. Herein, synthesis and characterization of the spin-crossover and valence tautomeric cobalt dioxolene complexes are reported. All the synthesized complexes contain N,N'-di-tert-butyl-2,11-diaza[3.3](2,6)pyridinophane (L-N4tBu2) as ancillary ligands. Only various types of co-ligands which are different dioxolene ligands, have been used. The mononuclear cobalt dioxolene complexes have been synthesized by using dideprotonated form of the dioxolene ligand 4,5-dichlorocatechol (H2DCCat) as co-ligands, and the cobalt bis(dioxolene) complexes have been synthesized by using dideprotonated form of the 3,3'-dihydroxy-diphenoquinone-(4,4') (H2(SQ-SQ)) as co-ligands. Analytically pure samples of the complexes [Co(L-N4tBu2)(DCCat)] (1), [Co(L-N4tBu2)(DCCat)](BPh4) (2b), [Co2(L-N4tBu2)2(SQ-SQ)](BPh4)2.4 DMF (3b), [Co2(L-N4tBu2)2(Cat-SQ)](BF4)2.Et2O (3d), have been synthesized and characterized by X-ray crystallography, magnetic and electrochemical measurements. The complexes have been investigated by UV/Vis/NIR-, IR-, and NMR spectroscopic measurements. The complex [Co(L-N4tBu2)(DCCat)] (1) shows temperature invariant high-spin cobalt(II) catecholate state. One-electron oxidation of 1 has yielded the complex [Co(L-N4tBu2)(DCCat)](BPh4) (2b). The solid state properties of 2b are best described by the low-spin cobalt(III) catecholate state, but the solution state properties of the complex 2b are best described by the valence tautomeric transition from the low-spin cobalt(III) catecholate to the low-spin cobalt(II) semiquinonate state. For the cobalt bis(dioxolene) complexes, it is found that spin-crossover for the two cobalt(II) centers is accompanied by the electronic state changes of the coordinated bis(dioxolene) unit from singlet open-shell biradicaloid to singlet closed-shell quinonoid form in complex 3b. Approaching similar synthetic method to 3b, but performing the metathesis reaction with sodium tetrafluoroborate rather than sodium tetraphenylborate has resulted in the formation of the complex [Co2(L-N4tBu2)2(Cat-SQ)](BF4)2.Et2O (3d). The solid state properties of the complex are best described by the temperature induced valence tautomeric transition for the low-spin cobalt(III) center which is accompanied by the spin-crossover process for the cobalt(II) center. Thus, the electronic state of the complex 3d changes from LS-CoIII-Cat-SQ-CoII-LS to HS-CoII-(SQ-SQ)CS-CoII-HS state upon change in temperature. Temperature-induced electronic configuration changes of the (SQ-SQ)CS2- ligands from open-shell biradicaloid to closed-shell quinonoid configurations are not observed for the nickel-, copper- and zinc bis(dioxolene) complexes 4a, 5a and 6b, respectively. For these complexes, the metal ions are bridged by (SQ-SQ)CS2- ligand and the paramagnetic metal ions are very weakly antiferromagnetically coupled.

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Author:Ramapada Dolai
URN (permanent link):urn:nbn:de:hbz:386-kluedo-58818
Advisor:Hans-Jörg Krüger
Document Type:Doctoral Thesis
Language of publication:English
Publication Date:2020/02/03
Year of Publication:2020
Publishing Institute:Technische Universität Kaiserslautern
Granting Institute:Technische Universität Kaiserslautern
Acceptance Date of the Thesis:2020/01/30
Date of the Publication (Server):2020/02/04
Number of page:XI, 336
Faculties / Organisational entities:Fachbereich Chemie
DDC-Cassification:5 Naturwissenschaften und Mathematik / 540 Chemie
Licence (German):Creative Commons 4.0 - Namensnennung (CC BY 4.0)