Adducts of cobalt(ii) bis(salicylaldiminates) and redox-active phenoxazin-1-one: synthesis, structure, and magnetic properties

Antipin, M. Yu.; Ivakhnenko, E. P.; Koshchienko, Yu. V.; Knyazev, Pavel A.; Korobov, M. S.; Chernyshev, A. V.; Starikov, А. G.

doi:10.1007/s11172-013-0251-6

Cited by 33 publications

(8 citation statements)

References 24 publications

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“…5,19,50−57 Solution T 1/2 values are crucial, as VT in the solid-state is also governed by crystal-packing and supramolecular interactions. 23,58,59 A new member of the family, [Co(dbdiox)(dbsq)(MeO-bpy)] (1; MeO-bpy = 4,4′-dimethoxy-2,2′-bipyridine) was first synthesized and characterized to increase the available range of experimental T 1/2 values for comparison with calculated values. We then developed a dispersion-corrected DFT protocol incorporating real physical and environmental effects and applied it to the [Co(dbdiox)(dbsq)(N 2 L)] family, where N 2 L = MeO-bpy, bpy, 4,4′-dimethyl-2,2′-bipyridine (Me-bpy), 1,10′-phenanthroline (phen), 2,2′-bipyrimidine (bpym) and 2,2′-bipyrazine (bpyz).…”

Section: ■ Introductionmentioning

confidence: 99%

“…69,70 To develop the model, we investigated the [Co(dbdiox)(dbsq)(N 2 L)] complexes where N 2 L = MeObpy, Me-bpy, bpy, phen, bpym, and bpyz, which offer a wide T 1/2 (toluene) range of 190−336 K (Table S1). 21,23,27,66,84 Solution state transition temperatures were employed due to the complications of solid state and packing effects associated with solid state values, 23,58,59 with toluene providing the most comprehensive set of experimental values. The analogue with the 4,4′-diphenyl-2,2′-bipyridine ancillary ligand displays unexplained anomalous behavior, with the experimentally observed T 1/2 very high for the ΔH and ΔS values, and was not included.…”

Section: ■ Introductionmentioning

confidence: 99%

“…We have developed the first efficient DFT method for reliable screening of candidate VT molecules and prediction of T 1/2 values. The [Co(dbdiox)(dbsq)(N 2 L)] family of VT complexes was selected for this study, as it offers the largest reported range of solution (toluene) T 1/2 values as well as providing the basis for various multifunctional materials. ,,− Solution T 1/2 values are crucial, as VT in the solid-state is also governed by crystal-packing and supramolecular interactions. ,, A new member of the family, [Co(dbdiox)(dbsq)(MeO-bpy)] ( 1 ; MeO-bpy = 4,4′-dimethoxy-2,2′-bipyridine) was first synthesized and characterized to increase the available range of experimental T 1/2 values for comparison with calculated values. We then developed a dispersion-corrected DFT protocol incorporating real physical and environmental effects and applied it to the [Co(dbdiox)(dbsq)(N 2 L)] family, where N 2 L = MeO-bpy, bpy, 4,4′-dimethyl-2,2′-bipyridine (Me-bpy), 1,10′-phenanthroline (phen), 2,2′-bipyrimidine (bpym) and 2,2′-bipyrazine (bpyz).…”

Section: Introductionmentioning

confidence: 99%

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A Convenient DFT-Based Strategy for Predicting Transition Temperatures of Valence Tautomeric Molecular Switches

et al. 2021

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The ability to identify promising candidate switchable molecules computationally, prior to synthesis, represents a considerable advance in the development of switchable molecular materials. Even more useful would be the possibility of predicting the switching temperature. Cobalt-dioxolene complexes can exhibit thermally induced valence tautomeric switching between low-spin CoIII-catecholate and high-spin CoII-semiquinonate forms, where the half-temperature (T 1/2) is the temperature at which there are equal amounts of the two tautomers. We report the first simple computational strategy for accurately predicting T 1/2 values for valence tautomeric complexes. Dispersion-corrected density functional theory (DFT) methods have been applied to the [Co(dbdiox)(dbsq)(N2L)] (dbdiox/dbsq•– = 3,5-di-tert-butyldioxolene/semiquinonate; N2L = diimine) family of valence tautomeric complexes, including the newly reported [Co(dbdiox)(dbsq)(MeO-bpy)] (1) (MeO-bpy = 4,4′-dimethoxy-2,2′-bipyridine). The DFT strategy has been thoroughly benchmarked to experimental data, affording highly accurate spin-distributions and an excellent energy match between experimental and calculated spin-states. Detailed orbital analysis of the [Co(dbdiox)(dbsq)(N2L)] complexes has revealed that the diimine ligand tunes the T 1/2 value primarily through π-acceptance. We have established an excellent correlation between experimental T 1/2(toluene) values for [Co(dbdiox)(dbsq)(N2L)] complexes and the calculated lowest unoccupied molecular orbital energy of the corresponding diimine ligand. The model affords accurate T 1/2(toluene) values for [Co(dbdiox)(dbsq)(N2L)] complexes, with an average error of only 3.7%. This quantitative and simple DFT strategy allows experimentalists to not only rapidly identify proposed VT complexes but also predict the transition temperature. This study lays the groundwork for future in silico screening of candidate switchable molecules prior to experimental investigation, with associated time, cost, and environmental benefits.

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Section: ■ Introductionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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A Convenient DFT-Based Strategy for Predicting Transition Temperatures of Valence Tautomeric Molecular Switches

et al. 2021

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“…13 By varying the substituents and ligating centers X and Y in the redox-active ligands of 2 and 3, the compounds have been found to have the predicted properties inherent in systems capable of VT rearrangements. The feasibility of such rearrangements was corroborated by the studies 14 of the adducts of bis-(salicylaldiminate)Co(II) with a redox-active 2,4,6,8-tetra-tert-butylphenoxazin-1-one (Phox) stabilized as the low-spin Co(III)•Phox •− species.…”

Section: Introductionmentioning

confidence: 91%

Valence tautomeric dinuclear adducts of Co(ii) diketonates with redox-active diquinones for the design of spin qubits: computational modeling

Старикова

Starikov

2015

Dalton Trans.

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The possibility of employing the mechanism of intramolecular electron transfer between metal and ligand centers in the valence tautomeric complexes formed as electrically neutral 2 : 1 adducts of Co(II) diketonates and redox-active tetradentate di-o-quinones, for quantum information processing, has been computationally studied using the DFT B3LYP*/6-311++G(d,p) method. It has been shown that by the proper choice of a linker group bridging the quinone rings and substituents in the diketonate fragments, complexes with the properties required in 2-qubit quantum gates (sufficiently narrow energy gaps between the spin states and weakly coupled paramagnetic centers) can be designed, in order to realize the mechanism of thermally driven migration of paramagnetic centers between the o-quinone fragments and metal atoms. These are exemplified by the adduct of bis-(hexafluoroacetylacetonate)Co(ii) with a diquinone containing dimethylene linker. Valence tautomerism is considered as a new, promising mechanistic paradigm for the molecular design of 2-qubit molecular systems.

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“…It has been recently shown that an expedient approach to the synthesis of VT transition metal complexes can be developed on the basis of stable adducts of tetracoordinate d 4 -d 7 metal complexes with electrically neutral bidentate redox-active ligands [24,25]. The feasibility of this approach has been verified by the synthesis [26] and computational studies of a broad series of 1:1 adducts of Co II diketonates with various redox-active ligands [27][28][29]. The goal of the present paper is an elucidation of the potential VT properties of 1:1 adducts of manganese diketonates with the most typical redox-active ligands -o-benzoquinone, its imine and diimine derivatives and model diimine.…”

Section: Introductionmentioning

confidence: 99%

Adducts of manganese diketonates with redox-active ligands: Computational modeling of valence tautomeric systems

Старикова

Starikov

2015

Computational and Theoretical Chemistry

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Adducts of cobalt(ii) bis(salicylaldiminates) and redox-active phenoxazin-1-one: synthesis, structure, and magnetic properties

Cited by 33 publications

References 24 publications

A Convenient DFT-Based Strategy for Predicting Transition Temperatures of Valence Tautomeric Molecular Switches

A Convenient DFT-Based Strategy for Predicting Transition Temperatures of Valence Tautomeric Molecular Switches

Valence tautomeric dinuclear adducts of Co(ii) diketonates with redox-active diquinones for the design of spin qubits: computational modeling

Adducts of manganese diketonates with redox-active ligands: Computational modeling of valence tautomeric systems

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