Computational modeling of structure and magnetic properties of dinuclear di-o-benzoquinone iron complexes with linear polycyclic linkers

Старикова, А. А.; Chegerev, M. G.; Starikov, А. G.

doi:10.1007/s11172-020-2747-1

Cited by 9 publications

(4 citation statements)

References 59 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…In contrast to the many MV complexes of dinuclear (diethynylacene)diyl com-plexes with smaller acene rings such as benzene, naphthalene, and anthracene, [16][17][18][19][20] the larger tetracene and pentacene derivatives have scarcely been reported, [21] while metal-higher acene conjugates have been an interest for theoretical studies. [22][23][24] Yip et al described the synthesis and photophysical properties of the diplatinum complexes with the (5,12diethynyltetracene)diyl (A1) and (6,13-diethynylpentacene)diyl BLs (A2), [25][26][27] but no redox chemistry has been unveiled due to the poor redox activity of the platinum fragments (Figure 1e). As a related work, Liu reported the diruthenium complex B with the 5,12-divinyltetracene linker (Figure 1e).…”

Section: Introductionmentioning

confidence: 99%

“…(Diethynylacene)diyls are fascinating candidates for the BLs because extension of the acene size causes narrowing of the HOMO‐LUMO gaps of the BL parts, which should bring about the stronger π interactions to lead to the charge delocalization over the molecule. In contrast to the many MV complexes of dinuclear (diethynylacene)diyl complexes with smaller acene rings such as benzene, naphthalene, and anthracene, [16–20] the larger tetracene and pentacene derivatives have scarcely been reported, [21] while metal‐higher acene conjugates have been an interest for theoretical studies [22–24] . Yip et al.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Acene Size‐Dependent Transition of The Radical Centers From the Metal to The Acene Parts In Monocationic Dinuclear (Diethynylacene)diyl Complexes

Tanaka

Kawano

Akita

2022

Chemistry A European J

View full text Add to dashboard Cite

Controlling radical localization/delocalization is important for functional materials. The present paper describes synthesis and results of electrochemical, spectroscopic, and theoretical studies of diruthenium (pdiethynylacene)diyl complexes, Me 3 Si-(C�C) 2 -Ru(dppe) 2 -C�CÀ Ar-C�CÀ Ru(dppe) 2 -(C�C) 2 -SiMe 3 (1-6) (dppe: 1,2bis(diphenylphosphino)ethane), and their monocationic radical species ([1] + -[6] + ). The HOMO-LUMO energy gaps can be finely tuned by the acene rings in the bridging ligands installed, as indicated by the absorption maxima of the electronic spectra of 1-6 ranging from the UV region even to the NIR region. The cationic species [1] + -[6] + show two characteristic NIR bands, which are ascribed to the charge resonance (CR) and π-π* transition bands, as revealed by spectroelectrochemistry. Expansion of the acene rings in [1] + -[6] + causes (1) blue shifts of the CR bands and red shifts of the π-π* transition bands and (2) charge localization on the acene parts as evidenced by the ESR, DFT and TD-DFT analyses. Notably, the monocationic complexes of the larger acene derivatives are characterized as the non-classical acene-localized radicals.

show abstract

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Acene Size‐Dependent Transition of The Radical Centers From the Metal to The Acene Parts In Monocationic Dinuclear (Diethynylacene)diyl Complexes

Tanaka

Kawano

Akita

2022

Chemistry A European J

View full text Add to dashboard Cite

show abstract

“…The DFT calculations were performed using the Gaussian 16 program package with the UOPBE , functional and the standard 6-311++G(d,p) basis set including diffuse and polarization functions at all atoms. Mononuclear Fe(III)-cat systems have been investigated with DFT, ,, but to date, DFT calculations on dinuclear Fe(III)-catecholate compounds have been applied only to hypothetical complexes. , …”

Section: Results and Discussionmentioning

confidence: 99%

“…Mononuclear Fe(III)-cat systems have been investigated with DFT, 35,41,43 but to date, DFT calculations on dinuclear Fe(III)-catecholate compounds have been applied only to hypothetical complexes. 71,72 Previous work on mononuclear Fe(III)-cat systems utilized the UTPSSh functional, which has performed well in VT and SCO complexes. 24,35,73,74 However, for Fe(III)-cat complexes, UTPSSh/6-311++G(d,p) calculations have overstabilized the LS-Fe(III) state energy, inconsistent with experimental evidence.…”

mentioning

confidence: 99%

Controlling Spin Crossover in a Family of Dinuclear Fe(III) Complexes via the Bis(catecholate) Bridging Ligand

Janetzki,

Chegerev,

Gransbury

et al. 2023

Inorg. Chem.

View full text Add to dashboard Cite

Spin crossover (SCO) complexes can reversibly switch between low spin (LS) and high spin (HS) states, affording possible applications in sensing, displays, and molecular electronics. Dinuclear SCO complexes with access to [LS−LS], [LS−HS], and [HS−HS] states may offer increased levels of functionality. The nature of the SCO interconversion in dinuclear complexes is influenced by the local electronic environment. We report the synthesis and characterization of [{Fe III (tpa)} 2 spiro]-(PF 6 ) 2 (1), [{Fe I I I (tpa)} 2 Br 4 spiro](PF 6 ) 2 (2), and [{Fe III (tpa)} 2 thea](PF 6 ) 2 (3) (tpa = tris(2-pyridylmethyl)amine, spiroH 4 = 3,3,3′,3′-tetramethyl-1,1′-spirobi(indan)-5,5′,6,6′-tetraol, Br 4 spiroH 4 = 3,3,3′,3′-tetramethyl-1,1′-spirobi(indan)-4,4′,7,7′-tetrabromo-5,5′,6,6′-tetraol, theaH 4 = 2,3,6,7-tetrahydroxy-9,10-dimethyl-9,10-dihydro-9,10-ethanoanthracene), utilizing non-conjugated bis(catecholate) bridging ligands. In the solid state, magnetic and structural analysis shows that 1 remains in the [HS−HS] state, while 2 and 3 undergo a partial SCO interconversion upon cooling from room temperature involving the mixed [LS−HS] state. In solution, all complexes undergo SCO from [HS−HS] at room temperature, via [LS−HS] to mixtures including [LS−LS] at 77 K, with the extent of SCO increasing in the order 1 < 2 < 3. Gas phase density functional theory calculations suggest a [LS−LS] ground state for all complexes, with the [LS− HS] and [HS−HS] states successively destabilized. The relative energy separations indicate that ligand field strength increases following spiro 4− < Br 4 spiro 4− < thea 4− , consistent with solid-state magnetic and EPR behavior. All three complexes show stabilization of the [LS−HS] state in relation to the midpoint energy between [LS−LS] and [HS−HS]. The relative stability of the [LS−HS] state increases with increasing ligand field strength of the bis(catecholate) bridging ligand in the order 1 < 2 < 3. The bromo substituents of Br 4 spiro 4− increase the ligand field strength relative to spiro 4− , while the stronger ligand field provided by thea 4− arises from extension of the overlapping π-orbital system across the two catecholate units. This study highlights how SCO behavior in dinuclear complexes can be modulated by the bridging ligand, providing useful insights for the design of molecules that can be interconverted between more than two states.

show abstract

Electronic Lability of Quinonoid‐Bridged Dinuclear 3 d‐Metal Complexes with Tetradentate N‐Donor Bases

Chegerev

Старикова

2021

Eur J Inorg Chem

View full text Add to dashboard Cite

Bimetallic coordination compounds prone to spin‐state‐switching rearrangements via spin‐crossover or valence tautomerism mechanisms are of ongoing interest due to their unique magnetic characteristics. Dinuclear transition metal (Cr, Mn, Fe, Co, Ni, Cu) complexes with redox‐active bridging ligands (tetraoxolenes and their imine derivatives, di‐o‐quinones bearing linker groups) and tetradentate nitrogen‐containing bases (tetraazacyclotetradecane, tris(2‐pyridylmethyl)amine and N,N′‐dialkyl‐2,11‐diaza[3.3]‐(2,6)pyridinophane derivatives) are described from the viewpoint of their electronic structure and magnetic properties. The present review summarizes data on comprehensive investigations of bi‐ and polystable species of such structural architectures, which might be valuable for the chemists and materials scientists involved in the creation of new promising magnetic materials − building blocks for electronic devices of future generations.

show abstract

Computational modeling of structure and magnetic properties of dinuclear di-o-benzoquinone iron complexes with linear polycyclic linkers

Cited by 9 publications

References 59 publications

Acene Size‐Dependent Transition of The Radical Centers From the Metal to The Acene Parts In Monocationic Dinuclear (Diethynylacene)diyl Complexes

Acene Size‐Dependent Transition of The Radical Centers From the Metal to The Acene Parts In Monocationic Dinuclear (Diethynylacene)diyl Complexes

Controlling Spin Crossover in a Family of Dinuclear Fe(III) Complexes via the Bis(catecholate) Bridging Ligand

Electronic Lability of Quinonoid‐Bridged Dinuclear 3 d‐Metal Complexes with Tetradentate N‐Donor Bases

Contact Info

Product

Resources

About