Influence of Jahn−Teller Coupling on the Magnetic Properties of Transition Metal Complexes with Orbital Triplet Ground Terms:  Magnetization and Electronic Raman Studies of the Titanium(III) Hexa-Aqua Cation

Tregenna‐Piggott, Philip L. W.; Güdel, Hans-Ueli

doi:10.1021/ic010277f

Cited by 15 publications

(12 citation statements)

References 40 publications

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“…The authors attributed the Raman peaks in [Fe II (H 2 O) 6 ] 2+ to the presence of orbital angular momentum in the ZFS states. To the best of our knowledge, Raman spectroscopy has not been used to probe molecular magnetism in other complexes, although electronic transitions have been probed 29 – 35 .…”

Section: Introductionmentioning

confidence: 99%

Spin–phonon couplings in transition metal complexes with slow magnetic relaxation

Moseley¹,

Stavretis²,

et al. 2018

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Spin–phonon coupling plays an important role in single-molecule magnets and molecular qubits. However, there have been few detailed studies of its nature. Here, we show for the first time distinct couplings of g phonons of CoII(acac)2(H2O)2 (acac = acetylacetonate) and its deuterated analogs with zero-field-split, excited magnetic/spin levels (Kramers doublet (KD)) of the S = 3/2 electronic ground state. The couplings are observed as avoided crossings in magnetic-field-dependent Raman spectra with coupling constants of 1–2 cm−1. Far-IR spectra reveal the magnetic-dipole-allowed, inter-KD transition, shifting to higher energy with increasing field. Density functional theory calculations are used to rationalize energies and symmetries of the phonons. A vibronic coupling model, supported by electronic structure calculations, is proposed to rationalize the behavior of the coupled Raman peaks. This work spectroscopically reveals and quantitates the spin–phonon couplings in typical transition metal complexes and sheds light on the origin of the spin–phonon entanglement.

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Section: Introductionmentioning

confidence: 99%

Spin–phonon couplings in transition metal complexes with slow magnetic relaxation

Moseley¹,

Stavretis²,

et al. 2018

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“…He temperatures. 38 The electronic Raman spectrum of GuVSH is unusual in this respect, as it can still be readily discerned at ϳ80 K. Note also that the bandwidth increases across the spectrum, to higher energy. In the 5.0 and 14.5 K spectra, where the resolution is optimum and the Boltzmann population of all three spinor levels of the 3 A ͑C 3 ͒ ground term significant, an additional broad weak band is identified at ϳ2855 cm −1 , indicated by the symbol † in Fig.…”

Section: Resultsmentioning

confidence: 91%

Electronic Raman spectroscopy of the vanadium(III) hexaaqua cation in guanidinium vanadium sulphate: Quintessential manifestation of the dynamical Jahn–Teller effect

Carver

Spichiger²,

Tregenna‐Piggott³

2005

The Journal of Chemical Physics

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Single-crystal Raman spectra are presented for the salt [C(NH2)3][V(OH2)6](SO4)2, displaying electronic transitions between the trigonal components of the vanadium(III) 3T1g(Oh) ground term. The 3A-->3E(C3) electronic Raman band is centered at approximately 2720 cm-1, and exhibits extensive structure, revealing the energies of the spinor components of the 3E(C3) term for the two crystallographically distinct [V(OH2)6]3+ cations. The data are interpreted in conjunction with parameters previously reported from an electron paramagnetic resonance study of the salt. A satisfactory reproduction of the electronic Raman profile and ground-state spin-Hamiltonian parameters is achieved by employing a (3A plus sign in circle3E)multiply sign in circle e vibronic coupling model, in which the spin-orbit splitting of the 3E(C3) is quenched significantly by the Ham effect, and the intensity of harmonics of the Jahn-Teller active vibration enhanced by their proximity to the electronic Raman bands. The model gives an excellent account of the intensities of the electronic Raman bands, which are shown to depend profoundly on both temperature and the selected component of the polarizability tensor. The electronic Raman profile changes notably upon deuteriation, a result that exposes deficiencies in the single-mode coupling model.

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“…Unexpectedly large high-order contributions to the magnetization, ascribable to the Jahn-Teller effect, have permitted determination of Zeeman coefficients to third order for the ground state, which are themselves highly concentration-dependent. 48 has the cis configuration in the solid state; it displays enantiomeric disorder, with each site equally occupied by each enantiomorph. 50 Oxydiacetate complexes of Zr IV have been studied in solution by NMR, where 1 : 1, 1 : 2 and 1 : 3 complexes have been identified, as well as in the solid state by CP-MAS NMR.…”

Section: Other Complexesmentioning

confidence: 99%

10 Titanium, zirconium and hafnium

Cotton¹

2002

Annu. Rep. Prog. Chem., Sect. A: Inorg. Chem.

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A new book dealing with metal alkoxides and aryloxides, many of Group IV elements, has appeared. 1 Halides and their complexesThe octahedral complexes [TiF 4 L 2 ] (L = Ph 3 PO, Me 2 SO, (MeO) 3 PO, Et 2 O and MeCN) have been synthesised and shown to be present in solution mainly as the cis isomers. 2 Ligand exchange in [TiF 4 ((MeO) 3 PO) 2 ] occurs by a dissociative mechanism. When subjected to electron-beam irradiation, ZrCl 4 chains contained in single-walled carbon nanotubes undergo reductive conversion to clusters. 3 Mixtures of TiCl 4 with R 3 N (R e.g. Et) catalyse the reaction of in situ generated iminium salts with diarylketones to form 3,3-diarylcyclobutanones. 4 Similarly, ZrCl 4 -Pr i 2 EtN mediates Claisen ester condensations of α,α-dialkylated esters to afford thermodynamically unfavourable α,α-dialkylated β-ketoesters. 5 HfCl 4 catalyses the reaction of alkylvinylketones with N-tert-butylarylmethylideamine N-oxides to form 4-methylene-4,5-dihydroisoxazoles. 6 Reduction of TiCl 4 with Ti in the presence of ethers affords 7 complexes such as TiCl 3 (thf ) 3 . The structure of X[TiF 5 (H 2 O)] (X = piperazinium) has been reported; strong hydrogen bonds are formed between the fluorines and the diprotonated piperazinium ions, leading to a zig-zag chain structure. 8 A Raman study of ZrF 4 -KF melts indicates that co-ordination behaviour depends upon both composition and temperature. 9 KF-rich melts have an equilibrium between [ZrF 6 ] 2Ϫ and [ZrF 7 ] 3Ϫ , whilst in melts with high ZrF 4 content there is bridging of [ZrF 6 ] 2Ϫ octahedra yielding oligomers. Self-ionisation was suggested to occur in molten ZrF 4 . (H 3 N(CH 2 ) 4 NH 3 )[TiF 4 O] has a structure involving vertex-shared TiF 4 O 2/2 octahedra. 10 A range of six-co-ordinate [TiX 4 (L-L)] (X = Cl, Br; L-L = Ph 2 PCH 2 PPh 2 , Ph 2 -P(CH 2 ) 2 PPh 2 , Ph 2 P(CH 2 ) 3 PPh 2 , o-C 6 H 4 (PPh 2 ) 2 , o-C 6 H 4 (PMe 2 ) 2 , Ph 2 As(CH 2 ) 2 AsPh 2 , o-C 6 H 4 (AsMe 2 ) 2 and MeC(CH 2 AsMe 2 ) 3 ) and eight-co-ordinate [TiX 4 (L-L) 2 ] (L = o-C 6 H 4 (PMe 2 ) 2 and o-C 6 H 4 (AsMe 2 ) 2 ) have been investigated, with structures described for [TiCl 4 (o-C 6 H 4 (PMe 2 ) 2 )], [TiCl 4 (o-C 6 H 4 (PMe 2 ) 2 ) 2 ], [TiBr 4 (o-C 6 H 4 (PMe 2 ) 2 ) 2 ],

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Influence of Jahn−Teller Coupling on the Magnetic Properties of Transition Metal Complexes with Orbital Triplet Ground Terms: Magnetization and Electronic Raman Studies of the Titanium(III) Hexa-Aqua Cation

Cited by 15 publications

References 40 publications

Spin–phonon couplings in transition metal complexes with slow magnetic relaxation

Spin–phonon couplings in transition metal complexes with slow magnetic relaxation

Electronic Raman spectroscopy of the vanadium(III) hexaaqua cation in guanidinium vanadium sulphate: Quintessential manifestation of the dynamical Jahn–Teller effect

10 Titanium, zirconium and hafnium

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