High-Frequency EPR Studies of New 2p-3d Complexes Based on a Triazolyl-Substituted Nitronyl Nitroxide Radical: The Role of Exchange Anisotropy in a Cu-Radical System.

Using the 1-(m-tolyl)-1H-1,2,3-triazole-4-(4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide) (TlTrzNIT) radical and metal ß-diketonate complexes [M(hfac)2(H2O)2], where hfac is hexafluoroacetylacetonato, three new 2p-3d heterospin complexes were synthesized. Their structures were solved using single crystal X-ray diffraction data, and magnetic investigation was performed by DC and AC measurements and multifrequency EPR spectroscopy. Compounds 1 and 2 are isostructural complexes with molecular formula [M3(TlTrzNIT)2(hfac)6] (MII = Mn or Cu) while compound 3 is the mononuclear [Co(TlTrzNIT)(hfac)2] complex. In all complexes, the radical acts as a bidentate ligand through the oxygen atom of the nitroxide moiety and the nitrogen atom from the triazole group. Furthermore, in compounds 1 and 2, the TlTrzNIT is bridge-coordinated between two metal centers, leading to the formation of trinuclear complexes. The fitting of the static magnetic behavior reveals antiferromagnetic and ferromagnetic intramolecular interactions for complexes 1 and 2, respectively. The EPR spectra of 1 are well described by an isolated ferrimagnetic S = 13/2 (= 5/2 - 1/2 + 5/2 - 1/2 + 5/2) ground state with a biaxial zero-field splitting (ZFS) interaction characterized, respectively, by 2nd order axial and rhombic parameters, D and E, such that E/D is close to the maximum of 0.33. Meanwhile, EPR spectra for 2 are explained in terms of a ferromagnetic model with weakly anisotropic Cu-radical exchange interactions, giving rise to an isolated S = 5/2 (= 5 × 1/2) ground state with both an anisotropic g tensor and a weak ZFS interaction. Complex 2 represents one of only a few examples of Cu-radical moieties with measurable exchange anisotropy.

Exploring the Organometallic Route to Molecular Spin Qubits: The [CpTi(cot)] Case.

The coherence time of the 17-electron, mixed sandwich complex [CpTi(cot)], (η8 -cyclooctatetraene)(η5 -cyclopentadienyl)titanium, reaches 34 µs at 4.5 K in a frozen deuterated toluene solution. This is a remarkable coherence time for a highly protonated molecule. The intramolecular distances between the Ti and H atoms provide a good compromise between instantaneous and spin diffusion sources of decoherence. Ab initio calculations at the molecular and crystal packing levels reveal that the characteristic low-energy ring rotations of the sandwich framework do not yield a too detrimental spin-lattice relaxation because of their small spin-phonon coupling. The volatility of [CpTi(cot)] and the accessibility of the semi-occupied, non-bonding d z 2 orbital make this neutral compound an ideal candidate for single-qubit addressing on surface and quantum sensing in combination with scanning probe microscopy.

Magnetic Cationic Copper(II) Chains and a Mononuclear Cobalt(II) Complex Containing [Ln(hfac)4]- Blocks as Counterions.

Four new heterospin compounds with molecular formula {[Cu2(hfac)3(TlTrzNIT)2][Ln(hfac)4]} n·C7H16 (LnIII = Gd (1), Tb (2), or Dy (3)) and [Co(hfac)(TlTrzNIT)2][Dy(hfac)4] (4), where hfac is hexafluoroacetylacetonato and TlTrzNIT is the nitronylnitroxide radical 1-( m-tolyl)-1 H-1,2,3-triazole-4-(4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide), were obtained. All structures were determined by single-crystal X-ray diffraction. In compounds 1-3, the TlTrzNIT radical is bridge-coordinated to copper(II) ions, leading to positively charged copper(II)-radical chains containing [Ln(hfac)4]- as counterions. In compound 4, the cobalt(II) ion is coordinated to two TlTrzNIT radicals and one hfac ligand in bidentate mode leading to a mononuclear cationic complex that contains [Dy(hfac)4]- as counterion. Magnetic measurements of all complexes were performed. Magnetic data were fit considering the contributions of the copper(II)-radical chain and a paramagnetic gadolinium(III) ion for 1. The sign and magnitude of the magnetic coupling constants extracted from the fit were confirmed by density functional theory calculations. The obtained spin topology shows an alternated ferro-antiferromagnetic chain. Field-induced single molecule magnet behavior was observed for the Dy derivatives 3 and 4, in agreement with CASSCF calculations performed for the latter system.

A Rare Example of Four-Coordinate Nonoxido Vanadium(IV) Alkoxide in the Solid State: Structure, Spectroscopy, and Magnetization Dynamics.

The distorted tetrahedral [V(OAd)4] alkoxide (OAd = 1-adamantoxide, complex 1) is the first homoleptic, mononuclear vanadium(IV) alkoxide to be characterized in the solid state by X-ray diffraction analysis. The compound crystallizes in the cubic P4̅3 n space group with two highly disordered, crystallographically independent molecules in the asymmetric unit. Spin Hamiltonian parameters extracted from low temperature X- and Q-band electron paramagnetic resonance (EPR) experiments performed for polycrystalline samples of 1, both in the concentrated (bulk) form and diluted in the diamagnetic [Ti(OAd)4] analogue, reveal a fully axial system with g z < g x, g y and A z ≫ A x, A y. Complex 1 has also been characterized by alternate current susceptometry with varying temperature (3-30 K) and static magnetic field (up to 8.5 T), showing field-induced slow relaxation of the magnetization with relaxation times ranging from ca. 3 ms at 3 K to 0.02-0.03 ms at 30 K, in line with relevant results described recently for other potential molecular quantum bits. Pulsed EPR measurements, in turn, disclosed long coherence times of ca. 4 µs at temperatures lower than 40 K, despite the presence of the H-rich ligands. The slow spin relaxation in 1 is the first observed for a tetracoordinate nonoxido vanadium(IV) complex, and results are compared here to those generated by square-pyramidal VIV(O)2+ and trigonal prismatic V4+ with oxygen donor atom sets. Considering that the number of promising d1 complexes investigated in detail for slow magnetization dynamics is still small, the present work contributes to the establishment of possible structural/electronic correlations of interest to the field of quantum information processing.

A new ring-like arrangement of vanadyl(IV) groups bridged by monodentate alkoxides: cyclo-decakis(µ-cyclohexylmethanolato)pentakis[oxidovanadium(IV)].

The pentanuclear title compound, [V(5)(C(7)H(13)O)(10)O(5)], has a metal-oxygen core that consists of five vanadyl(IV) centres bridged by the O atoms of cyclohexylmethanolate ligands. This particular ring topology is new to oxovanadium(IV) chemistry and resembles the structure proposed for [V(5)O(15)](5-) on the basis of (51)V NMR studies in aqueous solution. The bulky cyclohexylmethanolate ligands adopt chair-like conformations and project outwards from the central cyclic core. The title compound crystallizes in a centrosymmetric triclinic unit cell, which contains four independent but chemically identical molecules in the asymmetric unit. The crystal structure is devoid of any significant intermolecular interactions.

Cobalt(II) chloride adducts with acetonitrile, propan-2-ol and tetrahydrofuran: considerations on nuclearity, reactivity and synthetic applications.

High-spin cobalt(II) complexes are considered useful building blocks for the synthesis of single-molecule magnets (SMM) because of their intrinsic magnetic anisotropy. In this work, three new cobalt(II) chloride adducts with labile ligands have been synthesized from anhydrous CoCl2, to be subsequently employed as starting materials for heterobimetallic compounds. The products were characterized by elemental, spectroscopic (EPR and FT-IR) and single-crystal X-ray diffraction analyses. trans-Tetrakis(acetonitrile-κN)bis(tetrahydrofuran-κO)cobalt(II) bis[(acetonitrile-κN)trichloridocobaltate(II)], [Co(C2H3N)4(C4H8O)2][CoCl3(C2H3N)]2, (1), comprises mononuclear ions and contains both acetonitrile and tetrahydrofuran (thf) ligands, The coordination polymer catena-poly[[tetrakis(propan-2-ol-κO)cobalt(II)]-µ-chlorido-[dichloridocobalt(II)]-µ-chlorido], [Co2Cl4(C3H8O)4], (2'), was prepared by direct reaction between anhydrous CoCl2 and propan-2-ol in an attempt to rationalize the formation of the CoCl2-alcohol adduct (2), probably CoCl2(HOiPr)m. The binuclear complex di-µ-chlorido-1:2κ4Cl:Cl-dichlorido-2κ2Cl-tetrakis(tetrahydrofuran-1κO)dicobalt(II), [Co2Cl4(C4H8O)4], (3), was obtained from (2) after recrystallization from tetrahydrofuran. All three products present cobalt(II) centres in both octahedral and tetrahedral environments, the former usually less distorted than the latter, regardless of the nature of the neutral ligand. Product (2') is stabilized by an intramolecular hydrogen-bond network that appears to favour a trans arrangement of the chloride ligands in the octahedral moiety; this differs from the cis disposition found in (3). The expected easy displacement of the bound solvent molecules from the metal coordination sphere makes the three compounds good candidates for suitable starting materials in a number of synthetic applications.

Non-oxo vanadium(IV) alkoxide chemistry: solid state structures, aggregation equilibria and thermochromic behaviour in solution.

The reversible thermochromic behaviour of homoleptic [{V(OR)(4)}(n)] complexes in solution [R = Pr(i) (product I), Bu(s) (B(s)), Nep (N) and Cy (C)] is accounted for the existence of an aggregation equilibrium involving dimeric and monomeric species in which vanadium(iv) is respectively five- and four-coordinate. Bulky R groups such as Bu(t) and Pe(t) (tert-pentoxide) prevent aggregation and therefore give rise to exclusively mononuclear compounds (B(t) and P(t), respectively) that are not thermochromic. The complexes and their temperature-dependent interconversion were characterised by single crystal X-ray diffractometry, magnetic susceptibility measurements and electronic, FTIR and EPR spectroscopies in a wide temperature range. Equilibrium constants and enthalpy and entropy changes for the dimerization reactions have been determined and compared with literature data.