Danna E. Freedman

Slow magnetic relaxation in a high-spin iron(II) complex.

Slow magnetic relaxation is observed for [(tpa(Mes))Fe](-), a trigonal pyramidal complex of high-spin iron(II), providing the first example of a mononuclear transition metal complex that behaves as a single-molecule magnet. Dc magnetic susceptibility and magnetization measurements reveal a strong uniaxial magnetic anisotropy (D = -39.6 cm(-1)) acting on the S = 2 ground state of the molecule. Ac magnetic susceptibility measurements indicate the absence of slow relaxation under zero applied dc field as a result of quantum tunneling of the magnetization. Application of a 1500 Oe dc field initiates slow magnetic relaxation, which follows a thermally activated tunneling mechanism at high temperature to give an effective spin-reversal barrier of U(eff) = 42 cm(-1) and follows a temperature-independent tunneling mechanism at low temperature. In addition, the magnetic relaxation time shows a pronounced dc-field dependence, with a maximum occurring at approximately 1500 Oe.

Slow Magnetic Relaxation in a Family of Trigonal Pyramidal Iron(II) Pyrrolide Complexes

We present a family of trigonal pyramidal iron(II) complexes supported by tris(pyrrolyl-α-methyl)amine ligands of the general formula [M(solv)(n)][(tpa(R))Fe] (M = Na, R = tert-butyl (1), phenyl (4); M = K, R = mesityl (2), 2,4,6-triisopropylphenyl (3), 2,6-difluorophenyl (5)) and their characterization by X-ray crystallography, Mössbauer spectroscopy, and high-field EPR spectroscopy. Expanding on the discovery of slow magnetic relaxation in the recently reported mesityl derivative 2, this homologous series of high-spin iron(II) complexes enables an initial probe of how the ligand field influences the static and dynamic magnetic behavior. Magnetization experiments reveal large, uniaxial zero-field splitting parameters of D = -48, -44, -30, -26, and -6.2 cm(-1) for 1-5, respectively, demonstrating that the strength of axial magnetic anisotropy scales with increasing ligand field strength at the iron(II) center. In the case of 2,6-difluorophenyl substituted 5, high-field EPR experiments provide an independent determination of the zero-field splitting parameter (D = -4.397(9) cm(-1)) that is in reasonable agreement with that obtained from fits to magnetization data. Ac magnetic susceptibility measurements indicate field-dependent, thermally activated spin reversal barriers in complexes 1, 2, and 4 of U(eff) = 65, 42, and 25 cm(-1), respectively, with the barrier of 1 constituting the highest relaxation barrier yet observed for a mononuclear transition metal complex. In addition, in the case of 1, the large range of temperatures in which slow relaxation is observed has enabled us to fit the entire Arrhenius curve simultaneously to three distinct relaxation processes. Finally, zero-field Mössbauer spectra collected for 1 and 4 also reveal the presence of slow magnetic relaxation, with two independent relaxation barriers in 4 corresponding to the barrier obtained from ac susceptibility data and to the 3D energy gap between the M(S) = ±2 and ±1 levels, respectively.

A Redox-Switchable Single-Molecule Magnet Incorporating [Re(CN)7]3-

Reaction of [Re(CN)7]3- (S = 1/2) with 4 equiv of [(PY5Me2)Mn(MeCN)]2+ (S = 5/2) in acetonitrile generates a blue solution containing the cyano-bridged cluster [(PY5Me2)4Mn4Re(CN)7]5+. At room temperature, the color of the reaction rapidly changes from blue to green to yellow, spontaneously generating the one-electron reduced species [(PY5Me2)4Mn4Re(CN)7]4+. Crystal structures show these two clusters share a star-like geometry, wherein four [(PY5Me2)Mn]2+ units are appended to a central, pentagonal bipyramidal [Re(CN)7]3-/4- complex. The dc magnetic properties of the 5+ cluster indicate the presence of ferromagnetic coupling to give an S = 21/2 ground state with an axial zero-field splitting of D = −0.44 cm-1. Ac magnetic susceptibility measurements reveal a spin relaxation barrier of Ueff = 33 cm-1, the largest barrier yet observed for a cyano-bridged single-molecule magnet. Upon reduction by one electron, the spin at the Re center is lost and the cluster switches behavior to that of a simple paramagnet ...

A mononuclear transition metal single-molecule magnet in a nuclear spin-free ligand environment

The high-spin pseudotetrahedral complex [Co(C3S5)2](2-) exhibits slow magnetic relaxation in the absence of an applied dc magnetic field, one of a small number of mononuclear complexes to display this property. Fits to low-temperature magnetization data indicate that this single-molecule magnet possesses a very large and negative axial zero-field splitting and small rhombicity. The presence of single-molecule magnet behavior in a zero-nuclear spin ligand field offers the opportunity to investigate the potential for this molecule to be a qubit, the smallest unit of a quantum information processing (QIP) system. However, simulations of electron paramagnetic resonance (EPR) spectra and the absence of EPR spectra demonstrate that this molecule is unsuitable as a qubit due to the same factors that promote single molecule magnet behavior. We discuss the influence of rhombic and axial zero-field splitting on QIP applications and the implications for future molecular qubit syntheses.

Millisecond coherence time in a tunable molecular electronic spin qubit

Quantum information processing (QIP) could revolutionize areas ranging from chemical modeling to cryptography. One key figure of merit for the smallest unit for QIP, the qubit, is the coherence time (T2), which establishes the lifetime for the qubit. Transition metal complexes offer tremendous potential as tunable qubits, yet their development is hampered by the absence of synthetic design principles to achieve a long T2. We harnessed molecular design to create a series of qubits, (Ph4P)2[V(C8S8)3] (1), (Ph4P)2[V(β-C3S5)3] (2), (Ph4P)2[V(α-C3S5)3] (3), and (Ph4P)2[V(C3S4O)3] (4), with T2s of 1–4 μs at 80 K in protiated and deuterated environments. Crucially, through chemical tuning of nuclear spin content in the vanadium(IV) environment we realized a T2 of ∼1 ms for the species (d20-Ph4P)2[V(C8S8)3] (1′) in CS2, a value that surpasses the coordination complex record by an order of magnitude. This value even eclipses some prominent solid-state qubits. Electrochemical and continuous wave electron paramagnetic resonance (EPR) data reveal variation in the electronic influence of the ligands on the metal ion across 1–4. However, pulsed measurements indicate that the most important influence on decoherence is nuclear spins in the protiated and deuterated solvents utilized herein. Our results illuminate a path forward in synthetic design principles, which should unite CS2 solubility with nuclear spin free ligand fields to develop a new generation of molecular qubits.

Influence of Electronic Spin and Spin–Orbit Coupling on Decoherence in Mononuclear Transition Metal Complexes

Enabling the rational synthesis of molecular candidates for quantum information processing requires design principles that minimize electron spin decoherence. Here we report a systematic investigation of decoherence via the synthesis of two series of paramagnetic coordination complexes. These complexes, [M(C2O4)3](3-) (M = Ru, Cr, Fe) and [M(CN)6](3-) (M = Fe, Ru, Os), were prepared and interrogated by pulsed electron paramagnetic resonance (EPR) spectroscopy to assess quantitatively the influence of the magnitude of spin (S = (1)/2, (3)/2, (5)/2) and spin-orbit coupling (ζ = 464, 880, 3100 cm(-1)) on quantum decoherence. Coherence times (T2) were collected via Hahn echo experiments and revealed a small dependence on the two variables studied, demonstrating that the magnitudes of spin and spin-orbit coupling are not the primary drivers of electron spin decoherence. On the basis of these conclusions, a proof-of-concept molecule, [Ru(C2O4)3](3-), was selected for further study. The two parameters establishing the viability of a qubit are a long coherence time, T2, and the presence of Rabi oscillations. The complex [Ru(C2O4)3](3-) exhibits both a coherence time of T2 = 3.4 μs and the rarely observed Rabi oscillations. These two features establish [Ru(C2O4)3](3-) as a molecular qubit candidate and mark the viability of coordination complexes as qubit platforms. Our results illustrate that the design of qubit candidates can be achieved with a wide range of paramagnetic ions and spin states while preserving a long-lived coherence.

Site Specific X-ray Anomalous Dispersion of the Geometrically Frustrated Kagomé Magnet, Herbertsmithite, ZnCu3(OH)6Cl2

Structural characterization, exploiting X-ray scattering differences at elemental absorption edges, is developed to quantitatively determine crystallographic site-specific metal disorder. We apply this technique to the problem of Zn-Cu chemical disorder in ZnCu(3)(OH)(6)Cl(2). This geometrically frustrated kagomé antiferromagnet is one of the best candidates for a spin-liquid ground state, but chemical disorder has been suggested as a mundane explanation for its magnetic properties. Using anomalous scattering at the Zn and Cu edges, we determine that there is no Zn occupation of the intralayer Cu sites within the kagomé layer; however there is Cu present on the Zn intersite, leading to a structural formula of (Zn(0.85)Cu(0.15))Cu(3)(OH)(6)Cl(2). The lack of Zn mixing onto the kagomé lattice sites lends support to the idea that the electronic ground state in ZnCu(3)(OH)(6)Cl(2) and its relatives is nontrivial.

Slow magnetic relaxation and charge-transfer in cyano-bridged coordination clusters incorporating [Re(CN)(7)](3-/4-).

Treatment of the cyanometalate building unit [Re(CN)(7)](3-) with [(PY5Me(2))M(MeCN)](2+) (M = Co, Ni, Cu) affords a series of pentanuclear clusters of formulas [(PY5Me(2))(4)M(4)Re(CN)(7)](5+) (M = Co, Ni, Cu) and [(PY5Me(2))(4)Cu(4)Re(CN)(7)](4+). Single crystal X-ray diffraction analyses of the clusters reveal a star-like structure in which four [(PY5Me(2))M](2+) moieties are linked to a central [Re(CN)(7)](3-) unit via bridging cyanide ligands. An intramolecular Co(II) → Re(IV) charge-transfer accompanies the formation of the Co(II)(4)Re(IV) cluster, giving a Co(II)(3)Co(III)Re(III) species. Spectroelectrochemical methods and irradiation experiments are used to characterize the metal-metal charge-transfer bands of this compound. A rhenium-based thermally induced one-electron reduction is observed for the Cu(II)(4)Re(IV) cluster to give a Cu(II)(4)Re(III) complex; however, this reduction may be forestalled at low temperature. Finally, magnetic measurements reveal intracluster ferromagnetic exchange coupling, strong uniaxial magnetic anisotropy, and slow magnetic relaxation in the Ni(II)(4)Re(IV) and Cu(II)(4)Re(IV) clusters.

Topological Magnon Bands in a Kagome Lattice Ferromagnet

There is great interest in finding materials possessing quasiparticles with topological properties. Such materials may have novel excitations that exist on their boundaries which are protected against disorder. We report experimental evidence that magnons in an insulating kagome ferromagnet can have a topological band structure. Our neutron scattering measurements further reveal that one of the bands is flat due to the unique geometry of the kagome lattice. Spin wave calculations show that the measured band structure follows from a simple Heisenberg Hamiltonian with a Dzyaloshinkii-Moriya interaction. This serves as the first realization of an effectively two-dimensional topological magnon insulator--a new class of magnetic material that should display both a magnon Hall effect and protected chiral edge modes.

Multiple quantum coherences from hyperfine transitions in a vanadium(IV) complex.

We report a vanadium complex in a nuclear-spin free ligand field that displays two key properties for an ideal candidate qubit system: long coherence times that persist at high temperature, T2 = 1.2 μs at 80 K, and the observation of quantum coherences from multiple transitions. The electron paramagnetic resonance (EPR) spectrum of the complex [V(C8S8)3](2-) displays multiple transitions arising from a manifold of states produced by the hyperfine coupling of the S = ½ electron spin and I = 7/2 nuclear spin. Transient nutation experiments reveal Rabi oscillations for multiple transitions. These observations suggest that each pair of hyperfine levels hosted within [V(C8S8)3](2-) are candidate qubits. The realization of multiple quantum coherences within a transition metal complex illustrates an emerging method of developing scalability and addressability in electron spin qubits. This study presents a rare molecular demonstration of multiple Rabi oscillations originating from separate transitions. These results extend observations of multiple quantum coherences from prior reports in solid-state compounds to the new realm of highly modifiable coordination compounds.