Co(II)-Based single-ion magnets with 1,1'-ferrocenediyl-bis(diphenylphosphine) metalloligands.

Herein, we report on investigations of magnetic and spectroscopic properties of three heterobimetallic Fe(ii)-Co(ii) coordination compounds based on the tetracoordinate {CoP2X2} core encapsulated by dppf metalloligand, where X = Cl (1), Br (2), I (3), dppf = 1,1'-ferrocenediyl -bis(diphenylphosphine). The analysis of static magnetic data has revealed the presence of axial magnetic anisotropy in compounds (1) and (2) and this was further confirmed by high-frequency electron spin resonance (HF-ESR) spectroscopy. Dynamic magnetic data confirmed that (1) and (2) behave as field-induced Single-Ion Magnets (SIMs). Together with bulk studies, we have also tested the possibility of depositing (2) as thick films on Au(111), glass, and polymeric acetate by drop-casting as well as thermal sublimation, a key aspect for the development of future devices embedding these magnetic objects.

Multi-frequency rapid-scan HFEPR.

Gaining access to electron spin dynamics at (sub-)THz frequencies is highly challenging. However, this information is highly relevant for the understanding and development of spin polarization agents in dynamic nuclear polarization methods and single-molecule magnets for quantum computation. Here we demonstrate the first rapid-scan EPR experiment in 200 GHz frequency region. A voltage controlled oscillator (VCO) generated fast sinusoidal frequency sweeps with scan rates up to 3×105 THz/s after the frequency multiplication, which is equal to 107 T/s in field representation. Such high scan rates provide access to extremely short relaxation times T2=2π×sweeprate-0.5≈1 ns. The absence of a microwave cavity allowed us to perform multi-frequency experiments in the 170-250 GHz range. A further advantage of a cavity-less approach is the possibility to use vast sweeps, which in turn, allows the deconvolution using a linear sweep function. The deconvoluted spectra obtained with this method are identical to the slow-rate spectrum. We find spin-spin relaxation times of several nanoseconds for pure LiPc samples in this frequency range. These values cannot be obtained by means of conventional pulsed EPR methods.

Crystal Field Splittings in Lanthanide Complexes: Inclusion of Correlation Effects beyond Second Order Perturbation Theory.

State-averaged complete active space self-consistent field (CASSCF) calculations and a subsequent spin-orbit calculation mixing the CASSCF wave functions (CASSCF/state-interaction with spin-orbit coupling) is the conventional approach used for ab initio calculations of crystal-field splittings and magnetic properties of lanthanide complexes. However, this approach neglects dynamical correlation. Complete active space second-order perturbation theory (CASPT2) can be used to account for dynamical correlation but suffers from the well-known problems of multireference perturbation theory, e.g., intruder state problems. Variational multireference configuration interaction (MRCI) calculations do not show these problems but are usually not feasible due to the large size of real lanthanide complexes. Here, we present a quasi-local projected internally contracted MRCI approach which makes MRCI calculations of lanthanide complexes feasible and allows assessing the influence of dynamical correlation beyond second-order perturbation theory. We apply the method to two well-studied molecules, namely, [Er{N(SiMe3)2}3] and {C(NH2)3}5[Er(CO3)4]·11H2O.

Ultra-broadband EPR spectroscopy in field and frequency domains.

Electron paramagnetic resonance (EPR) is a powerful technique to investigate the electronic and magnetic properties of a wide range of materials. We present the first combined terahertz (THz) field and frequency domain electron paramagnetic resonance (HFEPR/FDMR) spectrometer designed to investigate the electronic structure and magnetic properties of molecular systems, thin films and solid state materials in a very broad frequency range of 85-1100 GHz. In this paper, we show high resolution frequency-field (Zeeman) maps (170-380 GHz by 0-15 T) recorded on two single-molecule magnets, [Mn2(saltmen)2(ReO4)2] and [Mn2(salpn)2(H2O)2](ClO4)2, which give direct access to the field-dependence of the energy level diagram. Furthermore, supression of standing waves in the described system and the sensitivity in field and frequency domain operations is evaluated and discussed.

Fast and reliable ab initio calculation of crystal field splittings in lanthanide complexes.

Ab initio calculations of crystal field splittings and magnetic properties of lanthanide complexes are usually performed using state-averaged complete active space self-consistent field (CASSCF) calculations and a subsequent spin-orbit calculation mixing the CASSCF wave functions (CASSCF/state interaction with spin-orbit coupling). Because this approach becomes very time-consuming for large molecules, simplifications have been proposed in the literature to determine the state-averaged orbitals by configuration-averaged Hartree-Fock (CAHF) instead of CASSCF. We present an approach which is an extension of the CAHF method. We combine the techniques of local density fitting with CAHF and achieve a significant speedup compared to CASSCF without loss in accuracy. To assess the performance of our method, we apply it to three well-known molecules, namely, Er[N(SiMe3)2]3, Er(trensal), and the double-decker (NBu4)+ [Er(Pc)2]-.

Membrane-based torque magnetometer: Enhanced sensitivity by optical readout of the membrane displacement.

The design and realization of a torque magnetometer is reported that reads the deflection of a membrane by optical interferometry. The compact instrument allows for low-temperature measurements of tiny crystals less than a microgram with a significant improvement in sensitivity, signal-to-noise ratio as well as data acquisition time compared with conventional magnetometry and offers an enormous potential for further improvements and future applications in different fields. Magnetic measurements on single-molecule magnets demonstrate the applicability of the membrane-based torque magnetometer.

Quantitative prediction of nuclear-spin-diffusion-limited coherence times of molecular quantum bits based on copper(ii).

We have investigated the electron spin dynamics in a series of copper(ii) ß-diketonate complexes both in frozen solutions and doped solids. Double digit microsecond coherence times were found at low temperatures. We report quantitative simulations of the coherence decays solely based on the crystal structure of the doped solids.

Molecular qubits based on potentially nuclear-spin-free nickel ions.

Molecular qubits with the longest coherence times thus far are based on nuclear-spin-carrying central ions. These nuclear spins can cause quantum state leakage, which is detrimental to quantum algorithm performance. We present two novel molecular qubits based on potentially nuclear spin-free Ni in the formal oxidation state 3+. (d20-PPh4)[Ni(mnt)2] (Ni-mnt, mnt2- = maleonitrile-1,2-dithiolate) possesses a coherence time of up to 38.7 µs at 7 K. Functionalization of the dithiolate ligand decreases the coherence time by a factor of only four in (HNEt3)[Ni(dip)2] (Ni-dip, dip2- = 3-(diphenylphosphoryl)-methylbenzene-1,2-dithiolate), indicating that monoanionic Ni-dithiolene complexes are promising and robust building blocks for polynuclear molecular qubit gates.

Coupling molecular spin centers to microwave planar resonators: towards integration of molecular qubits in quantum circuits.

We present spectroscopic measurements looking for the coherent coupling between molecular magnetic centers and microwave photons. The aim is to find the optimal conditions and the best molecular features to achieve the quantum strong coupling regime, for which coherent dynamics of hybrid photon-spin states take place. To this end, we used a high critical temperature YBCO superconducting planar resonator working at 7.7 GHz and at low temperatures to investigate three molecular mononuclear coordination compounds, namely (PPh4)2[Cu(mnt)2] (where mnt2- = maleonitriledithiolate), [ErPc2]-TBA+ (where pc2- is the phtalocyaninato and TBA+ is the tetra-n-butylammonium cation) and Dy(trensal) (where H3trensal = 2,2',2''-tris(salicylideneimino)triethylamine). Although the strong coupling regime was not achieved in these preliminary experiments, the results provided several hints on how to design molecular magnetic centers to be integrated into hybrid quantum circuits.

A Mn(iii) single ion magnet with tridentate Schiff-base ligands.

Single ion magnet behaviour is reported for a mononuclear Mn(iii) ion with tridentate Schiff-base ligands which exhibits a tetragonal Jahn-Teller elongation along the Namine-Mn-Namine axis and crystallises with two crystallographically distinct Mn(iii) cations (unit A and unit B). While magnetic measurements show a large and negative axial zero-field splitting (D = -4.73 cm(-1)), HF-EPR reveal two distinct large axial Ds (D = -4.60 cm(-1) for unit A and D = -4.18 cm(-1) for unit B), thus resulting in the largest D known to date for a Mn(iii) single ion magnet. AC magnetic measurements at 2000 Oe allowed determination of the energy barrier for spin reversal (10.19 K) and spin reversal relaxation time (1.476 × 10(-6) s) for the Mn(iii) ion. Computational studies were used to characterise the electronic structure and substantiate the zero field splitting in the Mn(iii) complex.

Magneto-optical investigations of molecular nanomagnet monolayers.

We report field-dependent magnetization measurements on monolayers of [Dy(Pc)2] on quartz, prepared by the Langmuir-Blodgett technique. The films are thoroughly characterized by means of X-ray reflectivity and atomic force microscopy. The magnetisation of the sample is measured through the magnetic circular dichroism of a ligand-based electronic transition.

Tuning of molecular qubits: very long coherence and spin-lattice relaxation times.

We report a pulsed EPR study on different transition metal phthalocyanines, elucidating the dependence of spin relaxation on solvent, ligand and metal ion. Coherence times of >40 µs and spin-lattice relaxation times of up to 2 s were found. Minimization of SOMO-environment overlap leads to increased coherence times.

Direct observation of finite size effects in chains of antiferromagnetically coupled spins.

Finite spin chains made of few magnetic ions are the ultimate-size structures that can be engineered to perform spin manipulations for quantum information devices. Their spin structure is expected to show finite size effects and its knowledge is of great importance both for fundamental physics and applications. Until now a direct and quantitative measurement of the spatial distribution of the magnetization of such small structures has not been achieved even with the most advanced microscopic techniques. Here we present measurements of the spin density distribution of a finite chain of eight spin-3/2 ions using polarized neutron diffraction. The data reveal edge effects that are a consequence of the finite size and of the parity of the chain and indicate a noncollinear spin arrangement. This is in contrast with the uniform spin distribution observed in the parent closed chain and the collinear arrangement in odd-open chains.

Gd-based single-ion magnets with tunable magnetic anisotropy: molecular design of spin qubits.

We report ac susceptibility and continuous wave and pulsed EPR experiments performed on GdW10 and GdW30 polyoxometalate clusters, in which a Gd3+ ion is coordinated to different polyoxometalate moieties. Despite the isotropic character of gadolinium as a free ion, these molecules show slow magnetic relaxation at very low temperatures, characteristic of single molecule magnets. For T≲200 mK, the spin-lattice relaxation becomes dominated by pure quantum tunneling events, with rates that agree quantitatively with those predicted by the Prokof'ev and Stamp model [Phys. Rev. Lett. 80, 5794 (1998)]. The sign of the magnetic anisotropy, the energy level splittings, and the tunneling rates strongly depend on the molecular structure. We argue that GdW30 molecules are also promising spin qubits with a coherence figure of merit Q(M)≳50.

New directions in electron paramagnetic resonance spectroscopy on molecular nanomagnets.

Recent developments and results in the area of electron paramagnetic resonance (EPR) in molecular nanomagnetism are reviewed. Emphasis is placed on unconventional measurement methods, such as frequency-domain magnetic resonance spectroscopy, interferometer-based Fourier-transform, terahertz spectroscopy, and terahertz time-domain spectroscopy. In addition, different methods to investigate EPR by monitoring the change in magnetization or magnetic torque in the presence of microwave radiation are discussed. Finally, an overview is given of application of pulse EPR in investigations of molecular nanomagnets.

Broadband electron spin resonance at 4-40 GHz and magnetic fields up to 10 T.

A broadband electron spin resonance spectrometer is described which operates at frequencies between 4 and 40 GHz and can be used in superconducting magnets. A tunable cylindrical cavity is connected to a vector network analyzer via coaxial cables, and the radiation is fed into the cavity by a coupling loop. No field modulation is employed. Resonance frequencies below 14 GHz are obtained by inserting dielectrics with different permittivities into the cavity. The setup allows for measurements with the microwave magnetic field either parallel or perpendicular to the external field.

Direct observation of quantum coherence in single-molecule magnets.

Direct evidence of quantum coherence in a single-molecule magnet in a frozen solution is reported with coherence times as long as T{2}=630+/-30 ns. We can strongly increase the coherence time by modifying the matrix in which the single-molecule magnets are embedded. The electron spins are coupled to the proton nuclear spins of both the molecule itself and, interestingly, also to those of the solvent. The clear observation of Rabi oscillations indicates that we can manipulate the spin coherently, an essential prerequisite for performing quantum computations.

Breakdown of the giant spin model in the magnetic relaxation of the Mn6 nanomagnets.

We study the spin dynamics in two variants of the high-anisotropy Mn6 nanomagnet by inelastic neutron scattering, magnetic resonance spectroscopy and magnetometry. We show that a giant-spin picture is completely inadequate for these systems and that excited S multiplets play a key role in determining the effective energy barrier for the magnetization reversal. Moreover, we demonstrate the occurrence of tunneling processes involving pair of states having different total spin.

UV-visible absorption spectra of [Ru(E)(E')(CO)(2)(iPr-DAB)] (E = E' = SnPh(3) or Cl; E = SnPh(3) or Cl, E' = CH(3); iPr-DAB = N,N'-Di-isopropyl-1,4-diaza-1,3-butadiene): combination of CASSCF/CASPT2 and TD-DFT calculations.

The UV-visible absorption spectra of [Ru(E)(E')(CO)(2)(iPr-DAB)] (E = E' = SnPh(3) or Cl; E = SnPh(3) or Cl, E' = CH(3); iPr-DAB = N,N'-di-isopropyl-1,4-diaza-1,3-butadiene) are investigated using CASSCF/CASPT2 and TD-DFT calculations on model complexes [Ru(E)(E')(CO)(2)(Me-DAB)] (E = E' = SnH(3) or Cl; E = SnH(3) or Cl, E' = CH(3); Me-DAB = N,N'-dimethyl-1,4-diaza-1,3-butadiene). The calculated transition energies and oscillator strengths allow an unambiguous assignment of the spectra of the nonhalide complexes [Ru(SnPh(3))(2)(CO)(2)(iPr-DAB)] and [Ru(SnPh(3))(Me)(CO)(2)(iPr-DAB)]. The agreement between the CASSCF/CASPT2 and TD-DFT approaches is remarkably good in the case of these nonhalide complexes. The lowest-energy part of the spectrum (visible absorption) originates in electronic transitions that correspond to excitations from the axial E-Ru-E' sigma(2) orbital into the low-lying pi(DAB) orbital (sigma-bond-to-ligand charge transfer, SBLCT, transitions), while the absorption between 25 000 and 35 000 cm(-1) is due to metal-to-ligand charge transfer (MLCT) excitations from the 4d(Ru) orbitals to pi(DAB) (MLCT). Above 35 000 cm(-1), the transitions mostly correspond to MLCT and SBLCT excitations into pi(CO) orbitals. Analysis of the occupied sigma orbitals involved in electronic transitions of the nonhalide complexes shows that the Kohn-Sham orbitals are generally more delocalized than their CASSCF/CASPT2 counterparts. The CASSCF/CASPT2 and TD-DFT approaches lead to different descriptions of electronic transitions of the halide complexes [Ru(Cl)(2)(CO)(2)(Me-DAB)] and [Ru(Cl)(Me)(CO)(2)(Me-DAB)]. CASSCF/CASPT2 reproduces well the observed blue-shift of the lowest absorption band on going from the nonhalide to halide complexes. TD-DFT systematically underestimates the transition energies of these complexes, although it reproduces the general spectral features. The CASSCF/CASPT2 and TD-DFT techniques differ significantly in their assessment of the chloride contribution. Thus, CASSCF/CASPT2 assigns the lowest-energy absorption to predominantly Ru --> DAB MLCT transitions, while TD-DFT predicts a mixed XLCT/MLCT character, with the XLCT component being predominant. (XLCT stands for halide (X)-to-ligand-charge transfer.) Analysis of Kohn-Sham orbitals shows a very important 3p(Cl) admixture into the high-lying occupied orbitals, in contrast to the CASSCF/CASSPT2 molecular orbitals which are nearly pure 4d(Ru) with the usual contribution of the back-donation to pi(CO) orbitals. Further dramatic differences were found between characters of the occupied sigma orbitals, as calculated by CASSCF/CASPT2 and DFT. They differ even in their bonding character with respect to the axial E-Ru and Cl-Ru bonds. These differences are attributed to a drawback of the DFT technique with respect to the dynamical correlation effects which become very important in complexes with a polar Ru-Cl bond. Similar differences in the CASSCF/CASPT2 and TD-DFT descriptions of the lowest allowed transition of [Ru(Cl)(2)(CO)(2)(Me-DAB)] and [Ru(Cl)(Me)(CO)(2)(Me-DAB)] were found by comparing the changes of Mulliken population upon excitation. This comparison also reveals that CASSCF/CASPT2 generally predicts smaller electron density redistribution upon excitation than TD-DFT, despite the more localized character of CASSCF/CASPT2 molecular orbitals.

The stable diiron(2.5) complex ion [(NC)(5)Fe(mu-tz)Fe(CN)5](5-), tz = 1,2,4,5-tetrazine, and its neighboring oxidation states.

The conceptually simple mixed-valent diiron compound (NEt(4))(5)[(NC)(5)Fe(mu-tz)Fe(CN)(5)] with the 1,2,4,5-tetrazine (tz) bridging ligand was obtained as a thermally and air-stable material that displays large and highly variable electrochemical comproportionation constants between about 10(8) (in water) and 10(19.0) (in acetonitrile). Strong metal-metal interaction is also evident from spectroscopic results obtained for the solid and for the dissolved species. The rather intense intervalence charge-transfer band occurs around 2400 nm; infrared and Mössbauer spectra reveal the high spectroscopic symmetry of the system according to an (Fe(2.5))(2) formulation. DFT calculations on the [(NC)(5)Fe(mu-tz)Fe(CN)(5)](6-) ion confirm the presence of very low-lying pi(tz) and high-lying d(Fe) orbitals.