Iron(II), Cobalt(II), and Nickel(II) Complexes of Bis(sulfonamido)benzenes: Redox Properties, Large Zero-Field Splittings, and Single-Ion Magnets.

Metal complexes of 1,2-diamidobenzenes have been long studied because of their intriguing redox properties and electronic structures. We present here a series of such complexes with 1,2-bis(sulfonamido)benzene ligands to probe the utility of these ligands for generating a large zero-field splitting (ZFS, D) in metal complexes that possibly act as single-ion magnets. To this end, we have synthesized a series of homoleptic ate complexes of the form (X)n[M{bis(sulfonamido)benzene}2] (n equals 4 minus the oxidation state of the metal), where M (Fe/Co/Ni), X [K+/(K-18-c-6)+/(HNEt3)+, with 18-c-6 = 18-crown ether 6], and the substituents (methyl and tolyl) on the ligand [bmsab = 1,2-bis(methanesulfonamido)benzene; btsab = 1,2-bis(toluenesulfonamido)benzene] were varied to analyze their effect on the ZFS, possible single-ion-magnet properties, and redox behavior of these metal complexes. A combination of X-ray crystallography, (spectro)electrochemistry, superconducting quantum interference device magnetometry, high-frequency electron paramagnetic resonance spectroscopy, and Mössbauer spectroscopy was used to investigate the electronic/geometric structures of these complexes and the aforementioned properties. These investigations show that the cobalt(II) complexes display very high negative D values in the range of -100 to -130 cm-1, and the nickel(II) complexes display very high positive D values of 76 and 58 cm-1. In addition, the cobalt(II) complexes shows barriers of 200-260 cm-1 and slow relaxation of the magnetization in the absence of an external magnetic field, underscoring the robustness of this class of complexes. The iron(II) complex exhibits a D value of -3.29 cm-1 and can be chemically oxidized to an iron(III) complex that has D = -1.96 cm-1. These findings clearly show that bis(sulfonamido)benzenes are ideally suited to stabilize ate complexes, to generate very high ZFSs at the metal centers with single-ion-magnet properties, and to induce exclusive oxidation at the metal center (for iron) despite the presence of ligands that are potentially noninnocent. Our results therefore substantially enhance the scope for this class of redox-active ligands.

Toward fast and accurate ab initio calculation of magnetic exchange in polynuclear lanthanide complexes.

Ab initio calculations of the magnetic exchange in polynuclear lanthanide complexes are very challenging and often not feasible, due to large active spaces, the large number of required states or the necessity to include dynamical correlation into the calculations. We present an approach which allows for the computationally efficient calculation of exchange splittings in polynuclear lanthanide complexes including dynamical correlation. This is achieved by extending the local-density-fitted configuration-averaged Hartree-Fock (LDF-CAHF) method to systems with more than one group of open-shell orbitals (e.g. at different metal atoms) and combining it with linear-scaling many-state pair-natural-orbital complete active space perturbation theory of second order (PNO-CASPT2). In order to assess the performance of the method, we apply it to the asymmetric dinuclear complex [hqH2][Yb2(hq)4(NO3)3]·MeOH (hqH = 8-hydroxyquinoline).

Strong Exchange Couplings Drastically Slow Down Magnetization Relaxation in an Air-Stable Cobalt(II)-Radical Single-Molecule Magnet (SMM).

The energy barrier leading to magnetic bistability in molecular clusters is determined by the magnetic anisotropy of the cluster constituents. By incorporating a highly anisotropic four-coordinate cobalt(II) building block into a strongly coupled fully air- and moisture-stable three-spin system, it proved possible to suppress under-barrier Raman processes leading to 350-fold increase of magnetization relaxation time and pronounced hysteresis. Relaxation times of up to 9 hours at low temperatures were found.

Chromium(iii)-based potential molecular quantum bits with long coherence times.

Molecular quantum bits based on copper(ii) or vanadium(iv) have been shown to possess long coherence times on multiple occasions. In contrast, studies in which non-spin-½ ions are employed are relatively scarce. High-spin ions provide additional states that can be used to encode further quantum bits. Furthermore, an optical rather than a microwave readout of molecular quantum bits is highly desirable, because in principle it could allow addressing at the single quantum bit level. The chromium(iii) complex [Cr(ddpd)2]3+ (ddpd = N,N'-dimethyl-N,N'-dipyridine-2-yl-pyridine-2,6-diamine) combines both the large spin (S = 3/2) and optical activity (strong, long lived luminescence). Here we demonstrate that the compound possesses coherence times of up to 8.4(1) µs, which are much longer (at least three times) than those for other chromium(iii)-based compounds. On the other hand, it is proved to be impossible to read out or influence the quantum state by optical means, underlining that further work is needed in this direction.

Vibrational analysis of methyl cation-Rare gas atom complexes: CH3 +-Rg (Rg = He, Ne, Ar, Kr).

The vibrational spectra of simple CH3 +-Rg (Rg = He, Ne, Ar, Kr) complexes have been studied by vibrational configuration interaction theory relying on multidimensional potential energy surfaces (PESs) obtained from explicitly correlated coupled cluster calculations, CCSD(T)-F12a. In agreement with experimental results, the series of rare gas atoms leads to rather unsystematic results and indicates huge zero point vibrational energy effects for the helium complex. In order to study these sensitive complexes more consistently, we also introduce configuration averaged vibrational self-consistent field theory, which is a generalization of standard vibrational self-consistent field theory to several configurations. The vibrational spectra of the complexes are compared to that of the methyl cation, for which corrections due to scalar-relativistic effects, high-order coupled-cluster terms, e.g., quadruple excitations, and core-valence correlation have explicitly been accounted for. The occurrence of tunneling splittings for the vibrational ground-state of CH3 +-He has been investigated on the basis of semiclassical instanton theory. These calculations and a direct comparison of the energy profiles along the intrinsic reaction coordinates with that of the hydronium cation, H3O+, suggest that tunneling effects for vibrationally excited states should be very small.

Spectroscopic Determination of the Electronic Structure of a Uranium Single-Ion Magnet.

Early actinide ions have large spin-orbit couplings and crystal field interactions, leading to large anisotropies. The success in using actinides as single-molecule magnets has so far been modest, underlining the need for rational strategies. Indeed, the electronic structure of actinide single-molecule magnets and its relation to their magnetic properties remains largely unexplored. A uranium(III) single-molecule magnet, [UIII {SiMe2 NPh}3 -tacn)(OPPh3 )] (tacn=1,4,7-triazacyclononane), has been investigated by means of a combination of magnetic, spectroscopic and theoretical methods to elucidate the origin of its static and dynamic magnetic properties.

Exchange coupling and single molecule magnetism in redox-active tetraoxolene-bridged dilanthanide complexes.

Tetraoxolene radical-bridged lanthanide SMM systems were prepared for the first time by reduction of the respective neutral compounds. Magnetic measurements reveal the profound influence of the radical center on magnetic behavior. Strong magnetic couplings are revealed in the radical species, which switch on SMM behavior under zero applied field for DyIII and TbIII compounds. HFEPR spectra unravel the contributions of the magnetic coupling and the magnetic anisotropy. For GdIII this results in much more accurate magnetic coupling parameters with respect to bulk magnetic measurements.