skip to main content

Title: A linear cobalt(II) complex with maximal orbital angular momentum from a non-Aufbau ground state
Orbital angular momentum is a prerequisite for magnetic anisotropy, although in transition metal complexes it is typically quenched by the ligand field. By reducing the basicity of the carbon donor atoms in a pair of alkyl ligands, we synthesized a cobalt(II) dialkyl complex, Co(C(SiMe 2 ONaph) 3 ) 2 (where Me is methyl and Naph is a naphthyl group), wherein the ligand field is sufficiently weak that interelectron repulsion and spin-orbit coupling play a dominant role in determining the electronic ground state. Assignment of a non-Aufbau (d x 2 –y 2 , d xy ) 3 (d xz , d yz ) 3 (d z 2 ) 1 electron configuration is supported by dc magnetic susceptibility data, experimental charge density maps, and ab initio calculations. Variable-field far-infrared spectroscopy and ac magnetic susceptibility measurements further reveal slow magnetic relaxation via a 450–wave number magnetic excited state.
; ; ; ; ; ; ; ; ;
Award ID(s):
Publication Date:
Journal Name:
Page Range or eLocation-ID:
Sponsoring Org:
National Science Foundation
More Like this
  1. This study presents the role of 5d orbitals in the bonding, and electronic and magnetic structure of Ce imido and oxo complexes synthesized with a tris(hydroxylaminato) [((2- t BuNO)C 6 H 4 CH 2 ) 3 N] 3− (TriNO x 3− ) ligand framework, including the reported synthesis and characterization of two new alkali metal-capped Ce oxo species. X-ray spectroscopy measurements reveal that the imido and oxo materials exhibit an intermediate valent ground state of the Ce, displaying hallmark features in the Ce L III absorption of partial f-orbital occupancy that are relatively constant for all measured compounds. These spectra feature a double peak consistent with other formal Ce( iv ) compounds. Magnetic susceptibility measurements reveal enhanced levels of temperature-independent paramagnetism (TIP). In contrast to systems with direct bonding to an aromatic ligand, no clear correlation between the level of TIP and f-orbital occupancy is observed. CASSCF calculations defy a conventional van Vleck explanation of the TIP, indicating a single-reference ground state with no low-lying triplet excited state, despite accurately predicting the measured values of f-orbital occupancy. The calculations do, however, predict strong 4f/5d hybridization. In fact, within these complexes, despite having similar f-orbital occupancies and therefore levels of 4f/5dmore »hybridization, the d-state distributions vary depending on the bonding motif (CeO vs. CeN) of the complex, and can also be fine-tuned based on varying alkali metal cation capping species. This system therefore provides a platform for understanding the characteristic nature of Ce multiple bonds and potential impact that the associated d-state distribution may have on resulting reactivity.« less
  2. The synthesis, crystal structure determination, magnetic properties and bonding interaction analysis of a novel 3 d transition-metal complex, [CrBr 2 (NCCH 3 ) 4 ](Br 3 ), are reported. Single-crystal X-ray diffraction results show that [CrBr 2 (NCCH 3 ) 4 ](Br 3 ) crystallizes in space group C 2/ m (No. 12) with a symmetric tribromide anion and the powder X-ray diffraction results show the high purity of the material specimen. X-ray photoelectron studies with a combination of magnetic measurements demonstrate that Cr adopts the 3+ oxidation state. Based on the Curie–Weiss analysis of magnetic susceptibility data, the Néel temperature is found to be around 2.2 K and the effective moment (μ eff ) of Cr 3+ in [CrBr 2 (NCCH 3 ) 4 ](Br 3 ) is ∼3.8 µ B , which agrees with the theoretical value for Cr 3+ . The direct current magnetic susceptibility of the molecule shows a broad maximum at ∼2.3 K, which is consistent with the theoretical Néel temperature. The maximum temperature, however, shows no clear frequency dependence. Combined with the observed upturn in heat capacity below 2.3 K and the corresponding field dependence, it is speculated that the low-temperature magnetic feature of a broad transition inmore »[CrBr 2 (NCCH 3 ) 4 ](Br 3 ) could originate from a crossover from high spin to low spin for the split d orbital level low-lying states rather than a short-range ordering solely; this is also supported by the molecular orbital diagram obtained from theoretical calculations.« less
  3. Iron-based extended metal atom chains (EMACs) are potentially high-spin molecules with axial magnetic anisotropy and thus candidate single-molecule magnets (SMMs). We herein compare the tetrairon( ii ), halide-capped complexes [Fe 4 (tpda) 3 Cl 2 ] ( 1Cl ) and [Fe 4 (tpda) 3 Br 2 ] ( 1Br ), obtained by reacting iron( ii ) dihalides with [Fe 2 (Mes) 4 ] and N 2 , N 6 -di(pyridin-2-yl)pyridine-2,6-diamine (H 2 tpda) in toluene, under strictly anhydrous and anaerobic conditions (HMes = mesitylene). Detailed structural, electrochemical and Mössbauer data are presented along with direct-current (DC) and alternating-current (AC) magnetic characterizations. DC measurements revealed similar static magnetic properties for the two derivatives, with χ M T at room temperature above that for independent spin carriers, but much lower at low temperature. The electronic structure of the iron( ii ) ions in each derivative was explored by ab initio (CASSCF-NEVPT2-SO) calculations, which showed that the main magnetic axis of all metals is directed close to the axis of the chain. The outer metals, Fe1 and Fe4, have an easy-axis magnetic anisotropy ( D = −11 to −19 cm −1 , | E / D | = 0.05–0.18), while the internal metals,more »Fe2 and Fe3, possess weaker hard-axis anisotropy ( D = 8–10 cm −1 , | E / D | = 0.06–0.21). These single-ion parameters were held constant in the fitting of DC magnetic data, which revealed ferromagnetic Fe1–Fe2 and Fe3–Fe4 interactions and antiferromagnetic Fe2–Fe3 coupling. The competition between super-exchange interactions and the large, noncollinear anisotropies at metal sites results in a weakly magnetic non-Kramers doublet ground state. This explains the SMM behavior displayed by both derivatives in the AC susceptibility data, with slow magnetic relaxation in 1Br being observable even in zero static field.« less
  4. A covalently-linked dimer of two single-molecule magnets (SMMs), [Mn 6 O(O 2 CMe) 6 (1,3-ppmd) 3 ](ClO 4 ) 2 , has been synthesized from the reaction of [Mn 3 O(O 2 CMe) 6 (py) 3 ](ClO 4 ) with 1,3-phenylene- bis (pyridin-2-ylmethanone) dioxime (1,3-ppmdH 2 ). It contains two [Mn III 3 O] +7 triangular units linked by three 1,3-ppmd 2− groups into an [Mn 3 ] 2 dimer with D 3 symmetry. Solid-state dc and ac magnetic susceptibility measurements showed that each Mn 3 subunit retains its properties as an SMM with an S = 6 ground state. Magnetization vs. dc field sweeps on a single crystal reveal hysteresis loops below 1.3 K exhibiting exchange-biased quantum tunnelling of magnetization (QTM) steps with a bias field of +0.06 T. This is the first example of a dimer of SMMs showing a positive exchange bias of the QTM steps in the hysteresis loops, and it has therefore been subjected to a detailed analysis. Simulation of the loops determines that each Mn 3 unit is exchange-coupled with its neighbour primarily through the 1,3-ppmd 2− linkers, confirming a weak ferromagnetic inter-Mn 3 interaction of J 12 ≈ +6.5 mK ( Ĥ =more »−2 JŜ i · Ŝ j convention). High-frequency EPR studies of a microcrystalline powder sample enable accurate determination of the zero-field splitting parameters of the uncoupled Mn 3 SMMs, while also confirming the weak exchange interaction between the two SMMs within each [Mn 3 ] 2 dimer. The combined results emphasize the ability of designed covalent linkers to generate inter-SMM coupling of a particular sign and relative magnitude, and thus the ability of such linkers to modulate the quantum physics. As such, this work supports the feasibility of using designed covalent linkers to develop molecular oligomers of SMMs, or other magnetic molecules, as multi-qubit systems and/or other components of new quantum technologies.« less
  5. Recently, the choice of ligand and geometric control of mononuclear complexes, which can affect the relaxation pathways and blocking temperature, have received wide attention in the field of single-ion magnets (SIMs). To find out the influence of the coordination environment on SIMs, two four-coordinate mononuclear Co( ii ) complexes [NEt 4 ][Co(PPh 3 )X 3 ] (X = Cl − , 1; Br − , 2) have been synthesized and studied by X-ray single crystallography, magnetic measurements, high-frequency and -field EPR (HF-EPR) spectroscopy and theoretical calculations. Both complexes are in a cubic space group Pa 3̄ (No. 205), containing a slightly distorted tetrahedral moiety with crystallographically imposed C 3 v symmetry through the [Co(PPh 3 )X 3 ] − anion. The direct-current (dc) magnetic data and HF-EPR spectroscopy indicated the anisotropic S = 3/2 spin ground states of the Co( ii ) ions with the easy-plane anisotropy for 1 and 2. Ab initio calculations were performed to confirm the positive magnetic anisotropies of 1 and 2. Frequency- and temperature-dependent alternating-current (ac) magnetic susceptibility measurements revealed slow magnetic relaxation for 1 and 2 at an applied dc field. Finally, the magnetic properties of 1 and 2 were compared to those ofmore »other Co( ii ) complexes with a [CoAB 3 ] moiety.« less