General requirements for obtaining DyIII single-molecule magnets (SMM) were studied by CASSCF+RASSI calculations on both real and model systems. A set of 20 complexes was considered using their X-ray crystal structure our calculations. Theoretical results compared with experimental slow relaxation data, general conclusions about the calculated key parameters related SMM behavior are presented. The effect coordination geometry nature ligands is discussed based We found two different patterns...

Polynuclear 3d transition metal-Gd complexes are good candidates to present large magnetocaloric effect. This effect is favored by the presence of weak ferromagnetic exchange interactions that have been investigated using methods based on Density Functional Theory. The first part study devoted dinuclear complexes, focusing nature and mechanism such interactions. two bridging ligands found more favorable for coupling than a triple-bridged assembly, especially with small M–O···O–Gd hinge...

Controlling the spin of electrons in nanoscale electronic devices is one most promising topics aiming at developing with rapid and high density information storage capabilities. The interface magnetism or spinterface resulting from interaction between a magnetic molecule metal surface, vice versa, has become key ingredient creating molecular novel functionalities. Here, we present single-molecule wire that displays large (>10000%) conductance switching by controlling spin-dependent transport...

Improved versions of the segmented all-electron relativistically contracted (SARC) basis sets for lanthanides are presented. The second-generation SARC2 maintain efficient construction their predecessors and individual adaptation to DKH2 ZORA Hamiltonians, but feature exponents optimized with a completely new orbital shape fitting procedure slightly expanded f space that results in sizable improvement CASSCF energies significantly more accurate prediction spin-orbit coupling parameters....

Coherent quantum transport calculations were performed for high- and low-spin states of a mononuclear FeII complex showing spin-crossover behavior using density functional theory methods combined with the non-equilibrium Green functions procedure. The high-spin state has larger conductivity than state; furthermore, it behaves as spin filter, giving β-polarized current.

Regularities among electronic configurations for common oxidation states in lanthanide complexes and the low involvement of f orbitals bonding result appearance several periodic trends along series. These can be observed on relatively different properties, such as distances or ionization potentials. Well-known concepts like contraction, double–double (tetrad) effect, similar chemistry series stem from these regularities. Periodic structural spectroscopic properties are examined through...

Inclusion of thiourea guest molecules in the tridimensional spin crossover porous coordination polymers {[Fe(pyrazine)[M(CN)(4)]} (M = Pd, Pt) leads to novel clathrates exhibiting unprecedented large thermal hysteresis loops ca. 60 K wide centered near room temperature.

Over recent decades, much effort has been made to lengthen spin relaxation/decoherence times of single-molecule magnets and molecular qubits by following different chemical design rules such as maximizing the total value, controlling symmetry, enhancing ligand field or inhibiting key vibrational modes. Simultaneously, electronic structure calculations have employed provide an understanding processes involved in dynamics systems served refine introduce new rules. This review focuses on...

Relaxation mechanisms limiting the blocking temperature for high-performance single molecule magnets (SMMs) are investigated. Best SMMs limited by exponential regime. Current <italic>ab initio</italic> methods can yield accurate estimations this limit.

Abstract Two novel trinuclear complexes [ZnCl(μ‐L)Ln(μ‐L)ClZn][ZnCl 3 (CH OH)]⋅3 CH OH (Ln III =Dy ( 1 ) and Er 2 )) have been prepared from the compartmental ligand N , ′‐dimethyl‐ ′‐bis(2‐hydroxy‐3‐formyl‐5‐bromo‐benzyl)ethylenediamine (H L). X‐ray studies reveal that Ln ions are coordinated by two [ZnCl(L)] − units through phenoxo aldehyde groups, giving rise to a LnO 8 coordination sphere with square‐antiprism geometry strong easy‐axis anisotropy of ground state. Ab initio CASSCF+RASSI...

Single-molecule magnets (SMMs) are promising candidates for molecule-based quantum information devices. Their main limitation is their cryogenic operative temperature. To achieve devices performing at higher temperatures, demagnetization mechanisms must be suppressed by chemical tuning. Electronic structure calculations can provide useful to rationalize SMM behavior, but they do not a direct prediction the key experimental parameters describing magnetic relaxation (i.e., tunneling time (τQT)...

We present a general relation between the magnetisation blocking temperature (TB) measured using zero-field cooling/field cooling technique (ZFC/FC) and their temperature-dependent spin relaxation time obtained from ac-susceptibility magnetisation...

A series of heterometallic [Ln(III)(x)Cu(II)(y)] complexes, [Gd2Cu2]n (1), [Gd4Cu8] (2), [Ln9Cu8] (Ln=Gd, 3·Gd; Ln=Dy, 3·Dy), were successfully synthesized by a one-pot route at room temperature with three kinds in situ carbonyl-related reactions: Cannizzaro reaction, aldol and oxidation. This strategy led to dysprosium analogues that behaved as single-molecule magnets (SMMs) gadolinium showed significant magnetocaloric effect (MCE). In this study numerical DFT approach is proposed using...

Structural, spectroscopic and magnetic methods have been used to characterize the tris(carbene)borate compound PhB(MesIm)₃MnN as a four-coordinate manganese(<sc>iv</sc>) complex with low spin (<italic>S</italic> = 1/2) configuration.

The chemisorption of sulfur dioxide (SO2) on the Hofmann-like spin crossover porous coordination polymer (SCO-PCP) {Fe(pz)[Pt(CN)4]} has been investigated at room temperature. Thermal analysis and adsorption–desorption isotherms showed that ca. 1 mol SO2 per was retained in pores. Nevertheless, loosely attached to walls host network completely released 24 h 298 K. Single crystals {Fe(pz)[Pt(CN)4]}·nSO2 (n ≈ 0.25) were grown water solutions saturated with SO2, its crystal structure analyzed...

The dominance of a self-condensed conjugated macrocycle over [2 + 2] conventional in weakening the transverse crystal field and boosting axiality provides new route to construct high-performance air-stable lanthanide SMMs.

Two 3d–4f nanomagnets, [DyIII2CuII7] (1) and [GdIII6CuII12] (2), are synthesized under a two-step in situ reaction of picolinaldehyde. Not only the final adduct (hemiacetal), but also intermediate (gem-diol) "visualized" by X-ray single crystal diffraction. The Dy complex behaves as single-molecule magnet, while Gd exhibits significant magnetocaloric effect. Theoretical calculations employed to obtain orientation magnetic moments exchange.

Abstract The synthesis, structure, and magnetic properties of three clathrate derivatives the spin‐crossover porous coordination polymer {Fe(pyrazine)[Pt(CN) 4 ]} ( 1 ) with five‐membered aromatic molecules furan, pyrrole, thiophene is reported. have a cooperative transition hysteresis loops 14–29 K wide average critical temperatures T c =201 1⋅fur ), 167 1⋅pyr 114.6 1⋅thio well below that parent compound =295 K), confirming stabilization HS state. complete takes place in two steps for ,...

Photo-induced spin transition in a molybdenum–zinc complex has been evidenced: unique Light-Induced Excited Spin State Trapping Effect (LIESST) on 4d metal ion.

Slow magnetization relaxation <italic>via</italic> the second excited state with a <italic>U</italic>_eff = 186 cm⁻¹ has been observed in Zn–Dy–Zn complex.

Herein we report a dinuclear [(μ-mbpymNO){(tmh)3Dy}2] (1) single-molecule magnet (SMM) showing two nonequivalent DyIII centers, which was rationally prepared from the reaction of Dy(tmh)3 moieties (tmh = 2,2,6,6-tetramethyl-3,5-heptanedionate) and asymmetric bis-bidentate bridging ligand 4-methylbipyrimidine (mbpymNO). Depending on whether ions coordinate to N^O or N^N bidentate donor sets, sites present NO7 ( D2 d geometry) N2O6 D4 d) coordination sphere. As consequence, different thermally...