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Nanostructures, fabricated by locating molecular building blocks in well-defined positions, for example, on a lattice, are ideal platforms for studying atomic-scale quantum effects. In this context, STM data obtained from self-assembled Bis(phthalocyaninato) Terbium (III) (TbPc2) single-molecule magnets on various substrates have raised questions about the conformation of the TbPc2 molecules within the lattice. In order to address this issue, molecular dynamics simulations were carried out on a 2D assembly of TbPc2 molecules. The calculations are in excellent agreement with the experiment, and thus improve our understanding of the self-assembly process. In particular, the calculated electron density of the molecular assembly compares well with STM contrast of self-assembled TbPc2 on Au(111), simultaneously providing the conformation of the two Pc ligands of the individual double-decker molecule. This approach proves valuable in the identification of the STM contrast of LnPc2 layers and could be used in similar cases where it is difficult to interpret the STM images of an assembly of molecular complexes.

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Hybrid layered materials assembled from atomically thin crystals and small molecules bring great promises in pushing the current information and quantum technologies beyond the frontiers. We demonstrate here a class of layered valley-spin hybrid (VSH) materials composed of a monolayer two-dimensional (2D) semiconductor and double-decker single molecule magnets (SMMs). We have materialized a VSH prototype by thermal evaporation of terbium bis-phthalocyanine onto a MoS2 monolayer and revealed its composition and stability by both microscopic and spectroscopic probes. The interaction of the VSH components gives rise to the intersystem crossing of the photogenerated carriers and moderate p-doping of the MoS2 monolayer, as corroborated by the density functional theory calculations. We further explored the valley contrast by helicity-resolved photoluminescence (PL) microspectroscopy carried out down to liquid helium temperatures and in the presence of the external magnetic field. The most striking feature of the VSH is the enhanced A exciton-related valley emission observed at the out-of-resonance condition at room temperature, which we elucidated by the proposed nonradiative energy drain transfer mechanism. Our study thus demonstrates the experimental feasibility and great promises of the ultrathin VSH materials with chiral light emission, operable by physical fields for emerging opto-spintronic, valleytronic, and quantum information concepts.

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Nitronyl nitroxides are functional building blocks in cutting-edge research fields, such as the design of molecular magnets, the development of redox and photoswitchable molecular systems and the creation of redox-active components for organic and hybrid batteries. The key importance of the nitronyl nitroxide function is to translate molecular-level-optimized structures into nano-scale devices and new technologies. In spite of great importance, efficient and versatile synthetic approaches to these compounds still represent a challenge. Particularly, methods for the direct introduction of a nitronyl nitroxide moiety into aromatic systems possess many limitations. Here, we report gold derivatives of nitronyl nitroxide that can enter Pd(0)-catalysed cross-coupling reactions with various aryl bromides, affording the corresponding functionalized nitronyl nitroxides. Based on the high thermal stability and enhanced reactivity in catalytic transformation, a new reagent is suggested for the synthesis of radical systems via a universal cross-coupling approach.

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2D magnets provoke a surge of interest in large anisotropy in reduced dimensions and are promising for next-generation information technology where dynamic magnetic tuning is essential. Until recently, the crucial metal-organic magnet Cr(pyz)2 ·xLiCl·yTHF with considerable high coercivity and high-temperature magnetic order opens up a new platform to control magnetism in metal-organic materials at room temperature. Here, an in-situ chemical tuning route is reported to realize the controllable transformation of low-temperature magnetic order into room-temperature hard magnetism in Cr(pyz)2 ·xLiCl·yTHF. The chemical tuning via electrochemical lithiation and solvation/desolvation exhibits continuously variable magnetic features from cryogenic magnetism to the room-temperature optimum performance of coercivity (Hc ) of 8500 Oe and energy product of 0.6 MGOe. Such chemically flexible tunability of room-temperature magnetism is ascribed to the different degrees of lithiation and solvation that modify the stoichiometry and Cr-pyrazine coordination framework. Furthermore, the additively manufactured hybrid magnets show air stability and electromagnetic induction, providing potential applications. The findings here suggest chemical tuning as a universal approach to control the anisotropy and magnetism of 2D hybrid magnets at room temperature, promising for data storage, magnetic refrigeration, and spintronics.

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To understand how polyethyleneimine (PEI), as a ligand, affects structure and properties of the transition metals hexacyanoferrates (HCFs) immobilized in cross-linked PEI matrix, we have synthesized Cu(II), Zn(II), and Fe(III) HCFs via successive ion-exchange reactions with metal salts and K4[FeII(CN)6] or K3[FeIII(CN)6]. The structure and properties of the obtained materials in comparison with the crystalline HCF analogs were investigated with FT-IR, Mössbauer, and UV-Vis spectroscopy. Complete reduction of Fe(III) to Fe(II) by PEI in HCF(III) was confirmed. When synthesis was performed at pH favoring binding of precursor metal ions by PEI, cyano-bridged hybrids rather than polymer-HCFs composites were formed. Although the obtained hybrids did not demonstrate sorption activity toward cesium ions, known for crystalline HCFs, they are of interest for the other applications. SQUID measurements revealed a significant difference in magnetic properties of PEI-HCFs hybrids in comparison with crystalline HCFs. Due to the Fe(III) to Fe(II) reduction in HCF ions, Cu(II) and Fe(III) HCFs(III) lost the molecular magnets properties in PEI matrix, but magnetic ordering, including ferromagnet-antiferromagnet interactions, was observed in all hybrids over the broad temperature range.

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In this report, we study the ordering of C60 , Sc3 N@C80 , and Dy2 ScN@C80 molecules on different metallic and dielectric surfaces such as Ag(100), Au(111), and MgO(100). By using DFT techniques, we can classify different types of cage-to-surface arrangements and their relative energies. Using a proposed homogenous sampling of the conformational space for the M3 N cluster, we determine a potential energy map that is capable of providing a structural distribution for a given energy window. We find that Coulomb interaction is a dominant force that governs the system's stability and order. However, a deep analysis of the charge density rearrangements reveals that even though the integral charges may be considered as a qualitative control parameter, it fails to provide quantitative data due to the importance of spatial characteristics of charge densities.

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Magnetoactive coordination compounds exhibiting bi- or multistability between two or more magnetic stable states present an attractive example of molecular switches. Currently, the research is focused on molecular nanomagnets, especially single molecule magnets (SMMs), which are molecules, where the slow relaxation of the magnetization based on the purely molecular origin is observed. Contrary to ferromagnets, the magnetic bistability of SMMs does not require intermolecular interactions, which makes them particularly interesting in terms of application potential, especially in the high-density storage of data. This paper aims to introduce the readers into a basic understanding of SMM behaviour, and furthermore, it provides an overview of the attractive Co(II) SMMs with emphasis on the relation between structural features, magnetic anisotropy, and slow relaxation of magnetization in tetra-, penta-, and hexacoordinate complexes.

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[Gd5 (L)16 (H2 O)8 ](Tf2 N)15 was obtained from reaction of Gd2 O3 with 1-carboxymethyl-3-ethylimidazolium chloride (LHCl). The material was found to be an ionic liquid that freezes to glassy state on cooling to -30 °C. Variable-temperature magnetic studies reveal the presence of weak magnetic intramolecular interactions in the glass. Isothermal variable-field magnetization demonstrates a magnetocaloric effect (MCE), which is the first finding of such an effect in a molecular glass. This MCE is explainable by an uncoupled representation, with a magnetic entropy change of -11.36 J K-1 kg-1 at 1.8 K for a 0-7 T magnetic field change, and with a refrigerant capacity of 125.9 J kg-1 , in the 1.8-50 K interval.

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Organic-molecular magnets based on a metal-organic framework with chemically tuned electronic and magnetic properties have been attracting tremendous attention due to their promising applications in molecular magnetic sensors, magnetic particle medicines, molecular spintronics, etc. Here, we investigated the magnetic behavior of a heterojunction comprising a ferromagnetic nickel (Ni) film and an organic semiconductor (OSC) 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4-TCNQ) layer. Through the magneto-optical Kerr effect (MOKE), a photoemission electron microscopy (PEEM), X-ray magnetic circular dichroism (XMCD), and X-ray photoelectron spectroscopy (XPS), we found that the adsorption of F4-TCNQ on Cu(100)/Ni not only reverses the in-plane magnetization direction originally exhibited by the Ni layer but also results in enhanced magnetic ordering. Furthermore, the cyano group (CN) in adsorbed F4-TCNQ was found spin-polarized along with conspicuous charge transfer with Ni. The density functional theory (DFT) calculations suggest that the experimentally found spin polarization originates from hybridization between the CN group's π orbitals and Ni's d band. These findings signify that the hybrid states at the organic-ferromagnet interface play a key role in tailoring the magnetic behavior of interfaces. For the case of the F4-TCNQ and Ni heterojunction reported here, interface coupling is an antiferromagnetic one.

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The first X-band EPR spectrum containing only non-overlapping signals of septet pyridyl-2,4,6-trinitrene and triplet pyridylnitrenes is reported. This spectrum was recorded after photolysis of 2,4,6-triazidopyridine in solid argon at 5 K. The zero-field splitting (ZFS) parameters of this trinitrene as well as of intermediate triplet mononitrenes and quintet dinitrenes formed at early stages of the photolysis were determined using the combination of modern computer line-shape spectral simulations and density functional theory (DFT) calculations. It was found that septet pyridyl-2,4,6-trinitrene has the record negative parameter DS = -0.1031 cm-1 among all known to date septet pyridyl-2,4,6-trinitrenes and may be of interest as a model multi-qubit spin system for investigations of quantum computation processing.

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RESUMEN

Host-guest electron transfer (HGET) in molecular framework systems is a critical trigger for drastic functional changes in both host framework and guest. A reversible magnetic phase transition was achieved via HGET in a layered framework, [{Ru2 (2,6-F2 PhCO2 )4 }2 (BTDA-TCNQ)] (1), where 2,6-F2 PhCO2 - and BTDA-TCNQ represent 2,6-difluorobenzoate and bis[1,2,5]dithiazolotetracyanoquinodimethane, respectively. The guest-free 1 with an antiferromagnetic ground state transformed into a paramagnet, [{Ru2 (2,6-F2 PhCO2 )4 }2 (BTDA-TCNQ)]I3 (1-I3 ), by adsorbing iodine (I2 ). The local charge distribution of [{Ru2 II,III }+ -(BTDA-TCNQ).- -{Ru2 II,II }] in 1 was reversibly modified to [{Ru2 II,III }+ -(BTDA-TCNQ)0 -{Ru2 II,II }](I3 - ) in 1-I3 through HGET. Theoretical calculations of 1-I3 indicated a partial charge delocalization as [{Ru2 }(1-δ)+ -(BTDA-TCNQ)0 -{Ru2 }δ+ ](I3 - ) with δ≈0.2, aided by weak ferromagnetic coupling. 1-I3 exhibited a hundred-fold enhancement in electrical conductivity compared to that of 1.

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We present a combined experimental and theoretical study of the ultrafast transient absorption spectroscopy results of a {Ni2 Dy2 }-compound in DMF, which can be considered as a prototypic molecule for single molecule magnets. We apply state-of-the-art ab initio quantum chemistry to quantitatively describe the optical properties of an inorganic complex system comprising ten atoms to form the chromophoric unit, which is further stabilized by surrounding ligands. Two different basis sets are used for the calculations to specifically identify two dominant peaks in the ground state. Furthermore, we theoretically propagate the compound's correlated many-body wavefunction under the influence of a laser pulse as well as relaxation processes and compare against the time-resolved absorption spectra. The experimental data can be described with a time constant of several hundreds of femtoseconds attributed to vibrational relaxation and trapping into states localized within the band gap. A second time constant is ascribed to the excited state while trap states show lifetimes on a longer timescale. The theoretical propagation is performed with the density-matrix formalism and the Lindblad superoperator, which couples the system to a thermal bath, allowing us to extract relaxation times from first principles.

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A series of six seven-coordinate pentagonal-bipyramidal (PBP) erbium complexes, with acyclic pentadentate [N3O2] Schiff-base ligands, 2,6-diacetylpyridine bis-(4-methoxybenzoylhydrazone) [H2DAPMBH], or 2,6-diacethylpyridine bis(salicylhydrazone) [H4DAPS], and various apical ligands in different charge states were synthesized: [Er(DAPMBH)(C2H5OH)Cl] (1); [Er(DAPMBH)(H2O)Cl]·2C2H5OH (2); [Er(DAPMBH)(CH3OH)Cl] (3); [Er(DAPMBH)(CH3OH)(N3)] (4); [(Et3H)N]+[Er(H2DAPS)Cl2]- (5); and [(Et3H)N]+[Y0.95Er0.05(H2DAPS)Cl2]- (6). The physicochemical properties, crystal structures, and the DC and AC magnetic properties of 1-6 were studied. The AC magnetic measurements revealed that most of Compounds 1-6 are field-induced single-molecule magnets, with estimated magnetization energy barriers, Ueff ≈ 16-28 K. The experimental study of the magnetic properties was complemented by theoretical analysis based on ab initio and crystal field calculations. An experimental and theoretical study of the magnetism of 1-6 shows the subtle impact of the type and charge state of the axial ligands on the SMM properties of these complexes.

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We study the magnetic properties of the erbium based compounds, Na9[Er(W5O18)2] and [(Pc)Er{Pc{N(C4H9)2}8}]·/-, in the framework of an effective spin exchange model involving delocalized electrons occupying molecular orbitals. The calculations successfully reproduce the experimental data available in the literature for the magnetic spectrum, magnetization and molar susceptibility in dc and ac fields. Owing to their similar molecular geometry, the compounds' magnetic behaviors are interpreted in terms of the same set of active orbitals and thus the same effective spin coupling scheme. For all three complexes, the model predicts a prompt change in the ground state from a Kramer's doublet at zero fields to a fully polarized quartet one brought about by the action of an external magnetic field without Zeeman splitting. This alteration is attributed to the enhancement of the effect of orbital interactions over the spin exchange as the magnitude of the external magnetic field increases.

RESUMEN

The pentakis dodecahedron, the dual of the truncated icosahedron, consists of 60 edge-sharing triangles. It has 20 six-fold and 12 five-fold coordinated vertices, with the former forming a dodecahedron, and each of the latter connected to the vertices of one of the 12 pentagons of the dodecahedron. When spins mounted on the vertices of the pentakis dodecahedron interact according to the nearest-neighbor antiferromagnetic Heisenberg model, the two different vertex types necessitate the introduction of two exchange constants. As the relative strength of the two constants is varied the molecule interpolates between the dodecahedron and a molecule consisting only of quadrangles. The competition between the two exchange constants, frustration, and an external magnetic field results in a multitude of ground-state magnetization and susceptibility discontinuities. At the classical level the maximum is ten magnetization and one susceptibility discontinuities when the 12 five-fold vertices interact with the dodecahedron spins with approximately one-half the strength of their interaction. When the two interactions are approximately equal in strength the number of discontinuities is also maximized, with three of the magnetization and eight of the susceptibility. At the full quantum limit, where the magnitude of the spins equals12, there can be up to three ground-state magnetization jumps that have thez-component of the total spin changing by ΔSz= 2, even though quantum fluctuations rarely allow discontinuities of the magnetization. The full quantum case also supports a ΔSz= 3 discontinuity. Frustration also results in nonmagnetic states inside the singlet-triplet gap. These results make the pentakis dodecahedron the molecule with the largest number of magnetization and susceptibility discontinuities from the quantum to the classical level, taking its size also into account.

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Over recent years, investigations of coordination polymer thin films have been initiated due to their unique properties, which are expected to be strongly enhanced in the thin film form. In this work, a crystalline [FeII(H2O)2]2[NbIV(CN)8]∙4H2O (1) film on a transparent Nafion membrane was obtained, for the first time, via ion-exchange synthesis. The proper film formation and its composition was confirmed with the use of energy dispersive X-ray spectroscopy and infrared spectroscopy, as well as in situ Ultraviolet-Visible (UV-Vis) spectroscopy. The obtained film were also characterized by scanning electron microscopy, X-ray diffraction, and magnetic measurements. The [FeII(H2O)2]2[NbIV(CN)8]∙4H2O film shows a sharp phase transition to a long-range magnetically ordered state at Tc = 40 K. The 1 film is a soft ferromagnet with the coercive field Hc = 1.2 kOe. Compared to the bulk counterpart, a decrease in critical temperature and a significant increase in the coercive field were observed in the films indicating a distinct size effect. The decrease in Tc could also have been related to the possible partial oxidation of FeII ions to FeIII, which could be efficient, due to the large surface of the thin film sample.

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The electric control of magnetic properties based on magnetoelectric effect is crucial for the development of future data storage devices. Here, based on first-principles calculations, a strong magnetoelectric effect is proposed to effectively switch on/off the magnetic states as well as alter the in-plane/perpendicular easy axes of metal-phthalocyanine molecules (MPc) by reversing the electric polarization of the underlying two-dimensional (2D) ferroelectric α-In2Se3 substrate with the application of an external electric field. The mechanism originates from the different hybridization between the molecule and the ferroelectric substrate in which the different electronic states of surface Se layer play a dominant role. Moreover, the magnetic moments and magnetic anisotropy energies (MAE) of OsPc/In2Se3 can be further largely enhanced by a functionalized atom atop the OsPc molecule. The I-OsPc/In2Se3 system possesses large MAE up to 30 meV at both polarization directions, which is sufficient for room-temperature applications. These findings provide a feasible scheme to realize ferroelectric control of magnetic states in 2D limit, which have great potential for applications in nanoscale electronics and spintronics.

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We investigate the energetics and magnetic signatures of the parent molecular magnet Mn12 -Acetate [Mn12 O12 (COOR)16 (H2 O)4 ] and a chemically decomposed version of this structure, in which the four water molecules are converted to hydroxyl groups and hydrogen molecules. We determine electron addition and water decomposition energetics for this water-containing molecule using density-functional methods and include the recent Fermi-Löwdin-Orbital self-interaction correction. We find that it only costs 0.32 eV to add four electrons to the parent molecule. Furthermore, due to the strong Coulomb attractions between hydroxyl anions and the Mn cations, the energy cost for breaking the four coordinating water molecules into four coordinating hydroxyls and two hydrogen molecules is decreased in the tetra-anionic structure relative to the neutral structure. We calculate magnetic anisotropy barriers for the neutral molecule and the dehydrogenated tetra-anion and show that large changes in the magnetic anisotropy arise the strong attraction between the hydroxyl anions and four of the crown Mn cations. We suggest that the large changes in magnetic signals associated with the [Mn12 O12 (COOR)16 (HOH)4 ] to [Mn12 O12 (COOR)16 (OH- )4 + 2H2 ] decomposition could provide a nondestructive spectroscopic method for learning about water decomposition mechanisms in a class of realizable model catalytic systems that have been synthesized recently. © 2019 Wiley Periodicals, Inc.

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By using paramagnetic [Fe(CN)6 ]3- anions in place of diamagnetic [Co(CN)6 ]3- anions, two field-induced mononuclear single-molecular magnets, [Nd(18-crown-6)(H2 O)4 ][Co(CN)6 ]⋅2 H2 O (1) and [Nd(18-crown-6)(H2 O)4 ][Fe(CN)6 ]⋅2 H2 O (2), have been synthesized and characterized. Single-crystal X-ray diffraction analysis revealed that compounds 1 and 2 were ionic complexes. The NdIII ions were located inside the cavities of the 18-crown-6 ligands and were each bound by four water molecules on either side of the crown ether. Magnetic investigations showed that these compounds were both field-induced single-molecular magnets. By comparing the slow relaxation behaviors of compounds 1 and 2, we found significant differences between the direct and Raman processes for these two complexes, with a stronger direct process in compound 2 at low temperatures. Complete active space self-consistent field (CASSCF) calculations were also performed on two [Nd(18-crown-6)(H2 O)4 ]3+ fragments of compounds 1 and 2. Ab initio calculations showed that the magnetic anisotropies of the NdIII centers in complexes 1 and 2 were similar to each other, which indicated that the difference in relaxation behavior was not owing to the magnetic anisotropy of NdIII . Our analysis showed that the magnetic interaction between the NdIII ion and the low-spin FeIII ion in complex 2 played an important role in enhancing the direct process and suppressing the Raman process of the single-molecular magnet.

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Molecular magnets are demonstrated to provide a promising way to realize nanometer-scale structures with a stable spin orientation. Herein, first a description of conventional molecular magnets coupled with sp2 carbon materials, such as carbon nanotubes and graphenes, is given. Then, progress on ferromagnetism in sp2 carbon nanomaterials due to the existence of defects or topological structures as the spin units, which makes the sp2 materials themselves act as a novel class of molecular magnets, is reviewed, and a scheme of controllable synthesis of the molecular magnets at the sheared ends of carbon nanotubes is proposed. To conclude, remarks on some challenges and perspectives in the synthesis of carbon nanotube arrays with orderly sheared ends as integrated molecular magnets are provided.