Triindenotriphenylenes: Spin-Frustrated Triskelion Triradicals with Excellent Ambient Stability.

A triskelion-shaped triradical triindeno[1,2-a:1',2'-g : 1'',2''-m]triphenylen-7-yl (1) and its internally fused derivative (2) obtained by oxidative cyclization were prepared in a straightforward synthetic sequence. Both compounds were confirmed to be triradicals and to possess intramolecular antiferromagnetic exchange interactions between spins, displaying a spin-frustrated doublet ground state with doublet-quartet energy gaps of -0.14 kcal/mol for 1 and -0.06 kcal/mol for 2. Despite their open-shell character, they were sufficiently stable to be handled under ambient conditions on a timescale of days. Both compounds could be reversibly reduced to mono-, di-, and trianions and oxidized to 1+ and 22+, with strong NIR absorptions (1800 to over 3200 nm) observed for all open-shell ions.

Phase Transition Control in Molecular Solids via Complementarity of Hydrogen-Bond Strength.

Phase transitions in molecular solids involve synergistic changes in chemical and electronic structures, leading to diversification in physical and chemical properties. Despite the pivotal role of hydrogen bonds (H-bonds) in many phase-transition materials, it is rare and challenging to chemically regulate the dynamics and to elucidate the structure-property relationship. Here, four high-spin CoII compounds were isolated and systematically investigated by modifying the ligand terminal groups (X=S, Se) and substituents (Y=Cl, Br). S-Cl and Se-Br undergo a reversible structural phase transition near room temperature, triggering the rotation of 15-crown-5 guests and the swing between syn- and anti-conformation of NCX- ligands, accompanied by switchable magnetism. Conversely, S-Br and Se-Cl retain stability in ordered and disordered phases, respectively. H-bonds geometric analysis and ab initio calculations reveal that the electronegativity of X and Y affects the strength of NY-ap-H⋅⋅⋅X interactions. Entropy-driven structural phase transitions occur when the H-bond strength is appropriate; otherwise, the phase stays unchanged if it is too strong or weak. This work highlights a phase transition driven by H-bond strength complementarity - pairing strong acceptor with weak donor and vice versa, which offers a straightforward and effective approach for designing phase-transition molecular solids from a chemical perspective.

Field-Induced Slow Magnetization Relaxation of a Tetrahedral S=2 FeIIS4-Containing Complex.

In the work described herein, the spin relaxation properties of the mononuclear tetrahedral S=2 [Fe{(SPiPr2)2N}2] complex (1) were studied by employing static and dynamic magnetic measurements at liquid helium temperatures. In the absence of an external direct current (DC) magnetic field, 1 exhibits fast magnetization relaxation. However, in the presence of external magnetic fields of a few kOe, slow relaxation is induced as monitored by alternating current (AC) magnetic susceptibility measurements up to 10 kHz, in the temperature range 2-5 K. Analysis of the temperature dependence of the corresponding relaxation time reveals contributions by Quantum Tunnelling of Magnetization, and the Direct and Orbach processes in the magnetization relaxation mechanism of 1. The energy barrier, Ueff, of the Orbach process, as determined by this analysis, is compared with that related to the zero-field splitting parameters of 1 which were previously determined by high- frequency and -field electron paramagnetic resonance and Mössbauer spectroscopies.

Quantum Mimicry With Inorganic Chemistry.

Quantum objects, such as atoms, spins, and subatomic particles, have important properties due to their unique physical properties that could be useful for many different applications, ranging from quantum information processing to magnetic resonance imaging. Molecular species also exhibit quantum properties, and these properties are fundamentally tunable by synthetic design, unlike ions isolated in a quadrupolar trap, for example. In this comment, we collect multiple, distinct, scientific efforts into an emergent field that is devoted to designing molecules that mimic the quantum properties of objects like trapped atoms or defects in solids. Mimicry is endemic in inorganic chemistry and featured heavily in the research interests of groups across the world. We describe a new field of using inorganic chemistry to design molecules that mimic the quantum properties (e.g. the lifetime of spin superpositions, or the resonant frequencies thereof) of other quantum objects, "quantum mimicry." In this comment, we describe the philosophical design strategies and recent exciting results from application of these strategies.

Understanding the Electronic Structure of Magnetic Trinuclear Complexes Based on the Tris-Dioxolene Triphenylene Non-Innocent Bridging Ligand, a Theoretical Study.

A complete theoretical analysis using first the simple Hückel model followed by more sophisticated multi-reference calculations on a trinuclear Ni(II) complex (Tp#Ni3 HHTP), bearing the non-innocent bridging ligand HHTP3- , is carried out. The three semiquinone moieties of HHTP3- couple antiferromagnetically and lead to a single unpaired electron localized on one of the moieties. The calculated exchange coupling integrals together with the zero-field parameters allow, when varied within a certain range, reproducing the experimental data. These results are generalized for two similar other trinuclear complexes containing Ni(II) and Cu(II). The electronic structure of HHTP3- turns out to be independent of both the chemical nature and the geometry of the metal ions. We also establish a direct correlation between the geometrical and the electronic structures of the non-innocent ligand that is consistent with the results of calculations. It allows experimentalists to get insight into the magnetic behavior of this type of complexes by an analysis of their X-ray structure.

Magnetic Relaxations of Chromium Nitride Porphyrinato Complexes Driven by the Anisotropic g-Factor.

Molecule-based magnetic materials are useful candidates as the spin qubit due to their long coherence time and high designability. The anisotropy of the g-values of the metal complexes can be utilized to access the individual spin of the metal complexes, making it possible to achieve the scalable molecular spin qubit. For this goal, it is important to evaluate the effect of g-value anisotropy on the magnetic relaxation behaviour. This study reports the slow magnetic relaxation behaviour of chromium nitride (CrN2+ ) porphyrinato complex (1), which is structurally and magnetically similar with the vanadyl (VO2+ ) porphyrinato complex (2) which is known as the excellent spin qubit. Detailed analyses for vibrational and dynamical magnetism of 1 and 2 revealed that g-value anisotropy accelerates magnetic relaxations greater than the internal magnetic field from nuclear spin does. These results provide a design criterion for construction of multiple spin qubit based on g-tensor engineering.

Observation of High Magnetic Bistability in Lanthanide (Ln = Gd, Tb and Dy)-Grafted Carbon Nanotube Hybrid Molecular System.

There is an immense research interest in molecular hybrid materials posing novel magnetic properties for usage in spintronic devices and quantum technological applications. Although grafting magnetic molecules onto carbon nanotubes (CNTs) is nontrivial, there is a need to explore their single molecule magnetic (SMM) properties post-grafting to a greater degree. Here, we report a one-step chemical approach for lanthanide-EDTA (Ln = GdIII, 1; TbIII, 2 and DyIII, 3) chelate synthesis and their effective grafting onto MWCNT surfaces with high magnetic bistability retention. The magnetic anisotropy of an Ln-CNT hybrid molecular system by replacing the central ions in the hybrid complex was studied and it was found that system 1 exhibited a magnetization reversal from positive to negative values at 70 K with quasi-anti-ferromagnetic ordering, 2 showed diamagnetism to quasi-ferromagnetism and 3 displayed anti-ferromagnetic ordering as the temperature was lowered at an applied field of 200 Oe. A further analysis of magnetization (M) vs. field (H) revealed 1 displaying superparamagnetic behavior, and 2 and 3 displaying smooth hysteresis loops with zero-field slow magnetic relaxation. The present work highlights the importance of the selection of lanthanide ions in designing SMM-CNT hybrid molecular systems with multi-functionalities for building spin valves, molecular transistors, switches, etc.

Slow Magnetic Relaxation and Modulated Photoluminescent Emission of Coordination Polymer Based on 3-Amino-4-hydroxybenzoate Zn and Co Metal Ions.

As a starting point, a new 3D porous framework with the {[CoL]·0.5DMF·H2O}n chemical formula (where L = 3-amino-4-hydroxybenzoate) is described. Its performance as a single molecule magnet was explored. The study of magnetic properties reveals that Co-MOF shows no frequency-fdependant alternating current (ac) signals under zero direct current (dc) magnetic field, whereas single-molecule magnet behaviour is achieved when CoII ions are diluted in a ZnII based matrix. Interestingly, this strategy renders a bifunctional [CoxZn1-xL]n material that is also characterized by a strong photoluminescent emitting capacity.

Observation of Exchange Interaction in Iron(II) Spin Crossover Molecules in Contact with Passivated Ferromagnetic Surface of Co/Au(111).

Spin crossover (SCO) complexes sensitively react on changes of the environment by a change in the spin of the central metallic ion making them ideal candidates for molecular spintronics. In particular, the composite of SCO complexes and ferromagnetic (FM) surfaces would allow spin-state switching of the molecules in combination with the magnetic exchange interaction to the magnetic substrate. Unfortunately, when depositing SCO complexes on ferromagnetic surfaces, spin-state switching is blocked by the relatively strong interaction between the adsorbed molecules and the surface. Here, the Fe(II) SCO complex [FeII (Pyrz)2 ] (Pyrz = 3,5-dimethylpyrazolylborate) with sub-monolayer thickness in contact with a passivated FM film of Co on Au(111) is studied. In this case, the molecules preserve thermal spin crossover and at the same time the high-spin species show a sizable exchange interaction of > 0.9 T with the FM Co substrate. These observations provide a feasible design strategy in fabricating SCO-FM hybrid devices.

Control of Molecular Orbital Ordering Using a van der Waals Monolayer Ferroelectric.

2D ferroelectric materials provide a promising platform for the electrical control of quantum states. In particular, due to their 2D nature, they are suitable for influencing the quantum states of deposited molecules via the proximity effect. Here, electrically controllable molecular states in phthalocyanine molecules adsorbed on monolayer ferroelectric material SnTe are reported. The strain and ferroelectric order in SnTe are found to create a transition between two distinct orbital orders in the adsorbed phthalocyanine molecules. By controlling the polarization of the ferroelectric domain using scanning tunneling microscopy (STM), it is successfully demonstrated that orbital order can be manipulated electrically. The results show how ferroelastic coupling in 2D systems allows for control of molecular states, providing a starting point for ferroelectrically switchable molecular orbital ordering and ultimately, electrical control of molecular magnetism.

Magneto-Structural Correlations in a Mixed Porphyrin(Cu2+ )/Trityl Spin System: Magnitude, Sign, and Distribution of the Exchange Coupling Constant.

Tetrathiatriarylmethyl radicals (TAM or trityl) are receiving increasing attention in various fields of magnetic resonance such as imaging, dynamic nuclear polarization, spin labeling, and, more recently, molecular magnetism and quantum information technology. Here, a trityl radical attached via a phenyl bridge to a copper(II)tetraphenylporphyrin was synthesized, and its magnetic properties studied by multi-frequency continuous-wave electron paramagnetic resonance (EPR) spectroscopy and magnetic measurements. EPR revealed that the electron spin-spin coupling constant J between the trityl and Cu2+ spin centers is ferromagnetic with a magnitude of -2.3 GHz (-0.077 cm-1 , + J S → 1 S → 2 ${+J{\vec{S}}_{1}{\vec{S}}_{2}}$ convention) and a distribution width of 1.2 GHz (0.040 cm-1 ). With the help of density functional theory (DFT) calculations, the obtained ferromagnetic exchange coupling, which is unusual for para-substituted phenyl-bridged biradicals, could be related to the almost perpendicular orientation of the phenyl linker with respect to the porphyrin and trityl ring planes in the energy minimum, while the J distribution was rationalized by the temperature weighted rotation of the phenyl bridge about the molecular axis connecting both spin centers. This study exemplifies the importance of molecular dynamics for the homogeneity (or heterogeneity) of the magnetic properties of trityl-based systems.

Emergence of Spinmerism for Molecular Spin-Qubits Generation.

Molecular platforms are regarded as promising candidates in the generation of units of information for quantum computing. Herein, a strategy combining spin-crossover metal ions and radical ligands is proposed from a model Hamiltonian first restricted to exchange interactions. Unusual spin states structures emerge from the linkage of a singlet/triplet commutable metal centre with two doublet-radical ligands. The ground state nature is modulated by charge transfers and can exhibit a mixture of triplet and singlet local metal spin states. Besides, the superposition reaches a maximum for 2 K M = K 1 + K 2 ${2{K}_{M}={K}_{1}+{K}_{2}}$ , suggesting a necessary competition between the intramolecular K M ${{K}_{M}}$ and inter-metal-ligand K 1 ${{K}_{1}}$ and K 2 ${{K}_{2}}$ direct exchange interactions. The results promote spinmerism, an original manifestation of quantum entanglement between the spin states of a metal centre and radical ligands. The study provides insights into spin-coupled compounds and inspiration for the development of molecular spin-qubits.

Nanostructures as the Substrate for Single-Molecule Magnet Deposition.

Anchoringsingle-molecule magnets (SMMs) on the surface of nanostructures is gaining particular interest in the field of molecular magnetism. The accurate organization of SMMs on low-dimensional substrates enables controlled interactions and the possibility of individual molecules' manipulation, paving the route for a broad range of nanotechnological applications. In this comprehensive review article, the most studied types of SMMs are presented, and the quantum-mechanical origin of their magnetic behavior is described. The nanostructured matrices were grouped and characterized to outline to the reader their relevance for subsequent compounding with SMMs. Particular attention was paid to the fact that this process must be carried out in such a way as to preserve the initial functionality and properties of the molecules. Therefore, the work also includes a discussion of issues concerning both the methods of synthesis of the systems in question as well as advanced measurement techniques of the resulting complexes. A great deal of attention was also focused on the issue of surface-molecule interaction, which can affect the magnetic properties of SMMs, causing molecular crystal field distortion or magnetic anisotropy modification, which affects quantum tunneling or magnetic hysteresis, respectively. In our opinion, the analysis of the literature carried out in this way will greatly help the reader to design SMM-nanostructure systems.

Structure and Properties of Heterometallics Based on Lanthanides and Transition Metals with Methoxy-ß-Diketonates.

The possibility of obtaining volatile polynuclear heterometallic complexes containing lanthanides and transition metals bound by methoxy-ß-diketonates was studied. New compounds were prepared by cocrystallization of monometallic complexes from organic solvents. Ln(tmhd)3 were used as initial monometallic complexes (Ln = La, Pr, Sm, Gd, Tb, Dy, Lu; tmhd = 2,2,6,6-tetramethylheptane-3,5-dionate) in combination with TML2 in various ratios (TM = Cu, Co, Ni, Mn; L: L1 = 1,1,1-trifluoro-5,5-dimethoxypentane-2,4-dionate, L2 = 1,1,1-trifluoro-5,5-dimethoxy-hexane-2,4-dionate, L3 = 1,1,1-trifluoro-5-methoxy-5-methylhexane-2,4-dionate). Heterometallic complexes of the composition [(LnL2tmhd)2TM(tmhd)2] were isolated for light lanthanides Ln= La, Pr, Sm, Gd, and L= L1 or L2. By single crystal XRD, it has been established that heterometallic compounds containing La, Pr, Cu, Co, and Ni are isostructural linear coordination polymers of alternating mononuclear transition metal complexes and binuclear heteroleptic lanthanide complexes, connected by donor-acceptor interactions between oxygen atoms of the methoxy groups and transition metal atoms. A comparison of powder XRD patterns has shown that all heterometallic complexes obtained are isostructural. Havier lanthanides Ln = Tb, Dy, Lu did not form heterometallics. Instead, homometallic complexes Ln(L3)3 were identified for Ln = Dy, Lu as well as for Ln = La. The thermal properties of the complexes were investigated by TG-DTA and vacuum sublimation tests. The heterometallic complexes were found to be not volatile and decomposed under heating to produce inorganic composites of TM oxides and Ln fluorides. In contrast, Ln(L3)3 is volatile and may be sublimed in a vacuum. Results of magnetic measurements are discussed for several heterometallic and homometallic complexes.

Modelling Conformational Flexibility in a Spectrally Addressable Molecular Multi-Qubit Model System.

Dipolar coupled multi-spin systems have the potential to be used as molecular qubits. Herein we report the synthesis of a molecular multi-qubit model system with three individually addressable, weakly interacting, spin 1 / 2 ${{ 1/2 }}$ centres of differing g-values. We use pulsed Electron Paramagnetic Resonance (EPR) techniques to characterise and separately address the individual electron spin qubits; CuII , Cr7 Ni ring and a nitroxide, to determine the strength of the inter-qubit dipolar interaction. Orientation selective Relaxation-Induced Dipolar Modulation Enhancement (os-RIDME) detecting across the CuII spectrum revealed a strongly correlated CuII -Cr7 Ni ring relationship; detecting on the nitroxide resonance measured both the nitroxide and CuII or nitroxide and Cr7 Ni ring correlations, with switchability of the interaction based on differing relaxation dynamics, indicating a handle for implementing EPR-based quantum information processing (QIP) algorithms.

Influence of the Coordinated Transition Metal Ion on Magnetic Relaxation of Lanthanide Based Complexes with Imino Nitroxide Biradical Ligands.

In spite of achievement of a lot of Ln-radical SMMs, how to improve magnetic behavior of Ln-radical system remains challenging. Here, two series of Ln-radical complexes have successfully been built using an imino nitroxide biradical, namely, [Ln2 (hfac)6 (ImPhPyobis)2 ] (LnIII =Gd 1, Tb 2, Dy 3) and [Ln2 Cu2 (hfac)10 (ImPhPyobis)2 ] (LnIII =Gd 4, Dy 5; hfac=hexafluoroacetylacetonate and ImPhPyobis=5-(4-oxypyridinium-1-yl)-1,3-bis(1'-oxyl-4',4',5',5'-tetramethyl-4,5-hydro-1H-imidazol-2-yl)benzene). For these biradical-metal complexes, two imino nitroxide biradicals bind two Ln(III) ions via their oxygen atoms coming from 4-oxypyridinium units to produce a binuclear {Ln2 O2 } unit. Those imino nitroxide groups are free for complexes 1-3, however one of imino nitroxide groups of the biradical is ligated to the copper(II) ion for complexes 4 and 5. The distinct magnetic relaxation behaviors are observed for two Dy derivatives, as revealed by ac magnetic studies: complex 3 presents one magnetic process with the effective energy barrier(Ueff ) of 74.0 K while complex 5 exhibits dual relaxation processes with Ueff values for the fast- and slow-relaxation being 20.2 K and 30.9 K, respectively, which implies that the second coordination sphere of Dy ion plays a critical role for magnetic relaxation.

Benzenetriimide-Based Molecular Conductor with Antiferro- to Ferromagnetic Switching Induced by Structural Change of π-stacked Array.

Benzenetriimide (BTI) is a promising building block for materials chemistry due to its characteristic 3-fold symmetry and redox properties, whereas little is known about its conductive and magnetic properties. In this study, we synthesized three charge-transfer complexes based on N,N',N''-trimethylbenzenetriimide (BTI-Me). One of the complexes contains isolated dimers of BTI-Me radical anion (BTI-Me⋅- ), while the other two have the infinite π-stacked array of BTI-Me with the formal charge of -0.5. The latter two complexes did not show metallic behavior but showed semiconducting behavior probably due to the characteristic insulation in one-dimensional electron system, so-called charge ordering and dimer-Mott insulation. The magnetic susceptibility of the complex in dimer-Mott state exhibits an unusual transition from antiferromagnetic to ferromagnetic spin states with the hysteresis loop of 15 K derived from the structural phase transition around 130 K. These properties were also supported by DFT calculations.

Synthesis, Crystal Structure and Magnetic Properties of a Trinuclear Copper(II) Complex Based on P-Cresol-Substituted Bis(α-Nitronyl Nitroxide) Biradical.

Trinuclear copper(II) complex [CuII3(NIT2PhO)2Cl4] was synthesized with p-cresol-substituted bis(α-nitronyl nitroxide) biradical: 4-methyl-2,6-bis(1-oxyl-3-oxido-4,4,5,5-tetramethyl-2-imidazolin-2-yl)phenol (NIT2PhOH). The crystal structure of this heterospin complex was determined using single-crystal X-ray diffraction analysis and exhibits four unusual seven-membered metallocycles formed from the coordination of oxygen atoms of the N-O groups and of bridging phenoxo (µ-PhO-) moieties with copper(II) ions. The crystal structure analysis reveals an incipient agostic interaction between a square planar copper center and a hydrogen-carbon bond from one methyl group carried on the coordinated nitronyl-nitroxide radical. The intramolecular Cu∙∙∙H-C interaction involves a six-membered metallocycle and may stabilize the copper center in square planar coordination mode. From the magnetic susceptibility measurements, the complex, which totals seven S = 1/2 spin carriers, has almost a ground state spin S = 1/2 at room temperature ascribed to strong antiferromagnetic interaction between the nitronyl nitroxide moieties and the copper(II) centers and in between the copper(II) centers through the bridging phenoxo oxygen atom.

Magnetic Interplay between π-Electrons of Open-Shell Porphyrins and d-Electrons of Their Central Transition Metal Ions.

Magnetism is typically associated with d- or f-block elements, but can also appear in organic molecules with unpaired π-electrons. This has considerably boosted the interest in such organic materials with large potential for spintronics and quantum applications. While several materials showing either d/f or π-electron magnetism have been synthesized, the combination of both features within the same structure has only scarcely been reported. Open-shell porphyrins (Pors) incorporating d-block transition metal ions represent an ideal platform for the realization of such architectures. Herein, the preparation of a series of open-shell, π-extended Pors that contain magnetically active metal ions (i.e., CuII , CoII , and FeII ) through a combination of in-solution and on-surface synthesis is reported. A detailed study of the magnetic interplay between π- and d-electrons in these metalloPors has been performed by scanning probe methods and density functional theory calculations. For the Cu and FePors, ferromagnetically coupled π-electrons are determined to be delocalized over the Por edges. For the CoPor, the authors find a Kondo resonance resulting from the singly occupied CoII dz 2 orbital to dominate the magnetic fingerprint. The Fe derivative exhibits the highest magnetization of 3.67 µB (S≈2) and an exchange coupling of 16 meV between the π-electrons and the Fe d-states.

Combining Open-Shell Verdazyl Environment and Co(II) Spin-Crossover: Spinmerism in Cobalt Oxoverdazyl Compound.

The spin states of a Co(II) oxoverdazyl compound are investigated by means of wavefunction-based calculations. Within a ca. 233 K energy window, the ground state and excited states display a structure-sensitive admixture of low-spin SM =1/2 in a dominant high-spin SM =3/2 Co(II) ion as indicated by the localized molecular orbitals. The puzzling spin zoology that results from the coupling between open-shell radical ligands and a spin-crossover metal ion gives rise to this unusual scenario, which extends the views in molecular magnetism. In agreement with experimental observation, the low-energy spectroscopy is very sensitive to deformations of the coordination sphere, and a growing admixture of Co(II) low-spin is evidenced from the calculations. In analogy with mesomerism that accounts for charge delocalization, entanglement combines different local spin states to generate a given total spin multiplicity, a spinmerism phenomenon.