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.

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.

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 obtained by oxidative cyclization (2) 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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

Lanthanoid Complexes as Molecular Materials: The Redox Approach.

The development of molecular materials with novel functionality offers promise for technological innovation. Switchable molecules that incorporate redox-active components are enticing candidate compounds due to their potential for electronic manipulation. Lanthanoid metals are most prevalent in their trivalent state and usually redox-activity in lanthanoid complexes is restricted to the ligand. The unique electronic and physical properties of lanthanoid ions have been exploited for various applications, including in magnetic and luminescent materials as well as in catalysis. Lanthanoid complexes are also promising for applications reliant on switchability, where the physical properties can be modulated by varying the oxidation state of a coordinated ligand. Lanthanoid-based redox activity is also possible, encompassing both divalent and tetravalent metal oxidation states. Thus, utilization of redox-active lanthanoid metals offers an attractive opportunity to further expand the capabilities of molecular materials. This review surveys both ligand and lanthanoid centered redox-activity in pre-existing molecular systems, including tuning of lanthanoid magnetic and photophysical properties by modulating the redox states of coordinated ligands. Ultimately the combination of redox-activity at both ligands and metal centers in the same molecule can afford novel electronic structures and physical properties, including multiconfigurational electronic states and valence tautomerism. Further targeted exploration of these features is clearly warranted, both to enhance understanding of the underlying fundamental chemistry, and for the generation of a potentially important new class of molecular material.

From the {FeIII 2 Ln2 } Butterfly's Perspective: the Magnetic Benefits and Challenges of Cooperativity within 3 d-4 f Based Coordination Clusters.

In this Review we discuss the tuning handles which can be used to steer the magnetic properties of FeIII -4 f "butterfly" compounds. The majority of presented compounds were produced in the context of project A3 "Di- to tetranuclear compounds incorporating highly anisotropic paramagnetic metal ions" within the SFB/TRR88 "3MET". These contain {FeIII 2 Ln2 } cores encapsulated in ligand shells which are easy to tune in a "test-bed" system. We identify the following advantages and variables in such systems: (i) the complexes are structurally simple usually with one crystallographically independent FeIII and LnIII , respectively. This simplifies theory and anaylsis; (ii) choosing Fe allows 57 Fe Mössbauer spectroscopy to be used as an additional technique which can give information about oxidation levels and spin states, local moments at the iron nuclei and spin-relaxation and, more importantly, about the anisotropy not only of the studied isotope, but also of elements interacting with this isotope; (iii) isostructural analogues with all the available (i. e. not Pm) 4 f ions can be synthesised, enabling a systematic survey of the influence of the 4 f ion on the electronic structure; (iv) this cluster type is obtained by reacting [FeIII 3 O(O2 CR)6 (L)3 ](X) (X=anion, L=solvent such as H2 O, py) with an ethanolamine-based ligand L' and lanthanide salts. This allows to study analogues of [FeIII 2 Ln2 (µ3 -OH)2 (L')2 (O2 CR)6 ] using the appropriate iron trinuclear starting materials. (v) the organic main ligand can be readily functionalised, facilitating a systematic investigation of the effect of organic substituents on the ligands on the magnetic properties of the complexes. We describe and discuss 34 {MIII 2 Ln2 } (M=Fe or in one case Al) butterfly compounds which have been reported up to 2020. The analysis of these gives perspectives for designing new SMM systems with specific electronic and magnetic signatures.

Enhancing Magnetic Communication between Metal Centres: The Role of s-Tetrazine Based Radicals as Ligands.

Although 1,2,4,5-tetrazines or s-tetrazines have been known in the literature for more than a century, their coordination chemistry has become increasingly popular in recent years due to their unique redox activity, multiple binding sites and their various applications. The electron-poor character of the ring and stabilization of the radical anion through all four nitrogen atoms in their metal complexes provide new aspects in molecular magnetism towards the synthesis of new high performing Single Molecule Magnets (SMMs). The scope of this review is to examine the role of s-tetrazine radical ligands in transition metal and lanthanide based SMMs and provide a critical overview of the progress thus far in this field. As well, general synthetic routes and new insights for the preparation of s-tetrazines are discussed, along with their redox activity and applications in various fields. Concluding remarks along with the limitations and perspectives of these ligands are discussed.

[CrIII8NiII6]n+ Heterometallic Coordination Cubes.

Three new heterometallic [CrIII8NiII6] coordination cubes of formulae [CrIII8NiII6L24(H2O)12](NO3)12 (1), [CrIII8NiII6L24(MeCN)7(H2O)5](ClO4)12 (2), and [CrIII8NiII6L24Cl12] (3) (where HL = 1-(4-pyridyl)butane-1,3-dione), were synthesised using the paramagnetic metalloligand [CrIIIL3] and the corresponding NiII salt. The magnetic skeleton of each capsule describes a face-centred cube in which the eight CrIII and six NiII ions occupy the eight vertices and six faces of the structure, respectively. Direct current magnetic susceptibility measurements on (1) reveal weak ferromagnetic interactions between the CrIII and NiII ions, with JCr-Ni = + 0.045 cm-1. EPR spectra are consistent with weak exchange, being dominated by the zero-field splitting of the CrIII ions. Excluding wheel-like structures, examples of large heterometallic clusters containing both CrIII and NiII ions are rather rare, and we demonstrate that the use of metalloligands with predictable bonding modes allows for a modular approach to building families of related polymetallic complexes. Compounds (1)-(3) join the previously published, structurally related family of [MIII8MII6] cubes, where MIII = Cr, Fe and MII = Cu, Co, Mn, Pd.