Reduction of hexaazatrinaphthylenes by divalent lanthanocenes leads to ligand-based multiconfigurational properties.

Reduction of hexaazatrinaphthylene (HAN) and its hexamethyl derivative with [Cp*2Sm(THF)2] or [Cp*2Yb(OEt2)] produces [(Cp*2Ln)3(R6HAN)] (Ln = Sm, Yb; R = H, Me), where the heterocyclic ligand forms as a trianion. The magnetism and electronic structure of these compounds reflect unusual multiconfigurational character within the reduced ligand but not the lanthanide ions.

Bimetallic Synergy Enables Silole Insertion into THF and the Synthesis of Erbium Single-Molecule Magnets.

The potassium silole K2 [SiC4 -2,5-(SiMe3 )2 -3,4-Ph2 ] reacts with [M(η8 -COT)(THF)4 ][BPh4 ] (M=Er, Y; COT=cyclo-octatetraenyl) in THF to give products that feature unprecedented insertion of the nucleophilic silicon centre into a carbon-oxygen bond of THF. The structure of the major product, [(µ-η8 : η8 -COT)M(µ-L1 )K]∞ (1M ), consists of polymeric chains of sandwich complexes, where the spiro-bicyclic silapyran ligand [C4 H8 OSiC4 (SiMe3 )2 Ph2 ]2- (L1 ) coordinates to potassium via the oxygen. The minor product [(µ-η8 : η8 -COT)M(µ-L1 )K(THF)]2 (2M ) features coordination of the silapyran to the rare-earth metal. In forming 1M and 2M , silole insertion into THF only occurs in the presence of potassium and the rare-earth metal, highlighting the importance of bimetallic synergy. The lower nucleophilicity of germanium(II) leads to contrasting reactivity of the potassium germole K2 [GeC4 -2,5-(SiMe3 )2 -3,4-Me2 ] towards [M(η8 -COT)(THF)4 ][BPh4 ], with intact transfer of the germole occurring to give the coordination polymers [{η5 -GeC4 (SiMe3 )2 Me2 }M(η8 -COT)K]∞ (3M ). Despite the differences in reactivity induced by the group 14 heteroatom, the single-molecule magnet properties of 1Er , 2Er and 3Er are similar, with thermally activated relaxation occurring via the first-excited Kramers doublet, subject to effective energy barriers of 122, 80 and 91 cm-1 , respectively. Compound 1Er is also analysed by high-frequency dynamic magnetic susceptibility measurements up to 106  Hz.

Triply Bonded Pancake π-Dimers Stabilized by Tetravalent Actinides.

Aromatic π-stacking is a weakly attractive, noncovalent interaction often found in biological macromolecules and synthetic supramolecular chemistry. The weak nondirectional nature of π-stacking can present challenges in the design of materials owing to their weak, nondirectional nature. However, when aromatic π-systems contain an unpaired electron, stronger attraction involving face-to-face π-orbital overlap is possible, resulting in covalent so-called "pancake" bonds. Two-electron, multicenter single pancake bonds are well known, whereas four-electron double pancake bonds are rare. Higher-order pancake bonds have been predicted, but experimental systems are unknown. Here, we show that six-electron triple pancake bonds can be synthesized by a 3-fold reduction of hexaazatrinaphthylene (HAN) and subsequent stacking of the [HAN]3- triradicals. Our analysis reveals a multicenter covalent triple pancake bond consisting of a σ-orbital and two equivalent π-orbitals. An electrostatic stabilizing role is established for the tetravalent thorium and uranium ions in these systems. We also show that the electronic absorption spectrum of the triple pancake bonds closely matches computational predictions, providing experimental verification of these unique interactions. The discovery of conductivity in thin films of triply bonded π-dimers presents new opportunities for the discovery of single-component molecular conductors and other spin-based molecular materials.

Targeted Synthesis of End-On Dinitrogen-Bridged Lanthanide Metallocenes and Their Reactivity as Divalent Synthons.

High-yield syntheses of the lanthanide dinitrogen complexes [(Cp2tttM)2(µ-1,2-N2)] (1M, M = Gd, Tb, Dy; Cpttt = 1,2,4-C5tBu3H2), in which the [N2]2- ligands solely adopt the rare end-on or 1,2-bridging mode, are reported. The bulk of the tert-butyl substituents and the smaller radii of gadolinium, terbium, and dysprosium preclude formation of the side-on dinitrogen bonding mode on steric grounds. Elongation of the nitrogen-nitrogen bond relative to N2 is observed in 1M, and their Raman spectra show a major absorption consistent with N═N double bonds. Computational analysis of 1Gd identifies that the local symmetry of the metallocene units lifts the degeneracy of two 5dπ orbitals, leading to differing overlap with the π* orbitals of [N2]2-, a consequence of which is that the dinitrogen ligand occupies a singlet ground state. Magnetic measurements reveal antiferromagnetic exchange in 1M and single-molecule magnet (SMM) behavior in 1Dy. Ab initio calculations show that the magnetic easy axis in the ground doublets of 1Tb and 1Dy align with the {M-N═N-M} connectivity, in contrast to the usual scenario in dysprosium metallocene SMMs, where the axis passes through the cyclopentadienyl ligands. The [N2]2- ligands in 1M allow these compounds to be regarded as two-electron reducing agents, serving as synthons for divalent gadolinium, terbium, and dysprosium. Proof of principle for this concept is obtained in the reactions of 1M with 2,2'-bipyridyl (bipy) to give [Cp2tttM(κ2-bipy)] (2M, M = Gd, Tb, Dy), in which the lanthanide is ligated by a bipy radical anion, with strong metal-ligand direct exchange coupling.

Syntheses and Characterization of Main Group, Transition Metal, Lanthanide, and Actinide Complexes of Bidentate Acylpyrazolone Ligands.

The synthesis of acylpyrazolone salts and their complexes of main group elements, transition metals, lanthanides, and actinides are described and characterized inter alia by means of single-crystal X-ray crystallography, NMR, and IR spectroscopies. The complexes consist of two, three, or four acylprazolone ligands bound to the metal atom, resulting in a structurally diverse set of coordination complexes with (distorted) octahedral, pentagonal-bipyramidal, or antiprismatic arrangements. Several complexes proved to be polymeric in the solid state including heterobimetallic sodium/lanthanide coordination polymers. A selection of the polymeric compounds was analyzed via TG/DTA measurements to establish their stability. The ligands, in turn, were readily synthesized in good yields from commercially available hydrazine hydrochloride salts. These findings demonstrate that acylpyrazolone ligands can form complexes with metals of varying ionic radii, highlighted by their utility in other areas such as analytical and metal organic framework chemistry.

Structural and Magnetization Dynamics of Borohydride-Bridged Rare-Earth Metallocenium Cations.

The structure and magnetic properties of the bimetallic borohydride-bridged dysprosocenium compound [{(η5-Cpttt)(η5-CpMe4t)Dy}2(µ:κ2:κ2-BH4)]+[B(C6F5)4]- ([3Dy][B(C6F5)4]) are reported along with the solution-phase dynamics of the isostructural yttrium and lutetium analogues (Cpttt is 1,2,4-tri(tert-butyl)cyclopentadienyl, CpMe4t is tetramethyl(tert-butyl)cyclopentadienyl). The synthesis of [3M][B(C6F5)4] was accomplished in the 2:1 stoichiometric reactions of [(η5-Cpttt)(η5-CpMe4t)Dy(BH4)] (2M) with [CPh3][B(C6F5)4], with the metallocenes 2M obtained from reactions of the half-sandwich complexes [(η5-Cpttt)M(BH4)2(THF)] (1M) (M = Y, Dy, Lu) with NaCpMe4t. Crystallographic studies show significant lengthening of the M···B distance on moving through the series 1M, 2M, and 3M, with essentially linear {M···B···M} bridges in 3M. Multinuclear NMR spectroscopy indicates restricted rotation of the Cpttt ligands in 3Y and 3Lu in solution. The single-molecule magnet (SMM) properties of [3M][B(C6F5)4] are characterized by Raman and Orbach processes, with an effective barrier of 533(18) cm-1 and relaxation via the second-excited Kramers doublet. Although quantum tunneling of the magnetization (QTM) was not observed for [3M][B(C6F5)4], it was, surprisingly, found in its magnetically dilute version, which has a very similar barrier of Ueff = 499(21) cm-1. Consistent with this observation, slightly wider openings of the magnetic hysteresis loop at 2 K are found for [3M][B(C6F5)4] but not for the diluted analogue. The dynamic magnetic properties of the dysprosium SMMs and the role of exchange interactions in 3Dy are interpreted with the aid of multireference ab initio calculations.

Dynamic Magnetic Properties of Germole-ligated Lanthanide Sandwich Complexes.

The first germole-ligated single-molecule magnets are reported, with contrasting properties found for the near-linear sandwich complexes [(η8 -COT)Ln(η5 -CpGe ]- , where Ln=Dy (1Dy ) or Er (1Er ), COT is cyclo-octatetraenyl and CpGe is [GeC4 -2,5-(SiMe3 )2 -3,4-Me2 ]2- . Whereas 1Er has an energy barrier of 120(1) cm-1 in zero applied field and open hysteresis loops up to 10 K, the relaxation in 1Dy is characterized by quantum tunneling within the ground state.

Thorium- and Uranium-Mediated C-H Activation of a Silyl-Substituted Cyclobutadienyl Ligand.

Cyclobutadienyl complexes of the f-elements are a relatively new yet poorly understood class of sandwich and half-sandwich organometallic compounds. We now describe cyclobutadienyl transfer reactions of the magnesium reagent [(η4-Cb'''')Mg(THF)3] (1), where Cb'''' is tetrakis(trimethylsilyl)cyclobutadienyl, toward thorium(IV) and uranium(IV) tetrachlorides. The 1:1 stoichiometric reactions between 1 and AnCl4 proceed with intact transfer of Cb'''' to give the half-sandwich complexes [(η4-Cb'''')AnCl(µ-Cl)3Mg(THF)3] (An = Th, 2; An = U, 3). Using a 2:1 reaction stoichiometry produces [Mg2Cl3(THF)6][(η4-Cb'''')An(η3-C4H(SiMe3)3-κ-(CH2SiMe2)(Cl)] (An = Th, [Mg2Cl3(THF)6][4]; An = U [Mg2Cl3(THF)6][5]), in which one Cb'''' ligand has undergone cyclometalation of a trimethylsilyl group, resulting in the formation of an An-C σ-bond, protonation of the four-membered ring, and an η3-allylic interaction with the actinide. Complex solution-phase dynamics are observed with multinuclear nuclear magnetic resonance spectroscopy for both sandwich complexes. A computational analysis of the reaction mechanism leading to the formation of 4 and 5 indicates that the cyclobutadienyl ligands undergo C-H activation across the actinide center.

Identification of Oxidation State +1 in a Molecular Uranium Complex.

The concept of oxidation state plays a fundamentally important role in defining the chemistry of the elements. In the f block of the periodic table, well-known oxidation states in compounds of the lanthanides include 0, +2, +3 and +4, and oxidation states for the actinides range from +7 to +2. Oxidation state +1 is conspicuous by its absence from the f-block elements. Here we show that the uranium(II) metallocene [U(η5-C5iPr5)2] and the uranium(III) metallocene [IU(η5-C5iPr5)2] can be reduced by potassium graphite in the presence of 2.2.2-cryptand to the uranium(I) metallocene [U(η5-C5iPr5)2]- (1) (C5iPr5 = pentaisopropylcyclopentadienyl) as the salt of [K(2.2.2-cryptand)]+. An X-ray crystallographic study revealed that 1 has a bent metallocene structure, and theoretical studies and magnetic measurements confirmed that the electronic ground state of uranium(I) adopts a 5f3(7s/6dz2)1(6dx2-y2/6dxy)1 configuration. The metal-ligand bonding in 1 consists of contributions from uranium 5f, 6d, and 7s orbitals, with the 6d orbitals engaging in weak but non-negligible covalent interactions. Identification of the oxidation state +1 for uranium expands the range of isolable oxidation states for the f-block elements and potentially signposts a synthetic route to this elusive species for other actinides and the lanthanides.

Discovery of a Dysprosium Metallocene Single-Molecule Magnet with Two High-Temperature Orbach Processes.

Magnetic bistability in single-molecule magnets (SMMs) is a potential basis for new types of nanoscale information storage material. The standard model for thermally activated relaxation of the magnetization in SMMs is based on the occurrence of a single Orbach process. Here, we show that incorporating a phosphorus atom into the framework of the dysprosium metallocene [(CpiPr5)Dy(CpPEt4)]+[B(C6F5)4]- (CpiPr5 is penta-isopropylcyclopentadienyl, CpPEt4 is tetraethylphospholyl) leads to the occurrence of two distinct high-temperature Orbach processes, with energy barriers of 1410(10) and 747(7) cm-1, respectively. These barriers provide experimental evidence for two different spin-phonon coupling regimes, which we explain with the aid of ab initio calculations. The strong and highly axial crystal field in this SMM also allows magnetic hysteresis to be observed up to 70 K, using a scan rate of 25 Oe s-1. In characterizing this SMM, we show that a conventional Debye model and consideration of rotational contributions to the spin-phonon interaction are insufficient to explain the observed phenomena.

Dominance of Cyclobutadienyl Over Cyclopentadienyl in the Crystal Field Splitting in Dysprosium Single-Molecule Magnets.

Replacing a monoanionic cyclopentadienyl (Cp) ligand in dysprosium single-molecule magnets (SMMs) with a dianionic cyclobutadienyl (Cb) ligand in the sandwich complexes [(η4 -Cb'''')Dy(η5 -C5 Me4 t Bu)(BH4 )]- (1), [(η4 -Cb'''')Dy(η8 -Pn† )K(THF)] (2) and [(η4 -Cb'''')Dy(η8 -Pn† )]- (3) leads to larger energy barriers to magnetization reversal (Cb''''=C4 (SiMe3 )4 , Pn† =1,4-di(tri-isopropylsilyl)pentalenyl). Short distances to the Cb'''' ligands and longer distances to the Cp ligands in 1-3 are consistent with the crystal field splitting being dominated by the former. Theoretical analysis shows that the magnetic axes in the ground Kramers doublets of 1-3 are oriented towards the Cb'''' ligands. The theoretical axiality parameter and the relative axiality parameter Z and Zrel are introduced to facilitate comparisons of the SMM performance of 1-3 with a benchmark SMM. Increases in Z and Zrel when Cb''' replaces Cp signposts a route to SMMs with properties that could surpass leading systems.

Synthesis and single-molecule magnet properties of a trimetallic dysprosium metallocene cation.

The dimetallic fulvalene-bridged dysprosium complex [{Dy(Cp*)(µ-BH4)}2(Fvtttt)] (1, Cp* = C5Me5) is converted into the trimetallic borohydride-bridged species [{Dy(Cp*)(Fvtttt)}2Dy(µ-BH4)3] (2). In turn, 2 is reacted with a silylium electrophile to give [{Dy(Cp*)(µ-BH4)(Fvtttt)}2Dy][B(C6F5)4] ([3][B(C6F5)3]), the first trimetallic dysprosocenium cation. Compound [3][B(C6F5)3] can also be formed directly from 1 by adding two equivalents of the electrophile. A three-fold enhancement in the effective energy barrier from 2 to 3 is observed and interpreted with the aid of ab initio calculations.

Synthesis, bonding properties and ether activation reactivity of cyclobutadienyl-ligated hybrid uranocenes.

A series of hybrid uranocenes consisting of uranium(iv) sandwiched between cyclobutadienyl (Cb) and cyclo-octatetraenyl (COT) ligands has been synthesized, structurally characterized and studied computationally. The dimetallic species [(η4-Cb'''')(η8-COT)U(µ:η2:η8-COT)U(THF)(η4-Cb'''')] (1) forms concomitantly with, and can be separated from, monometallic [(η4-Cb'''')U(THF)(η8-COT)] (2) (Cb'''' = 1,2,3,4-tetrakis(trimethylsilyl)cyclobutadienyl, COT = cyclo-octatetraenyl). In toluene solution at room temperature, 1 dissociates into 2 and the unsolvated uranocene [(η4-Cb'''')U(η8-COT)] (3). By applying a high vacuum, both 1 and 2 can be converted directly into 3. Using bulky silyl substituents on the COT ligand allowed isolation of base-free [(η4-Cb'''')U{η8-1,4-(iPr3Si)2C8H6}] (4), with compounds 3 and 4 being new members of the bis(annulene) family of actinocenes and the first to contain a cyclobutadienyl ligand. Computational studies show that the bonding in the hybrid uranocenes 3 and 4 has non-negligible covalency. New insight into actinocene bonding is provided by the complementary interactions of the different ligands with uranium, whereby the 6d orbitals interact most strongly with the cyclobutadienyl ligand and the 5f orbitals do so with the COT ligands. The redox-neutral activation of diethyl ether by [(η4-Cb'''')U(η8-C8H8)] is also described and represents a uranium-cyclobutadienyl cooperative process, potentially forming the basis of further small-molecule activation chemistry.

Spin-Crossover Properties of an Iron(II) Coordination Nanohoop.

Addition of the bipyridyl-embedded cycloparaphenylene nanohoop bipy[9]CPP to [Fe{H2 B(pyz)2 }] (pyz=pyrazolyl) produces the distorted octahedral complex [Fe(bipy[9]CPP){H2 B(pyz)2 }2 ] (1). The molecular structure of 1 shows that the nanohoop ligand contains a non-planar bipy unit. Magnetic susceptibility measurements indicate spin-crossover (SCO) behaviour with a T1/2 of 130 K, lower than that of 160 K observed with the related compound [Fe(bipy){H2 B(pyz)2 }2 ] (2), which contains a conventional bipy ligand. A computational study of 1 and 2 reveals that the curvature of the nanohoop leads to the different SCO properties, suggesting that the SCO behaviour of iron(II) can be tuned by varying the size and diameter of the nanohoop.

Fulvalene as a platform for the synthesis of a dimetallic dysprosocenium single-molecule magnet.

The dinucleating fulvalenyl ligand [1,1',3,3'-(C5 t Bu2H2)2]2- (Fvtttt) was used to synthesize the dimetallic dysprosocenium cation [{Dy(η5-Cp*)}2(µ-BH4)(η5:η5-Fvtttt)]+ (3) as the salt of [B(C6F5)4]- (Cp* = C5Me5). Compound [3][B(C6F5)4] was obtained using a method in which the double half-sandwich complex [{Dy(BH4)2(THF)}2(Fvtttt)] (1) was reacted with KCp* to give the double metallocene [{Dy(Cp*)(µ-BH4)}2(Fvtttt)] (2), followed by removal of a bridging borohydride ligand upon addition of [(Et3Si)2(µ-H)][B(C6F5)4]. The dimetallic fulvalenyl complexes 1-3 give rise to single-molecule magnet (SMM) behaviour in zero applied field, with the effective energy barriers of 154(15) cm-1, 252(4) cm-1 and 384(18) cm-1, respectively, revealing a significant improvement in performance across the series. The magnetic properties are interpreted with the aid of ab initio calculations, which show substantial increases in the axiality of the crystal field from 1 to 2 to 3 as a consequence of the increasingly dominant role of the Fvtttt and Cp* ligands, with the barrier height and hysteresis properties being attenuated by the equatorial borohydride ligands. The experimental and theoretical results described in this study furnish a blueprint for the design and synthesis of poly-cationic dysprosocenium SMMs with properties that may surpass those of benchmark systems.

Enhanced single-molecule magnetism in dysprosium complexes of a pristine cyclobutadienyl ligand.

Intact transfer of the cyclobutadienyl ligand [C4(SiMe3)4]2- to yttrium and dysprosium (M) produces the half-sandwich complexes [M{η4-C4(SiMe3)4}(BH4)2(THF)]- as coordination polymers with bridging sodium or potassium ions. The dysprosium versions are single-molecule magnets (SMMs) with energy barriers of 371(7) and 357(4) cm-1, respectively. The pristine cyclobutadienyl ligands provide a strong axial crystal field that enhances the SMM properties relative to related cyclopentadienyl compounds.

Coupling of Nitric Oxide and Release of Nitrous Oxide from Rare-Earth-Dinitrosyliron Complexes.

Addition of Lewis acidic [Cp*2M]+ (M = Y, Gd) to the dinitrosyliron complexes (DNICs) [(NacNacAr)Fe(NO)2]- (Ar = mesityl, 2,6-diisopropylphenyl) results in formation of the isonitrosyl-bridged DNICs [(Cp*)2M(µ-ON)2Fe(NacNacAr)]. When Ar = 2,6-diisopropylphenyl, coupling of the NO ligands and release of N2O occur. Two factors contribute to this previously unobserved DNIC reactivity mode. First, the oxophilic rare-earth elements drive the formation of isonitrosyl bonds, forcing the DNIC nitrogen atoms into proximity. Second, the bulky substituents further squeeze the DNIC, which ultimately overcomes the barrier to NO coupling, demonstrating that N2O elimination can occur from a single iron center.

Carbonyl Back-Bonding Influencing the Rate of Quantum Tunnelling in a Dysprosium Metallocene Single-Molecule Magnet.

The isocarbonyl-ligated metallocene coordination polymers [Cp*2M(µ-OC)W(Cp)(CO)(µ-CO)]∞ were synthesized with M = Gd (1, L = THF) and Dy (2, no L). In a zero direct-current field, the dysprosium version 2 was found to be a single-molecule magnet (SMM), with analysis of the dynamic magnetic susceptibility data revealing that the axial metallocene coordination environment leads to a large anisotropy barrier of 557(18) cm-1 and a fast quantum-tunnelling rate of ∼3.7 ms. Theoretical analysis of two truncated versions of 2, [Cp*2Dy{(µ-OC)W(Cp)(CO)2}2]- (2a), and [Cp*2Dy(OC)2]+ (2b), in which the effects of electron correlation outside the 4f orbital space were studied, revealed that tungsten-to-carbonyl back-donation plays an important role in determining the strength of the competing equatorial field at dysprosium and, hence, the dynamic magnetic properties. The finding that a classical organo-transition-metal bonding scenario can be used as an indirect way of tuning the rate of quantum tunnelling potentially provides an alternative chemical strategy for utilizing the fast magnetic relaxation properties of SMMs.

Uranium(iv) cyclobutadienyl sandwich compounds: synthesis, structure and chemical bonding.

The 1 : 1 reactions of uranium(iv) tetrakis(borohydride) with the sodium and potassium salts of the cyclobutadienyl anion [C4(SiMe3)4]2- (Cb'''') produce the half-sandwich complexes [Na(12-crown-4)2][U(η4-Cb'''')(BH4)3] and [U(η4-Cb'''')(µ-BH4)3{K(THF)2}]2. In the 1 : 2 reaction of U(BH4)4 with Na2Cb'''', formation of [U(η4-Cb'''')(η3-C4H(SiMe3)3-κ-(CH2SiMe2)(BH4))]- reveals that a Cb'''' ligand undergoes an intramolecular deprotonation, resulting in an allyl/tuck-in bonding mode. A computational study reveals that the uranium-Cb'''' bonding has an appreciable covalent component with contributions from the uranium 5f and 6d orbitals.