Cycloheptatrienyl-Bridged Triple-Decker Complexes.

The first structurally characterized organometallic multidecker sandwich complexes featuring a cycloheptatrienyl ring (Cht, C7H73-) in the coordination sphere are presented. The synthesis of inverse sandwich complexes of the rare earth elements YIII and ErIII with a bridging cycloheptatrienyl ligand of the type [(thf)(BH4)2LnIII(µ-η7:η7-Cht)LnIII(BH4)(thf)2] is described first. The subsequent introduction of the CotTIPS ligand (CotTIPS = 1,4-(iPr3Si)2C8H62-) into the coordination sphere of the rare earth cations resulted in the isolation of unprecedented triple-decker compounds with the formula [(thf)3K{(η8-CotTIPS)LnIII}2(µ-η7:η7-Cht)], bearing a seven-membered aromatic carbon ring as a middle deck. These compounds are also the first examples of rare earth triple-decker complexes not bridged by a Cot derivative, based on purely carbon-based ligands. The magnetic properties of the respective ErIII congeners were investigated in detail, leading to the observation of antiferromagnetic coupling of the ErIII cations and a blocking temperature of 13.5 K. The conversion of the YIII compound [(thf)3K{(η8-CotTIPS)YIII}2(µ-η7:η7-Cht)] with [YIII(Cot)I(thf)2] resulted in ligand rearrangement and the selective formation of the first triple-decker complex ([(η8-CotTIPSYIII)2(µ-η8:η8-Cot)]) featuring two Cot ligands with different substituents in its coordination sphere.

Spectral hole-burning studies of a mononuclear Eu(III) complex reveal narrow optical linewidths of the 5D0 → 7F0 transition and seconds long nuclear spin lifetimes.

Coordination complexes of rare-earth ions (REI) show optical transitions with narrow linewidths enabling the creation of coherent light-matter interfaces for quantum information processing (QIP) applications. Among the REI-based complexes, Eu(III) complexes showing the 5D0 → 7F0 transition are of interest for QIP applications due to the narrow linewidths associated with the transition. Herein, we report on the synthesis, structure, and optical properties of a novel Eu(III) complex and its Gd(III) analogue composed of 2,9-bis(pyrazol-1-yl)-1,10-phenanthroline (dpphen) and three nitrate (NO3) ligands. The Eu(III) complex-[Eu(dpphen)(NO3)3]-showed sensitized metal-centred emission (5D0 → 7FJ; J = 0,1,2,3, 4, 5, or 6) in the visible region, upon irradiation of the ligand-centered band at 369 nm, with the 5D0 → 7F0 transition centred at 580.9 nm. Spectral hole-burning (SHB) studies of the complex with stoichiometric Eu(III) concentration revealed a narrow homogeneous linewidth (Γh) of 1.55 MHz corresponding to a 0.205 µs long optical coherence lifetime (T2opt). Remarkably, long nuclear spin lifetimes (T1spin) of up to 41 s have been observed for the complex. The narrow optical linewidths and long T1spin lifetimes obtained for the Eu(III) complex showcase the utility of Eu(III) complexes as tunable, following molecular engineering principles, coherent light-matter interfaces for QIP applications.

Synthesis, Structural Characterization, and Magnetic Properties of Lanthanide Arsolyl Sandwich Complexes.

A series of trivalent lanthanide sandwich complexes [(η5-C4R4As)Ln(η8-C8H8)] using three different arsolyl ligands are reported. The complexes were obtained via salt elimination reactions between potassium arsolyl salts and lanthanide precursors [LnI(COT)(THF)2] (Ln = Sm, Dy, Er; COT = η8-C8H8). The resulting compounds exhibit classical sandwich complex structures with one notable exception. Characterization was conducted in both the solid state using single-crystal X-ray diffraction and in solution for the Sm compounds using NMR spectroscopy. Furthermore, the magnetic properties of an Er complex were investigated, revealing distinctive single-molecule-magnet behavior characterized by an energy barrier of Ueff = 323.3 K. Theoretical calculations were employed to support and interpret the experimental findings, with a comparative analysis performed against previously reported complexes.

Hilbert Space in Isotopologue Dy(III) SMM Dimers: Dipole Interaction Limit in [163/164Dy2(tmhd)6(tape)]0 Complexes.

Single-molecule magnets are molecular complexes proposed to be useful for information storage and quantum information processing applications. In the quest for multilevel systems that can act as Qudits, two dysprosium-based isotopologues were synthesized and characterized. The isotopologues are [164Dy2(tmhd)6(tape)] (1(I=0)) and [163Dy2(tmhd)6(tape)] (2(I=5/2)), where tmhd = 2,2,6,6-tetramethylheptandionate and tape = 1,6,7,12-tetraazaperylene. Both complexes showed slow relaxation at a zero applied magnetic field with dominant Orbach and Raman relaxation mechanisms. µSQUID studies at milli-Kelvin temperatures reveal quasi-single ion loops, in contrast with the expected S-shape (near zero field) butterfly loops, characteristic of antiferromagnetically coupled dimeric complexes. Through analysis of the low-temperature data, we find that the interaction operating between Dy(III) is small, leading to a small exchange biasing from the zero-field transition. The resulting indirectly coupled nuclear states are degenerate or possess a small energy difference between them. We, therefore, conclude that for the creation of Qudits with enlarged Hilbert spaces, shorter Dy(III)···Dy(III) distances are deemed essential.

Terminal Ligand and Packing Effects on Slow Relaxation in an Isostructural Set of [Dy(H2 dapp)X2 ]+ Single Molecule Magnets*.

We report three structurally related single ion Dy compounds using the pentadentate ligand 2,6-bis((E)-1-(2-(pyridin-2-yl)-hydrazineylidene)ethyl)pyridine (H2 dapp) [Dy(H2 dapp)(NO3 )2 ]NO3 (1), [Dy(H2 dapp)(OAc)2 ]Cl (2) and [Dy(H2 dapp)(NO3 )2 ]Cl0.92 (NO3 )0.08 (3). The (H2 dapp) occupies a helical twisted pentagonal equatorial arrangement with two anionic ligands in the axial positions. Further influence on the electronic and magnetic structure is provided by a closely associated counterion interacting with the central N-H group of the (H2 dapp). The slow relaxation of the magnetisation shows that the anionic acetates give the greatest slowing down of the magnetisation reversal. Further influence on the relaxation properties of compounds1 and 2 is the presence of short nitrate-nitrate intermolecular ligand contact opening further lattice relaxation pathways.

Self-assembly of four Ni16 Molecular Wheels with Capsule and Tubular Supramolecular Architectures.

Four new Ni16 molecular wheels with the general formula [L4Ni16(RCOO)16(H2O)x(MeOH)12-x] (where H4L = 1,4-bis((E)-((2'-hydroxybenzyl)imino)methyl)-2,3-naphthalenediol, and R = H or Me) have been isolated and structurally characterised. Complexes C1 - C3 (R = Me)were formed using nickel(II) acetate and presented as polymorphs with the same formulation of charged components. The same wheel-like architecture was observed in C4 (R = H), which was prepared using nickel(II) formate, demonstrating the potential for further versatility of the system. In contrast to similar four-fold symmetric Ni(II) wheel clusters, measurements of the static magnetic properties of C1 indicated the presence of dominant antiferromagnetic interactions and an S = 0 ground state.

It's not just the size that matters: crystal engineering of lanthanide-based coordination polymers.

Synthesis and characterization of Lewis base free coordination polymers of selected lanthanides are presented. For this purpose, the substituted CotTIPS ligand (CotTIPS = 1,4-bis-triisopropylsilyl-cyclo-octatetraendiide) was used to synthesize homoleptic, anionic multidecker compounds of the type [K{LnIII(ɳ8-CotTIPS)2}]n. Depending on the solvent used for crystallization and the ionic radii of the lanthanide cations, three different categories of one-dimensional heterobimetallic coordination polymers were obtained in the solid state. For the early lanthanides La and Ce a unique helical conformation was obtained by crystallization from toluene, while the ionic radius of Pr seems to be a turning point towards the crystallization of zigzag polymers. For Er a third structural motif, a trapezoidal wave polymer was observed. Additionally, the zigzag polymer for all compounds could be obtained by changing the solvent from toluene to Et2O, reavealing a correlation between solid-state structure and ionic radii as well as solvent. While photoluminescence (PL) properties of Cot-lanthanide compounds are scarce, the La complexes show ligand centered green luminescence, whereas the Ce complexes reveal deep red emission origin from d-f transitions. The Er-compounds are single-molecule magnets, in which the magnetic relaxation of each Er ion occurs isolated from its neighbors at temperatures above 10 K, while below 9 K a strong antiferromagnetic coupling between the Er ions was seen.

Molecular cyclo-P3 complexes of the rare-earth elements via a one-pot reaction and selective reduction.

Synthesis of new organo-lanthanide polyphosphides with an aromatic cyclo-[P4]2- moiety and a cyclo-[P3]3- moiety is presented. For this purpose, the divalent LnII-complexes [(NON)LnII(thf)2] (Ln = Sm, Yb) ((NON)2- = 4,5-bis(2,6-diisopropylphenyl-amino)-2,7-di-tert-butyl-9,9-dimethylxanthene) and trivalent LnIII-complexes [(NON)LnIIIBH4(thf)2] (Ln = Y, Sm, Dy) were used as precursors in the reduction process of white phosphorus. While using [(NON)LnII(thf)2] as a one-electron reducing agent the formation of organo-lanthanide polyphosphides with a cyclo-[P4]2- Zintl anion was observed. For comparison, we investigated a multi-electron reduction of P4 by a one-pot reaction of [(NON)LnIIIBH4(thf)2] with elemental potassium. As products molecular polyphosphides with a cyclo-[P3]3- moiety were isolated. The same compound could also be obtained by reducing the cyclo-[P4]2- Zintl anion within the coordination sphere of SmIII in [{(NON)SmIII(thf)2}2(µ-η4:η4-P4)]. Reduction of a polyphosphide within the coordination sphere of a lanthanide complex is unprecedented. Additionally, the magnetic properties of the dinuclear DyIII-compound bearing a bridging cyclo-[P3]3- moiety were investigated.

Introduction of plumbole to f-element chemistry.

Herein, we present the synthesis and characterization of heteroleptic lanthanide complexes bearing a dianionic η5-plumbole ligand in their coordination sphere. The reaction proceeds via a salt elimination reaction between the dilithioplumbole ([Li(thf)]2[1,4-bis-tert-butyl-dimethylsilyl-2,3-bis-phenyl-plumbolyl] = [Li2(thf)2(η5-LPb)]) and specifically designed [Ln(η8-COTTIPS)BH4] precursors (Ln = lanthanide, La, Ce, Sm, Er; COTTIPS = 1,4-bis-triisopropylsilyl-cyclooctatetraenyl), that are capable of stabilizing a planar plumbole moiety in the coordination sphere of different trivalent lanthanide ions. In-depth ab initio calculations show that the aromaticity of the dianionic plumbole is retained upon coordination. Electron delocalization occurs from the plumbole HOMO to an orbital of mainly d-character at the lanthanide ion. The magnetic properties of the erbium congener were investigated in detail, leading to the observation of magnetic hysteresis up to 5 K (200 Oe s-1), an unequivocal proof for single molecule magnet behavior in this system. The magnetic behavior of the erbium species can be modulated by manipulating the position of the lithium cation in the complex, which directly influences the bonding metrics in the central [(η5-LPb)Er(η8-COTTIPS)]- fragment. This allowed us to assess a fundamental magneto-structural correlation in an otherwise identical inner coordination sphere.

Triangulo-{ErIII 3} complex showing field supported slow magnetic relaxation.

The triangulo-{Er3} complex [Er3Cl(o-van)3(OH)2(H2O)5]Cl3·nH2O (n = 9.4; H(o-van) = o-vanillin) (1) was generated by an in situ method. The isolated Er(iii) complex 1 was characterized by elemental analysis and molecular spectroscopy. The results of single crystal X-ray diffraction studies have shown that 1 is built up of trinuclear [Er3Cl(o-van)3(OH)2(H2O)5]3+ complex cations, chloride anions and water solvate molecules. Within the complex cation the three Er(iii) central atoms are placed at the apexes of a triangle which are bridged by three (o-van)- ligands with additional chelating functions and two µ3-OH- ligands. Additionally five aqua and one chlorido ligands complete the octa-coordination of the three Er(iii) atoms. AC susceptibility measurements reveal that the compound exhibits slow magnetic relaxation with two relaxation modes.

Heteroleptic, polynuclear dysprosium(iii)-carbamato complexes through in situ carbon dioxide capture.

Amine groups are among the most effective systems for carbon dioxide capture. Reminiscent of the activation of nature's most abundant enzyme RuBisCO, the treatment of amines with CO2 in the presence of oxophilic metal ions, e.g. Mg2+, results in the formation of carbamates. Here we report the synthesis, structure and magnetic properties of three new dysprosium-carbamato complexes. The reaction of gaseous CO2 with N,N-diisopropylamine and DyCl3(DME)2 (DME = Dimethoxyethane) in toluene leads to the formation of the tetrametallic complex [Dy4(O2CNiPr2)10(O-C2H4-OMe)2]. The addition of 2-hydroxy-3-methoxybenzaldehyde-N-methylimine yields the hexametallic compound [Dy6(O2CNiPr2)8(O-C2H4-OMe)2(CO3)2(C9O2NH10)4] in which the metal sites form a chair-like configuration; The same hexanuclear motif is obtained using N,N-dibenzylamine. We show that by employing CO2 as a feedstock, we are able to capture up to 2.5 molecules of CO2 per Dy ion. Magnetic measurements show a decreasing χMT at low temperatures. Combining the experimental magnetic data with ab initio calculations reveils tilting of the easy axes and implies the presence of antiferromagnetic interactions between the Dy(iii) metal ions.