Ultra-narrow optical linewidths in rare-earth molecular crystals.

Rare-earth ions (REIs) are promising solid-state systems for building light-matter interfaces at the quantum level1,2. This relies on their potential to show narrow optical and spin homogeneous linewidths, or, equivalently, long-lived quantum states. This enables the use of REIs for photonic quantum technologies such as memories for light, optical-microwave transduction and computing3-5. However, so far, few crystalline materials have shown an environment quiet enough to fully exploit REI properties. This hinders further progress, in particular towards REI-containing integrated nanophotonics devices6,7. Molecular systems can provide such capability but generally lack spin states. If, however, molecular systems do have spin states, they show broad optical lines that severely limit optical-to-spin coherent interfacing8-10. Here we report on europium molecular crystals that exhibit linewidths in the tens of kilohertz range, orders of magnitude narrower than those of other molecular systems. We harness this property to demonstrate efficient optical spin initialization, coherent storage of light using an atomic frequency comb, and optical control of ion-ion interactions towards implementation of quantum gates. These results illustrate the utility of rare-earth molecular crystals as a new platform for photonic quantum technologies that combines highly coherent emitters with the unmatched versatility in composition, structure and integration capability of molecular materials.

Altering Spin Distribution of Tb2Pc3 via Molecular Chirality Manipulation.

Manipulating the chirality of the spin-polarized electronic state is pivotal for understanding many unusual quantum spin phenomena, but it has not been achieved at the single-molecule level. Here, using scanning tunneling microscopy and spectroscopy (STM/STS), we successfully manipulate the chirality of spin distribution in a triple-decker single-molecule magnet tris(phthalocyaninato)bis(terbium(III)) (Tb2Pc3), which is evaporated on a Pb(111) substrate via molecular beam epitaxy. The otherwise achiral Tb2Pc3 becomes chiral after being embedded into the self-assembled monolayer films of bis(phthalocyaninato)terbium(III) (TbPc2). The chirality of the spin distribution in Tb2Pc3 is manifested via the spatial mapping of its Kondo resonance state from its ligand orbital. Our first-principles calculations revealed that the spin and molecular chirality are associated with a small rotation followed by a structural distortion of the top Pc, consistent with the experimental observation. By constructing tailored molecular clusters with the STM tip, a single Tb2Pc3 molecule can be manipulated among achiral and differently handed chiral configurations of spin distributions reversibly. This paves the way for designing chiral spin enantiomers for fundamental studies and developing functional spintronic devices.

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.

Yb-to-Eu Cooperative Sensitization Upconversion in a Multifunctional Molecular Nonanuclear Lanthanide Cluster in Solution.

Lanthanide metal clusters excel in combining molecular and material chemistry properties. Here, we report an efficient cooperative sensitization UC phenomenon of a Eu3+/Yb3+ nonanuclear lanthanide cluster in CD3OD. The synthesis and characterization of the heteronuclear cluster in the solid state and solution are described together with the UC phenomenon showing Eu3+ luminescence in the visible region upon 980 nm NIR excitation of Yb3+ at concentrations as low as 100 nM. Alongside being the Eu/Yb cluster to display UC (with a quantum yield value of 4.88 × 10-8 upon 1.13 W cm-2 excitation at 980 nm), the cluster exhibits downshifted light emission of Yb3+ in the NIR region upon 578 nm visible excitation of Eu3+, which is ascribed to sensitization pathways for Yb through the 5D0 energy levels of Eu3+. Additionally, a faint emission is also observed at ca. 500 nm upon 980 nm excitation, originating from the cooperative luminescence of Yb3+. The [Eu8Yb(BA)16(OH)10]Cl cluster (BA = benzoylacetonate) is also a field-induced single-molecular magnet (SMM) under 4K with a modest Ueff/kB of 8.48 K, thereby joining the coveted list of Yb-SMMs and emerging as a prototype system for next-generation devices, combining luminescence with single-molecular magnetism in a molecular cluster.

Selective Transition Enhancement in a g-Engineered Diradical.

A diradical with engineered g-asymmetry was synthesized by grafting a nitroxide radical onto the [Y(Pc)2]⋅ radical platform. Various spectroscopic techniques and computational studies revealed that the electronic structures of the two spin systems remained minimally affected within the diradical system. Fluid-solution Electron Paramagnetic Resonance (EPR) experiments revealed a weak exchange coupling with |J| ~ 0.014 cm-1, subsequently rationalized by CAS-SCF calculations. Frozen solution continuous-wave (CW) EPR experiments showed a complicated and power-dependent spectrum that eluded analysis using the point-dipole model. Pulse EPR manipulations with varying microwave powers, or under varying magnetic fields, demonstrated that different resonances could be selectively enhanced or suppressed, based on their different tipping angles. In particular, Field-Swept Echo-Detected (FSED) spectra revealed absorptions of MW power-dependent intensities, while Field-Swept Spin Nutation (FSSN) experiments revealed two distinct Rabi frequencies. This study introduces a methodology to synthesize and characterize g-asymmetric two-spin systems, of interest in the implementation of spin-based CNOT gates.

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.

Matrix effects on the magnetic properties of a molecular spin triangle embedded in a polymeric film.

Molecular triangles with competing Heisenberg interactions and significant Dzyaloshinskii-Moriya interactions (DMI) exhibit high environmental sensitivity, making them potential candidates for active elements for quantum sensing. Additionally, these triangles exhibit magnetoelectric coupling, allowing their properties to be controlled using electric fields. However, the manipulation and deposition of such complexes pose significant challenges. This work explores a solution by embedding iron-based molecular triangles in a polymer matrix, a strategy that offers various deposition methods. We investigate how the host matrix alters the magnetic properties of the molecular triangle, with specific focus on the magnetic anisotropy, aiming to advance its practical applications as quantum sensors.

Unique Double and Triple Decker Arrangements of Rare-Earth 9,10-Diborataanthracene Complexes Featuring Single-Molecule Magnet Characteristics.

Herein, we present the first report on the synthesis of rare-earth complexes featuring a 9,10-diborataanthracene ligand. This 14-π-electron ligand is highly reductive and was previously used in small-molecule activation. Salt elimination reactions between dipotassium 9,10-diethyl-9,10-diborataanthracene [K2(DEDBA)] and [LnIII(η8-CotTIPS)(BH4)(thf)x] (CotTIPS=1,4-(iPr3Si)2C8H6) in a 1 : 1 ratio yielded heteroleptic sandwich complexes [K(η8-CotTIPS)LnIII(η6-DEDBA)] (Ln=Y, Dy, Er). These compounds form Lewis-base-free one-dimensional coordination polymers when crystallised from toluene. In contrast, reaction of [K2(DEDBA)] and [LnIII(η8-CotTIPS)(BH4)(thf)x] in a 1 : 2 ratio led to the formation of heteroleptic triple-decker complexes [(η8-CotTIPS)LnIII(µ-η6:η6-DEDBA)LnIII(η8-CotTIPS)] (Ln=Y, Dy, Er). Notably, these are not only the first lanthanide triple-decker compounds featuring a six-membered ring as a deck but also the first trivalent lanthanide triple-decker featuring a heterocycle in the coordination sphere. Magnetic investigations reveal that [K(η8-CotTIPS)LnIII(η6-DEDBA)] (Ln=Dy, Er) and [(η8-CotTIPS)ErIII(µ-η6:η6-DEDBA)ErIII(η8-CotTIPS)] exhibit Single-Molecule Magnet (SMM) behaviour. In the case of [(η8-CotTIPS)LnIII(µ-η6:η6-DEDBA)LnIII(η8-CotTIPS)] (Ln=Dy, Er), the introduction of a second near lanthanide ion results in strong antiferromagnetic interactions, allowing the enhancement of the magnetic characteristic of the system, compared to the quasi isolated counterpart. This research renews the overlooked coordination chemistry of the DBA ligand and expands it to encompass rare-earth elements.

Molecular-Engineered Biradicals Based on the YIII-Phthalocyanine Platform.

A mixed-ligand phthalocyanine/porphyrin yttrium(III) radical double-decker complex (DD) was synthesized using the custom-made 5,10,15-tris(4-methoxyphenyl)-20-(4-((trimethylsilyl)ethynyl)phenyl)porphyrin. The trimethylsilyl functionality was then used to couple two such complexes into biradicals through rigid tethers. Glaser coupling was used to synthesize a short-tethered biradical (C1) and Sonogashira coupling to synthesize longer-tethered ones (C2 and C3). Field-swept echo-detected (FSED), saturation recovery, and spin nutation-pulsed electron paramagnetic resonance experiments revealed marked similarities of the magnetic properties of DD with those of the parent [Y(pc)2]• complex, both in the solid state and in CD2Cl2/CDCl3 4:1 frozen glasses. FSED experiments on the biradicals C2 and C3 revealed a spectral broadening with respect to the spectra of DD and [Y(pc)2]• assigned to the effect of dipolar interactions in solution. Apart from the main resonance, satellite features were also observed, which were simulated with dipole-dipole pairs of shortest distances, suggesting spin delocalization on the organic tether. FSED experiments on C1 yielded spectral line shapes that could not be simulated as the integration of the off-resonance echoes was complicated by field-dependent modulations. While, for all dimers, the on-resonance spin nutation experiments yielded Rabi oscillations of the same frequencies, off-resonance nutations on C1 yielded Rabi oscillations that could be assigned to a MS = -1 to MS = 0 transition within a S = 1 multiplet. The DFT calculations showed that the trans conformation of the complexes was significantly more stable than the cis one and that it induced a marked spin delocalization over the rigid organic tether. This "spin leakage" was most pronounced for the shortest biradical C1.

Thermalization of Nuclear Spins in Lanthanide Molecular Magnets.

Single-molecule magnets (SMMs) distinguish themselves in the field of quantum magnetism through the ability to combine fundamental research with promising applications. The evolution of quantum spintronics in the last decade exemplifies the potential held by molecular-based quantum devices. Notably, the readout and manipulation of the nuclear spin states embedded in a lanthanide-based SMM hybrid device were employed in proof of principle studies of quantum computation at the single-molecule level. In the quest for further understanding of the relaxation behavior in SMMs for their integration in novel applications, herein, we study the relaxation dynamics of the 159Tb nuclear spins in a diluted molecular crystal employing the recently acquired understanding of the nonadiabatic dynamics of TbPc2 molecules. Through numerical simulation, we find that phonon-modulated hyperfine interaction opens a direct relaxation channel between the nuclear spins and the phonon bath. The mechanism is of potential importance for the theory of spin bath and the relaxation dynamics of the molecular spins.

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.

Molecular Lanthanide Switches for Magnetism and Photoluminescence.

Solvation of [(CNT)Ln(η8 -COT)] (Ln=La, Ce, Nd, Tb, Er; CNT=cyclononatetraenyl, i.e., C9 H9 - ; COT=cyclooctatetraendiid, i.e., C8 H8 2- ) complexes with tetrahydrofuran (THF) gives rise to neutral [(η4 -CNT)Ln(thf)2 (η8 -COT)] (Ln=La, Ce) and ionic [Ln(thf)x (η8 -COT)][CNT] (x=4 (Ce, Nd, Tb), 3 (Er)) species in a solid-to-solid transformation. Due to the severe distortion of the ligand sphere upon solvation, these species act as switchable luminophores and single-molecule magnets. The desolvation of the coordinated solvents can be triggered by applying a dynamic vacuum, as well as a temperature gradient stimulus. Raman spectroscopic investigations revealed fast and fully reversible solvation and desolvation processes. Moreover, we also show that a Nd:YAG laser can induce the necessary temperature gradient for a self-sufficient switching process of the Ce(III) analogue in a spatially resolved manner.

Structural Insights into Hysteretic Spin-Crossover in a Set of Iron(II)-2,6-bis(1H-Pyrazol-1-yl)Pyridine) Complexes.

Bistable spin-crossover (SCO) complexes that undergo abrupt and hysteretic (ΔT1/2 ) spin-state switching are desirable for molecule-based switching and memory applications. In this study, we report on structural facets governing hysteretic SCO in a set of iron(II)-2,6-bis(1H-pyrazol-1-yl)pyridine) (bpp) complexes - [Fe(bpp-COOEt)2 ](X)2 ⋅CH3 NO2 (X=ClO4 , 1; X=BF4 , 2). Stable spin-state switching - T1/2 =288 K; ΔT1/2 =62 K - is observed for 1, whereas 2 undergoes above-room-temperature lattice-solvent content-dependent SCO - T1/2 =331 K; ΔT1/2 =43 K. Variable-temperature single-crystal X-ray diffraction studies of the complexes revealed pronounced molecular reorganizations - from the Jahn-Teller-distorted HS state to the less distorted LS state - and conformation switching of the ethyl group of the COOEt substituent upon SCO. Consequently, we propose that the large structural reorganizations rendered SCO hysteretic in 1 and 2. Such insights shedding light on the molecular origin of thermal hysteresis might enable the design of technologically relevant molecule-based switching and memory elements.

Indirect Spin-Readout of Rare-Earth-Based Single-Molecule Magnet with Scanning Tunneling Microscopy.

Rare-earth based single-molecule magnets are promising candidates for magnetic information storage including qubits as their large magnetic moments are carried by localized 4f electrons. This shielding from the environment in turn hampers a direct electronic access to the magnetic moment. Here, we present the indirect readout of the Dy moment in Bis(phthalocyaninato)dysprosium (DyPc_{2}) molecules on Au(111) using milli-Kelvin scanning tunneling microscopy. Because of an unpaired electron on the exposed Pc ligand, the molecules show a Kondo resonance that is, however, split by the ferromagnetic exchange interaction between the unpaired electron and the Dy angular momentum. Using spin-polarized scanning tunneling spectroscopy, we read out the Dy magnetic moment as a function of the applied magnetic field, exploiting the spin polarization of the exchange-split Kondo state.

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.

Chiral Resolution of Spin-Crossover Active Iron(II) [2x2] Grid Complexes.

Chiral magnetic materials are proposed for applications in second-order non-linear optics, magneto-chiral dichroism, among others. Recently, we have reported a set of tetra-nuclear Fe(II) grid complex conformers with general formula C/S-[Fe4 L4 ]8+ (L: 2,6-bis(6-(pyrazol-1-yl)pyridin-2-yl)-1,5-dihydrobenzo[1,2-d : 4,5-d']diimidazole). In the grid complexes, isomerism emerges from tautomerism and conformational isomerism of the ligand L, and the S-type grid complex is chiral, which originates from different non-centrosymmetric spatial organization of the trans type ligand around the Fe(II) center. However, the selective preparation of an enantiomerically pure grid complex in a controlled manner is difficult due to spontaneous self-assembly. To achieve the pre-synthesis programmable resolution of Fe(II) grid complexes, we designed and synthesized two novel intrinsically chiral ligands by appending chiral moieties to the parent ligand. The complexation of these chiral ligands with Fe(II) salt resulted in the formation of enantiomerically pure Fe(II) grid complexes, as unambiguously elucidated by CD and XRD studies. The enantiomeric complexes exhibited similar gradual and half-complete thermal and photo-induced SCO characteristics. The good agreement between the experimentally obtained and calculated CD spectra further supports the enantiomeric purity of the complexes and even the magnetic studies. The chiral resolution of Fe(II)- [2×2] grid complexes reported in this study, for the first time, might enable the fabrication of magneto-chiral molecular devices.

NiII 36 -Containing 54-Tungsto-6-Silicate: Synthesis, Structure, Magnetic and Electrochemical Studies.

The 36-NiII -containing 54-tungsto-6-silicate, [Ni36 (OH)18 (H2 O)36 (SiW9 O34 )6 ]6- (Ni36 ) was synthesized by a simple one-pot reaction of the Ni2 -pivalate complex [Ni2 (µ-OH2 )(O2 CCMe3 )4 (HO2 CCMe3 )4 ] with the trilacunary [SiW9 O34 ]10- polyanion precursor in water and structurally characterized by a multitude of physicochemical techniques including single-crystal XRD, FTIR, TGA, elemental analysis, magnetic and electrochemical studies. Polyanion Ni36 comprises six equivalent {NiII 6 SiW9 } units which are linked by Ni-O-W bridges forming a macrocyclic assembly. Magnetic studies demonstrate that the {Ni6 } building blocks in Ni36 remain magnetically intact while forming a hexagonal ring with antiferromagnetic exchange interactions between adjacent {Ni6 } units. Electrochemical studies indicate that the first reduction is reversible and associated with the WVI/V couple, whereas the second reduction is irreversible attributed to the NiII/0 couple.

Size-Controlled Hapticity Switching in [Ln(C9 H9 )(C8 H8 )] Sandwiches.

Sandwich complexes of lanthanides have recently attracted a considerable amount of interest due to their applications as Single Molecule Magnet (SMM). Herein, a comprehensive series of heteroleptic lanthanide sandwich complexes ligated by the cyclononatetraenyl (Cnt) and the cyclooctatetraenyl (Cot) ligand [Ln(Cot)(Cnt)] (Ln=Tb, Dy, Er, Ho, Yb, and Lu) is reported. The coordination behavior of the Cnt ligand has been investigated along the series and shows different coordination patterns in the solid-state depending on the size of the corresponding lanthanide ion without altering its overall anisotropy. Besides the characterization in the solid state by single-crystal X-ray diffraction and in solution by 1 H NMR, static magnetic studies and ab initio computational studies were performed.

Sublimable Spin-Crossover Complexes: From Spin-State Switching to Molecular Devices.

Spin-crossover (SCO) active transition metal complexes are an important class of switchable molecular materials due to their bistable spin-state switching characteristics at or around room temperature. Vacuum-sublimable SCO complexes are a subclass of SCO complexes suitable for fabricating ultraclean spin-switchable films desirable for applications, especially in molecular electronics/spintronics. Consequently, on-surface SCO of thin-films of sublimable SCO complexes have been studied employing spectroscopy and microscopy techniques, and results of fundamental and technological importance have been obtained. This Review provides complete coverage of advances made in the field of vacuum-sublimable SCO complexes: progress made in the design and synthesis of sublimable functional SCO complexes, on-surface SCO of molecular and multilayer thick films, and various molecular and thin-film device architectures based on the sublimable SCO complexes.