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Preprint of the paper:D. Serrano, S. K. Kuppusamy, B. Heinrich, O. Fuhr, D. Hunger, M. Ruben, and P. Goldner,Ultra-Narrow Optical Linewidths in Rare-Earth Molecular Crystals, Nature603, 241 (2022). Rare-earth ions are promising solid-state systems to build light-matter inter- faces at the quantum level. This relies on their potential to show narrow optical homogeneous linewidths or, equivalently, long-lived optical quantum states. In this letter, we report on europium molecular crystals that exhibit linewidths in the 10s of kHz range, orders of magnitude narrower than othermolecular centers. 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.

Bi-stable charge-neutral iron(ii) spin-crossover (SCO) complexes are a class of switchable molecular materials proposed for molecule-based switching and memory applications. In this study, we report on the SCO behavior of a series of iron(ii) complexes composed of rationally designed 2-(1H-pyrazol-1-yl)-6-(1H-tetrazol-5-yl)pyridine (ptp) ligands. The powder forms of [Fe2+(R-ptp-)2]0 complexes tethered with less-bulky substituents-R = H (1), R = CH2OH (2), and R = COOCH3 (3; previously reported)-at the 4-position of the pyridine ring of the ptp skeleton showed abrupt and hysteretic SCO at or above room temperature (RT), whereas complex 5 featuring a bulky pyrene substituent showed incomplete and gradual SCO behavior. The role of intermolecular interactions, lattice solvent, and electronic nature of the chemical substituents (R) in tuning the SCO of the complexes is elucidated.

Spin-crossover (SCO) active iron(II) complexes are an integral class of switchable and bistable molecular materials. Spin-state switching properties of the SCO complexes have been studied in the bulk and single-molecule levels to progress toward fabricating molecule-based switching and memory elements. Supramolecular SCO complexes featuring anchoring groups for metallic electrodes, for example, gold (Au), are ideal candidates to study spin-state switching at the single-molecule level. In this study, we report on the spin-state switching characteristics of supramolecular iron(II) complexes 1 and 2 composed of functional 4-([2,2′-bithiophen]-5-ylethynyl)-2,6-di(1H-pyrazol-1-yl)pyridine (L1) and 4-(2-(5-(5-hexylthiophen-2-yl)thiophen-2-yl)ethynyl)-2,6-di(1H-pyrazol-1-yl)pyridine (L2) ligands, respectively. Density functional theory (DFT) studies revealed stretching-induced spin-state switching in a molecular junction composed of complex 1, taken as a representative example, and gold electrodes. Single-molecule conductance traces revealed the unfavorable orientation of the complexes in the junctions to demonstrate the spin-state dependence of the conductance., Grant Agency Innovation FRC is acknowledged for the financial support for the project Self-assembly of spin-crossover (SCO) complexes on graphene. M.R. thanks the DFG priority program 1928 “COORNETS” for generous support. A.M. acknowledges the Alexander von Humboldt (AvH) Foundation for a postdoctoral fellowship. The research of A.G.-F. and J.F. was funded by project PGC2018-094783 (MCIU/AEI/FEDER, EU).

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., This review provides a complete account of the on‐surface spin‐state switching behavior of films of spin‐crossover (SCO) complexes of molecular to multilayer thickness. SCO‐based molecular and thin‐film device architectures fabricated employing vacuum sublimation are also described.

Studies on the spin-state switching characteristics of surface-bound thin films of spin-crossover (SCO) complexes are of interest to harness the device utility of the SCO complexes. Molecule-substrate interactions govern the SCO of surface-bound films in direct contact with the underlying substrates. In this study, we elucidate the role of molecule-substrate interactions on the thermal- and light-induced spin-state switching characteristics of a functional SCO-complex.[Fe(H2B(pz)(2))(2)COOC12H25-bipy] (pz = pyrazole, C-12-bpy = dodecyl[2,2'-bipyridine]-5-carboxylate) deposited at a submonolayer coverage on a highly oriented pyrolytic graphite (HOPG) substrate. A spin-state coexistence of 42% low-spin (LS) and 58% high-spin (HS) is observed for the 0.4 ML deposit of the complex at 40 K, in contrast to the complete spin-state switching observed in the bulk and in SiOx-bound 10 nm thick films. Cooling the sample to 10 K results in a decrease of the LS fraction to 36%, attributed to soft-X-ray-induced excited spin-state trapping (SOXIESST). Illumination of the sample with a green light (lambda = 520 nm) at 10 K caused the LS-to-HS switching of the remaining (36%) LS complexes, by a process termed light-induced excited spin-state trapping (LIESST). The mixed spin-state in the submonolayer coverage of [Fe(H2B(pz)(2))(2)COOC12H25-bipy] highlights the role of molecule-HOPG substrate interactions in tuning the thermal SCO characteristics of the complex. The 100% HS state obtained after light irradiation indicates the occurrence of efficient on-surface light-induced spin switching, encouraging the development of light-addressable molecular devices based on SCO complexes.

Spin-crossover (SCO) active transition metal complexes are a class of switchable molecular materials. Such complexes undergo hysteretic high-spin (HS) to low-spin (LS) transition, and vice versa, rendering them suitable for the development of molecule-based switching and memory elements. Therefore, the search for SCO complexes undergoing abrupt and hysteretic SCO, that is, bistable SCO, is actively carried out by the molecular magnetism community. In this study, we report the bistable SCO characteristics associated with a new series of iron(ii) complexes-[Fe(BPP-CN)2](X)2, X = BF4 (1a-d) or ClO4 (2)-belonging to the [Fe(BPP-R)2]2+ (BPP = 2,6-bis(pyrazol-1-yl)pyridine) family of complexes. Among the complexes, the lattice solvent-free complex 2 showed a stable and complete SCO (T1/2 = 241 K) with a thermal hysteresis width (ΔT) of 28 K-the widest ΔT reported so far for a [Fe(BPP-R)2](X)2 family of complexes, showing abrupt SCO. The reproducible and bistable SCO shown by the relatively simple [Fe(BPP-CN)2](X)2 series of molecular complexes is encouraging to pursue [Fe(BPP-R)2]2+ systems for the realization of technologically relevant SCO complexes.

The success of the emerging field of solid-state optical quantum information processing (QIP) critically depends on the access to resonant optical materials. Rare-earth ions (REIs) are suitable candidates for QIP protocols due to their extraordinary photo-physical and magnetic quantum properties such as long optical and spin coherence lifetimes ($T_2$). However, molecules incorporating REIs, despite having advantageous properties such as atomically exact quantum tunability, inherent scalability, and large portability, have not yet been studied for QIP applications. As a first testimony of the usefulness of REI molecules for optical QIP applications, we demonstrate in this study that narrow spectral holes can be burned in the inhomogeneously broadened $^5$D$_0\to^7$F$_0$ optical transition of a binuclear Eu(III) complex, rendering a homogeneous linewidth ($\Gamma_h$) = 22 $\pm$ 1 MHz, which translates as $T_2 = 14.5$ $\pm$ 0.7 ns at 1.4 K. Moreover, long-lived spectral holes are observed, demonstrating efficient polarization of Eu(III) ground state nuclear spins, a fundamental requirement for all-optical spin initialization and addressing. These results elucidate the usefulness of REI-based molecular complexes as versatile coherent light-spin interfaces for applications in quantum communications and processing., Comment: 31 pages, 9 figures

Luminescent oligo(p-phenylene ethynylene) (OPE) and spin-crossover (SCO) active Fe(II)2,6-di(pyrazol-1-yl) pyridine (BPP) systems are prominent examples proposed to develop functional materials such as molecular wires/memories. A marriage between OPE and Fe(II)-BPP systems is a strategy to obtain supramolecular luminescent ligands capable of metal coordination useful to produce novel spin-switchable hybrids with synergistic coupling between spin-state of Fe(II) and a physical property associated with the OPE skeleton, for example, electronic conductivity or luminescence. To begin in this direction, two novel ditopic ligands, namely L-1 and L-2, featuring OPE-type backbone end-capped with metal coordinating BPP were designed and synthetized. The ligand L-2 tailored with 2-ethylhexyloxy chains at the 2 and 5 positions of the OPE skeleton shows modulated optical properties and improved solubility in common organic solvents relative to the parent ligand L-1. Solution phase complexation of L-1 and L-2 with Fe(BF4)(2)center dot 6H(2)O resulted in the formation of insoluble materials of the composition [Fe(L-1)](n)(BF4)(2n) and [Fe(L-2)](n)(BF4)(2n) as inferred from elemental analyses. Complex [Fe(L-1)](n)(BF4)(2n) underwent thermal SCO centred at T-1/2 = 275 K as well as photoinduced low-spin to high-spin transition with the existence of the metastable high-spin state up to 52 K. On the other hand, complex [Fe(L-2)]n(BF4)(2n), tethered with 2-ethylhexyloxy groups, showed gradual and half-complete SCO with 50% of the Fe(II)-centres permanently blocked in the high-spin state due to intermolecular steric interactions. The small angle x-ray scattering (SAXS) pattern of the as-prepared solid complex [Fe(L-1)](n)(BF4)(2n) revealed the presence of nm-sized crystallites implying a possible methodology towards the template-free synthesis of functional-SCO nanostructures.

Spin-crossover (SCO) active transition metal complexes are a class of switchable molecular materials. Such complexes undergo hysteretic high-spin (HS) to low-spin (LS) transition, and vice versa, rendering them suitable for the development of molecule-based switching and memory elements. Therefore, the search for SCO complexes undergoing abrupt and hysteretic SCO, that is, bistable SCO, is actively carried out by the molecular magnetism community. In this study, we report the bistable SCO characteristics associated with a new series of iron(II) complexes-[Fe(BPP-CN)(2)](X)(2), X = BF4 (1a-d) or ClO4 (2)-belonging to the [Fe(BPP-R)(2)](2+) (BPP = 2,6-bis(pyrazol-1-yl)pyridine) family of complexes. Among the complexes, the lattice solvent-free complex 2 showed a stable and complete SCO (T-1/2 = 241 K) with a thermal hysteresis width (Delta T) of 28 K-the widest Delta T reported so far for a [Fe(BPP-R)(2)](X)(2) family of complexes, showing abrupt SCO. The reproducible and bistable SCO shown by the relatively simple [Fe(BPP-CN)(2)](X)(2) series of molecular complexes is encouraging to pursue [Fe(BPP-R)(2)](2+) systems for the realization of technologically relevant SCO complexes.

Bi-stable charge-neutral iron(ii) spin-crossover (SCO) complexes are a class of switchable molecular materials proposed for molecule-based switching and memory applications. In this study, we report on the SCO behavior of a series of iron(ii) complexes composed of rationally designed 2-(1H-pyrazol-1-yl)-6-(1H-tetrazol-5-yl)pyridine (ptp) ligands. The powder forms of [Fe

The design and synthesis of functional molecules with controllable properties are at the forefront of modern materials chemistry research due to their diverse applicability, especially in device miniaturization. Spin crossover (SCO) complexes can be switched between low (LS) and high spin (HS) magnetic states with the help of an external perturbation, and are promising candidates for the realization of molecule-based electronic and spintronic components, such as switching and memory elements. Although the area is relatively old and a multitude of SCO active transition metal complexes of d 4 -d 7 electronic configuration have been reported, the field continues to grow, and several interesting research directions have emerged. In this context, the present review attempts to give a concise overview of recent trends in SCO research. Attempts devoted towards rendering multifunctionality to the SCO systems in order to bridge the gap between laboratory and reality, and efforts made to study spin state dependence of physical property modulation such as electrical conductance from single molecule level to bulk, prerequisite for the realization of SCO-based devices, are emphasized by discussing the most relevant past and recent literature.

The spin-crossover (SCO) phenomenon is one of the most prominent examples of bi-stability in molecular chemistry, and the SCO complexes are proposed for nanotechnological applications such as memory units, sensors, and displays. Since the discovery of the SCO phenomenon in tris(N,N-dialkyldithiocarbamato)iron(iii) complexes, numerous investigations have been made to obtain bi-stable SCO complexes undergoing spin-state switching at or around room temperature (RT). Valiant efforts have also been made to elucidate the structure-property relationship in SCO complexes to understand the factors-such as ligand-field strength, molecular geometry, and intermolecular interactions-governing the SCO. Schiff base ligands are an important class of nitrogen-rich chelating ligands used to prepare SCO complexes, because the Schiff base ligands are easy to synthesize and tailor with additional functionalities. Iron(ii)-Schiff base SCO complexes are a well-studied class of SCO active complexes due to the propensity of the complexes to undergo bi-stable SCO. In this context, this perspective attempts to elucidate the structure-SCO property relationships governing SCO in selected mono-, bi-, and multi-nuclear iron(ii)-Schiff base complexes.

A highly distorted high spin Fe(ii)-complex, [Fe(1-BPP-COOC2H5)2](ClO4)2·CH3CN, with a trans-N(pyridine)-Fe-N(pyridine) angle (φ) of 158.83(17)° showed lattice solvent dependent bi-stable spin-state switching characteristics with T1/2 = ca. 233 K and a high thermal hysteresis width (ΔT) of 101 K, for the first cooling and heating cycle, unprecedented for the [Fe(BPP)2]2+ series of complexes; the results presented in this study are fundamentally important and have implications towards the realization of device architectures based on bi-stable SCO complexes.

A highly distorted high spin Fe(ii)-complex, [Fe(1-BPP-COOC2H5)(2)](ClO4)(2)CH3CN, with a trans-N(pyridine)-Fe-N(pyridine) angle (phi) of 158.83(17)degrees showed lattice solvent dependent bi-stable spin-state switching characteristics with T-1/2 = ca. 233 K and a high thermal hysteresis width (T) of 101 K, for the first cooling and heating cycle, unprecedented for the [Fe(BPP)(2)](2+) series of complexes; the results presented in this study are fundamentally important and have implications towards the realization of device architectures based on bi-stable SCO complexes.

One promising route toward encoding information is to utilize the two stable electronic states of a spin crossover molecule. However, while this property is clearly manifested in transport across single molecule junctions, evidence linking charge transport across a solid-state device to the molecular film's spin state has thus far remained indirect. To establish this link, we deploy materials-centric and device-centric operando experiments involving X-ray absorption spectroscopy. We find a correlation between the temperature dependencies of the junction resistance and the Fe spin state within the device's Fe(bpz)2(phen) molecular film. We also factually observe that the Fe molecular site mediates charge transport. Our dual operando studies reveal that transport involves a subset of molecules within an electronically heterogeneous spin crossover film. Our work confers an insight that substantially improves the state-of-the-art regarding spin crossover-based devices, thanks to a methodology that can benefit device studies of other next-generation molecular compounds., Typo in the first name of one of the authors updated (Jinje -> Jinjie)

Spin-crossover (SCO) molecules are versatile magnetic switches with applications in molecular electronics and spintronics. Downscaling devices to the single-molecule level remains, however, a challenging task since the switching mechanism in bulk is mediated by cooperative intermolecular interactions. Here, we report on electron transport through individual Fe-SCO molecules coupled to few-layer graphene electrodes via π-π stacking. We observe a distinct bistability in the conductance of the molecule and a careful comparison with density functional theory (DFT) calculations allows to associate the bistability with a SCO-induced orbital reconfiguration of the molecule. We find long spin-state lifetimes that are caused by the specific coordination of the magnetic core and the absence of intermolecular interactions according to our calculations. In contrast with bulk samples, the SCO transition is not triggered by temperature but induced by small perturbations in the molecule at any temperature. We propose plausible mechanisms that could trigger the SCO at the single-molecule level., We acknowledge financial support from the Dutch Organization for Fundamental research (NWO/FOM), the European Commission through an advanced ERC grant (Mols@Mols) and the Marie Curie ITN MOLESCO, from the Netherlands Organization for Scientific Research (NWO/OCW) as part of the Frontiers of Nanoscience program, and from the Spanish Ministerio de Economia y Competitividad through the project FIS2015-63918-R. EB thanks funds from the EU FP7 program through Project 618082 ACMOL and NWO through a VENI fellowship.

The advancement of molecular electronics and spintronics requires novel hybrid materials with synergistic magnetic and electrical properties. The non-covalent functionalization of highly conductive graphene with magnetically bistable spin crossover (SCO) complexes may yield such a multifunctional material. In this regard, a graphene-Fe(II) SCO complex hybrid (Gr-SCO) has been prepared by non-covalently anchoring a pyrene decorated SCO complex with solution phase pre-exfoliated few-layer graphene sheets. SQUID magnetometry revealed the preservation of SCO in the Gr-SCO hybrid material exhibiting more gradual spin state switching characteristics than in the bulk molecular complex. This persistence of SCO of a molecular Fe(II) complex upon anchoring on the graphene surface has consequences towards the realization of SCO based applications: in (i) reversible spin state dependent band gap tuning of graphene with an SCO complex analogous to chemical doping of graphene, and (ii) to probe the spin state dependence of electrical conductivity modulation by wiring the anchoring group (pyrene) tethered SCO complex between chemically robust few-layer graphene electrodes.

We report on the synthesis of tridentate-nitrogen pyrazole-pyridine-tetrazole (L(1)H) and pyrazole-pyridine-triazole (L(2)H) ligands and their complexation with lanthanides (Ln = Gd(iii), Eu(iii) and Tb(iii)) resulting in stable, charge-neutral complexes Ln(L(1))3 and Ln(L(2))3, respectively. X-ray crystallographic analysis of the complexes with L(1) ligands revealed tricapped trigonal coordination geometry around the lanthanide ions. All complexes show bright photoluminescence (PL) in the solid state, indicating efficient sensitization of the lanthanide emission via the triplet states of the ligands. In particular, the terbium complexes show high PL quantum yields of 65 and 59% for L(1) and L(2), respectively. Lower PL efficiencies of the europium complexes (7.5 and 9%, respectively) are attributed to large energy gaps between the triplet states of the ligands and accepting levels of Eu(iii). The triplet state energy can be reduced by introducing an electron withdrawing (EW) group at the 4 position of the pyridine ring. Such substitution of L(1)H with a carboxylic ester (COOMe) EW group leads to a europium complex with increased PL quantum yield of 31%. A comparatively efficient PL of the complexes dissolved in ethanol indicates that the lanthanide ions are shielded against nonradiative deactivation via solvent molecules.

A simple “isomer-like” variation of the spacer group in a set of Fe(II) spin crossover (SCO) complexes designed to probe spin state dependence of electrical conductivity in graphene-based molecular spintronic junctions led to the observation of remarkable variations in the thermal- and light-induced magnetic characteristics, paving a simple route for the design of functional SCO complexes with different temperature switching regimes based on a 2,6-bis(pyrazol-1-yl)pyridine ligand skeleton.