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.

Electronic properties of single Prussian Blue Analog nanocrystals determined by conductive-AFM.

We report a study of the electron transport (ET) properties at the nanoscale (conductive-AFM denoted as C-AFM hereafter) of individual Prussian Blue Analog (PBA) cubic nanocrystals (NCs) of CsCoIIIFeII, with a size between 15 and 50 nm deposited on HOPG. We demonstrate that these PBA NCs feature an almost size-independent electron injection barrier of 0.41 ± 0.02 eV and 0.27 ± 0.03 eV at the CsCoIIIFeII/HOPG and CsCoIIIFeII/C-AFM tip, respectively, and an intrinsic electron conductivity evolving from a large dispersion between ∼5 × 10-4 and 2 × 10-2 S cm-1 without a clear correlation with the nanocrystal size. The conductivity values measured on individual nanocrystals are up to fifty times higher than those reported on PBA films.

Interface versus Bulk Light-Induced Switching in Spin-Crossover Molecular Ultrathin Films Adsorbed on a Metallic Surface.

Spin-crossover molecules present the unique property of having two spin states that can be controlled by light excitation at low temperature. Here, we report on the photoexcitation of [FeII((3, 5-(CH3)2Pz)3BH)2] (Pz = pyrazolyl) ultrathin films, with thicknesses ranging from 0.9 to 5.3 monolayers, adsorbed on Cu(111) substrate. Using X-ray absorption spectroscopy measurements, we confirm the anomalous light-induced spin-state switching observed for sub-monolayer coverage and demonstrate that it is confined to the first molecular layer in contact with the metallic substrate. For higher coverages, the well-known light-induced excited spin-state trapping effect is recovered. Combining continuous light excitation with thermal cycling, we demonstrate that at low temperature light-induced thermal hysteresis is measured for the thicker films, while for sub-monolayer coverage, the light enables extension of the thermal conversion over a large temperature range. Mechanoelastic simulations underline that, due to the intermolecular interactions, opposite behaviors are observed in the different layers composing the films.

Terphenylthiazole-based self-assembled monolayers on cobalt with high conductance photo-switching ratio for spintronics.

Two new photo-switchable terphenylthiazole molecules are synthesized and self-assembled as monolayers on Au and on ferromagnetic Co electrodes. The electron transport properties probed by conductive atomic force microscopy in ultra-high vacuum reveal a larger conductance of the light-induced closed (c) form than for the open (o) form. We report an unprecedented conductance ratio of up to 380 between the closed and open forms on Co for the molecule with the anchoring group (thiol) on the side of the two N atoms of the thiazole unit. This result is rationalized by Density Functional Theory (DFT) calculations coupled to the Non-Equilibrium Green's function (NEGF) formalism. These calculations show that the high conductance in the closed form is due to a strong electronic coupling between the terphenylthiazole molecules and the Co electrode that manifests by a resonant transmission peak at the Fermi energy of the Co electrode with a large broadening. This behavior is not observed for the same molecules self-assembled on gold electrodes. These high conductance ratios make these Co-based molecular junctions attractive candidates to develop and study switchable molecular spintronic devices.

Voltage-Induced Bistability of Single Spin-Crossover Molecules in a Two-Dimensional Monolayer.

Bistable spin-crossover molecules are particularly interesting for the development of innovative electronic and spintronic devices as they present two spin states that can be controlled by external stimuli. In this paper, we report the voltage-induced switching of the high spin/low spin electronic states of spin-crossover molecules self-assembled in dense 2D networks on Au(111) and Cu(111) by scanning tunneling microscopy at low temperature. On Au(111), voltage pulses lead to the nonlocal switching of the molecules from any─high or low─spin state to the other followed by a spontaneous relaxation toward their initial state within minutes. On the other hand, on Cu(111), single molecules can be addressed at will. They retain their new electronic configuration after a voltage pulse. The memory effect demonstrated on Cu(111) is due to an interplay between long-range intermolecular interaction and molecule/substrate coupling as confirmed by mechanoelastic simulations.

Magnetic Hysteresis in a Monolayer of Oriented 6 nm CsNiCr Prussian Blue Analogue Nanocrystals.

Prussian blue analogue nanocrystals of the CsINiII[CrIII(CN)6] cubic network with 6 nm size were assembled as a single monolayer on highly organized pyrolytic graphite (HOPG). X-ray magnetic circular dichroism (XMCD) studies, at the Ni and Cr L2,3 edges, reveal the presence of an easy plane of magnetization evidenced by an opening of the magnetic hysteresis loop (coercive field of ≈200 Oe) when the magnetic field, B, is at 60° relative to the normal to the substrate. The angular dependence of the X-ray natural linear dichroism (XNLD) reveals both an orientation of the nanocrystals on the substrate and an anisotropy of the electronic cloud of the NiII and CrIII coordination sphere species belonging to the nanocrystals' surface. Ligand field multiplet (LFM) calculations that reproduce the experimental data are consistent with an elongated tetragonal distortion of surface NiII coordination sphere responsible for the magnetic behavior of monolayer.

Thermal Bistability of an Ultrathin Film of Iron(II) Spin-Crossover Molecules Directly Adsorbed on a Metal Surface.

Spin-crossover molecules are very attractive compounds to realize multifunctional spintronic devices. Understanding their properties when deposited on metals is therefore crucial for their future rational implementation as ultrathin films in such devices. Using X-ray absorption spectroscopy, we study the thermal transition of the spin-crossover compound FeII((3,5-(CH3)2Pz)3BH)2 from submonolayer to multilayers on a Cu(111) substrate. We determine how the residual fraction of high spin molecules at low temperature, as well as the bistability range and the temperature of switching, depends on the layer thickness. The most spectacular effect is the clear opening of a 35 ± 9 K thermal hysteresis loop for a 3.0 ± 0.7 monolayers thick film. To better understand the role played by the substrate and the dimensionality on the thermal bistability, we have performed Monte Carlo Arrhenius simulations in the framework of a mechanoelastic model that include a molecule-substrate interaction. This model reproduces well the main features observed experimentally and can predict how the spin-crossover transition is modified by the thickness and the substrate interaction.

Chemical tuning of spin clock transitions in molecular monomers based on nuclear spin-free Ni(ii).

We report the existence of a sizeable quantum tunnelling splitting between the two lowest electronic spin levels of mononuclear Ni complexes. The level anti-crossing, or magnetic "clock transition", associated with this gap has been directly monitored by heat capacity experiments. The comparison of these results with those obtained for a Co derivative, for which tunnelling is forbidden by symmetry, shows that the clock transition leads to an effective suppression of intermolecular spin-spin interactions. In addition, we show that the quantum tunnelling splitting admits a chemical tuning via the modification of the ligand shell that determines the crystal field and the magnetic anisotropy. These properties are crucial to realize model spin qubits that combine the necessary resilience against decoherence, a proper interfacing with other qubits and with the control circuitry and the ability to initialize them by cooling.

The design of magneto-plasmonic nanostructures formed by magnetic Prussian Blue-type nanocrystals decorated with Au nanoparticles.

We have developed a general protocol for the preparation of hybrid nanostructures formed by nanoparticles (NPs) of molecule-based magnets based on Prussian Blue Analogues (PBAs) decorated with plasmonic Au NPs of different shapes. By adjusting the pH, Au NPs can be attached preferentially along the edges of the PBA or randomly on the surface. The protocol allows tuning the plasmonic properties of the hybrids in the whole visible spectrum.

Charge transfer driven by ultrafast spin transition in a CoFe Prussian blue analogue.

Photoinduced charge-transfer is an important process in nature and technology and is responsible for the emergence of exotic functionalities, such as magnetic order for cyanide-bridged bimetallic coordination networks. Despite its broad interest and intensive developments in chemistry and material sciences, the atomic-scale description of the initial photoinduced process, which couples intermetallic charge-transfer and spin transition, has been debated for decades; it has been beyond reach due to its extreme speed. Here we study this process in a prototype cyanide-bridged CoFe system by femtosecond X-ray and optical absorption spectroscopies, enabling the disentanglement of ultrafast electronic and structural dynamics. Our results demonstrate that it is the spin transition that occurs first on the Co site within ~50 fs, and it is this that drives the subsequent Fe-to-Co charge-transfer within ~200 fs. This study represents a step towards understanding and controlling charge-transfer-based functions using light.

Long-range electron transport in Prussian blue analog nanocrystals.

We report electron transport measurements through nano-scale devices consisting of 1 to 3 Prussian blue analog (PBA) nanocrystals connected between two electrodes. We compare two types of cubic nanocrystals, CsCoIIIFeII (15 nm) and CsNiIICrIII (6 nm), deposited on highly oriented pyrolytic graphite and contacted by conducting-AFM. The measured currents show an exponential dependence with the length of the PBA nano-device (up to 45 nm), with low decay factors ß, in the range 0.11-0.18 nm-1 and 0.25-0.34 nm-1 for the CsCoFe and the CsNiCr nanocrystals, respectively. From the theoretical analysis of the current-voltage curve for the nano-scale device made of a single nanoparticle, we deduce that the electron transport is mediated by the localized d bands at around 0.5 eV from the electrode Fermi energy in the two cases. By comparison with previously reported ab initio calculations, we tentatively identify the involved orbitals as the filled Fe(ii)-t2g d band (HOMO) for CsCoFe and the half-filled Ni(ii)-eg d band (SOMO) for CsNiCr. Conductance values measured for multi-nanoparticle nano-scale devices (2 and 3 nanocrystals between the electrodes) are consistent with a multi-step coherent tunneling in the off-resonance regime between adjacent PBAs, a simple model gives a strong coupling (around 0.1-0.25 eV) between the adjacent PBA nanocrystals, mediated by electrostatic interactions.

Photoswitchable 11 nm CsCoFe Prussian Blue Analogue Nanocrystals with High Relaxation Temperature.

Photoswitchable 11 nm nanocrystals with the coordination network Cs{Co[Fe(CN)6]} were obtained using a template-free method. The nanocrystals were recovered from the colloidal solutions as solid materials surrounded by cetyltrimethylammonium (CTA) cations or embedded in the organic polymer polyvinylpyrrolidone (PVP). Complementary magnetic, spectroscopic, and structural techniques, including EPR spectroscopy, reveal a majority (∼70%) of the low-spin and photoactive diamagnetic CoIIIFeII pairs located in the core of the nanocrystals and a mixture of CoIIFeII and CoIIFeIII species present mainly within the shell of the objects. While bulk compounds with similar vacancy concentration do not exhibit noticeable photoinduced charge transfer, the observed photoactivity of the nanocrystals is ascribed to their nanometric size. The relaxation temperature of the photoinduced state shifts upward by ∼55 K when PVP is replaced by CTA. This is ascribed to the larger rigidity of the dense CsCoFe_CTA material, whose metastable state is lower than that for CsCoFe_PVP, leading to a larger relaxation energy barrier and, therefore, to a higher relaxation temperature.

Anomalous Light-Induced Spin-State Switching for Iron(II) Spin-Crossover Molecules in Direct Contact with Metal Surfaces.

Light-induced spin-state switching is one of the most attractive properties of spin-crossover materials. In bulk, low-spin (LS) to high-spin (HS) conversion via the light-induced excited spin-state trapping (LIESST) effect may be achieved with a visible light, while the HS-to-LS one (reverse-LIESST) requires an excitation in the near-infrared range. Now, it is shown that those phenomena are strongly modified at the interface with a metal. Indeed, an anomalous spin conversion is presented from HS state to LS state under blue light illumination for FeII spin-crossover molecules that are in direct contact with metallic (111) single-crystal surfaces (copper, silver, and gold). To interpret this anomalous spin-state switching, a new mechanism is proposed for the spin conversion based on the light absorption by the substrate that can generate low energy valence photoelectrons promoting molecular vibrational excitations and subsequent spin-state switching at the molecule-metal interface.

Magnetic Relaxation Studies on Trigonal Bipyramidal Cobalt(II) Complexes.

We report the preparation and the full characterization of a novel mononuclear trigonal bipyramidal CoII complex [Co(NS3 iPr )Br](BPh4 ) (1) with the tetradentate sulfur-containing ligand NS3 iPr (N(CH2 CH2 SCH(CH3 )2 )3 ). The comparison of its magnetic behaviour with those of two previously reported compounds [Co(NS3 iPr )Cl](BPh4 ) (2) and [Co(NS3 tBu )Br](ClO4 ) (3) (NS3 tBu =N(CH2 CH2 SC(CH3 )3 )3 ) with similar structures shows that 1 displays a single-molecule magnet behaviour with the longest magnetic relaxation time (0.051 s) at T=1.8 K, which is almost thirty times larger than that of 3 (0.0019 s) and more than three times larger than that of 2 (0.015 s), though its effective energy barrier (26 cm-1 ) is smaller. Compound 1, which contains two crystallographically independent molecules, presents smaller rhombic parameters (E=1.45 and 0.59 cm-1 ) than 2 (E=2.05 and 1.02 cm-1 ) and 3 (E=2.00 and 0.80 cm-1 ) obtained from theoretical calculations. Compounds 2 and 3 have almost the same axial (D) and rhombic (E) parameter values, but present a large difference of their effective energy barrier and magnetic relaxation which may be attributed to the larger volume of BPh4 - than ClO4 - leading to larger diamagnetic dilution (weaker magnetic dipolar interaction) for 2 than for 3. The combination of these factors leads to a much slower magnetic relaxation for 1 than for the two other compounds.

Electronic and spin delocalization in a switchable trinuclear triphenylene trisemiquinone bridged Ni3 complex.

A trinuclear triphenylene trisemiquinone complex containing paramagnetic NiII is obtained under ambient conditions from the reaction of deprotonated tricatecholate hexahydroxytriphenylene (H6HHTP) with NiII capped with a trispyrazolyl borate tridentate ligand. The magnetic and EPR data are consistent with delocalization of the electronic spin over the three NiII species. The two-electron reduced complex shows an EPR spectrum corresponding to a S = 1/2 species due to a large antiferromagnetic coupling between the radical and only one of the NiII ions highlighting the localization of the electronic spin. No EPR signal is observed for the one- and three-electron reduced species consistent with the closed shell of the bridging ligand.

Derivation of Lanthanide Series Crystal Field Parameters From First Principles.

Two series of lanthanide complexes have been chosen to analyze trends in the magnetic properties and crystal field parameters (CFPs) along the two series: The highly symmetric LnZn16 (picHA)16 series (Ln=Tb, Dy, Ho, Er, Yb; picHA=picolinohydroxamic acid) and the [Ln(dpa)3 ](C3 H5 N2 )3 ⋅3H2 O series (Ln=Ce-Yb; dpa=2,6-dipicolinic acid) with approximate three-fold symmetry. The first series presents a compressed coordination sphere of eight oxygen atoms whereas in the second series, the coordination sphere consists of an elongated coordination sphere formed of six oxygen atoms. The CFPs have been deduced from ab initio calculations using two methods: The AILFT (ab initio ligand field theory) method, in which the parameters are determined at the orbital level, and the ITO (irreducible tensor operator) decomposition, in which the problems are treated at the many-electron level. It has been found that the CFPs are transferable from one derivative to another, within a given series, as a first approximation. The sign of the second-order parameter B 0 2 differs in the two series, reflecting the different environments. It has been found that the use of the strength parameter S allows for an easy comparison between complexes. Furthermore, in both series, the parameters have been found to decrease in magnitude along the series, and this decrease is attributed to covalent effects.

Importance of Epitaxial Strain at a Spin-Crossover Molecule-Metal Interface.

Spin-crossover molecules are very appealing for use in multifunctional spintronic devices because of their ability to switch between high-spin and low-spin states with external stimuli such as voltage and light. In actual devices, the molecules are deposited on a substrate, which can modify their properties. However, surprisingly little is known about such molecule-substrate effects. Here we show for the first time, by grazing incidence X-ray diffraction, that an FeII spin-crossover molecular layer displays a well-defined epitaxial relationship with a metal substrate. Then we show, by both density functional calculations and a mechanoelastic model, that the resulting epitaxial strain and the related internal pressure can induce a partial spin conversion at low temperatures, which has indeed been observed experimentally. Our results emphasize the importance of substrate-induced spin state transitions and raise the possibility of exploiting them.

Influence of a Counteranion on the Zero-Field Splitting of Tetrahedral Cobalt(II) Thiourea Complexes.

Four mononuclear cobalt(II) complexes with pseudo tetrahedral geometry were isolated with different counteranions; their structure solution reveals the molecular formula as [Co(L1)4]X2 [where L1 = thiourea (NH2CSNH2) and X = NO3 (1), Br (2), and I (3)] and [Co(L1)4](SiF6) (4). The detailed analysis of direct-current (dc) magnetic data reveals a zero-field splitting (ZFS; D) with mS = ±3/2 as the ground levels (D < 0) for the four complexes. The magnitude of the ZFS parameter is larger, in absolute value, for 1 (D = -61.7 cm-1) than the other three complexes (-5.4, -5.1, and -12.2 cm-1 for 2-4, respectively). The sign of D for 1, 2, and 4 was unambiguously determined by X-band electron paramagnetic resonance (EPR) spectroscopy of the diluted samples (10%) at 5 K. For 3, the sign of D was naturally endorsed from the frequency-dependent out-of-phase signal (χM″) observed in the absence of an external dc magnetic field and confirmed by high-frequency EPR (70-600 GHz) experiments performed on a representative pure polycrystalline 3, which gave a quantitative D value of -5.10(7) cm-1. Further, the drastic changes in the spin Hamiltonian parameters and their related relaxation dynamics phenomena (of 2-4 compared to 1) were rationalized using ab initio complete-active-space self-consistent field/n-electron valence perturbation theory calculations. Calculations disclose that the anion-induced structural distortion observed in 2-4 leads to a nonfavorable overlap between the π orbital of cobalt(II) and the π* orbital of the sulfur atom that reduces the overall |D| value in these complexes compared to 1. The present study demonstrates that not only the first but also the second coordination sphere significantly influences the magnitude of the ZFS parameters. Particularly, a reduction of D of up to ∼90% occurs (in 2-4 compared to 1) upon a simple variation of the counteranions and offers a viable approach to modulate ZFS in transition-metal-containing single-molecule magnets.

Tuning bimetallic catalysts for a selective growth of SWCNTs.

Recent advances in structural control during the synthesis of SWCNTs have in common the use of bimetallic nanoparticles as catalysts, despite the fact that their exact role is not fully understood. We therefore analyze the effect of the catalyst's chemical composition on the structure of the resulting SWCNTs by comparing three bimetallic catalysts (FeRu, CoRu and NiRu). A specific synthesis protocol is designed to impede the catalyst nanoparticle coalescence mechanisms and stabilize their diameter distributions throughout the growth. Owing to the ruthenium component which has a limited carbon solubility, tubes grow in tangential mode and their diameter is close to that of their seeding nanoparticles. By using the as-synthesized SWCNTs as a channel material infield effect transistors, we show how the chemical composition of the catalysts and temperature can be used as parameters to tune the diameter distribution and semiconducting-to-metallic ratio of SWCNT samples. Finally, a phenomenological model, based on the dependence of the carbon solubility as a function of catalyst nanoparticle size and nature of the alloying elements, is proposed to interpret the results.

Substituted versus Naked Thiourea Ligand Containing Pseudotetrahedral Cobalt(II) Complexes: A Comparative Study on Its Magnetization Relaxation Dynamics Phenomenon.

A series of mononuclear tetrahedral cobalt(II) complexes with the general molecular formula [Co(L1)2X2] [where L1 = tetramethylthiourea ([(CH3)2N]2C═S) and X = Cl (1), Br (2), and I (3)] were isolated, and their structures were characterized by single-crystal X-ray diffraction. The experimental direct-current magnetic data are excellently reproduced by fitting both χM T( T) and M( H) simultaneously using the spin Hamiltonian (SH) parameters D1 = -18.1 cm-1 and g1,iso = 2.26, D2 = -16.4 cm-1 and g2,iso = 2.33, and D3 = -22 cm-1 and g3,iso = 2.4 for 1-3, respectively, and the sign of D was unambiguously confirmed from X-band electron paramagnetic resonance measurements. The effective energy barrier extracted for the magnetically diluted complexes 1-3 (10%) is larger than the barrier observed for the pure samples and implies a nonzero contribution of dipolar interaction to the magnetization relaxation dynamics. The SH parameters extracted for the three complexes drastically differ from their respective parent complexes that possess the general molecular formula [Co(L)2X2] [where L = thiourea [(NH2)2C═S] and X = Cl (1a), Br (2a), and I (3a)], which is rationalized by detailed ab initio calculations. An exhaustive theoretical study reveals that both the ground and excited states are not pure but rather multideterminental in nature (1-3). Noticeably, the substitution of L by L1 induces structural distortion in 1-3 on the level of the secondary coordination sphere compared to 1a-3a. This distortion leads to an overall reduction in | E/ D| of 1-3 compared to 1a-3a. This may be one of the reasons for the origin of the slower relaxation times of 1-3 compared to 1a-3a.