Interplay between transition-metal K-edge XMCD, slight structural distortions and magnetism in a series of trimetallic (CoxNi(1-x))4[Fe(CN)6]3/8 Prussian blue analogues.

The magnetic properties of a series of trimetallic (Co,Ni)Fe Prussian blue analogues (PBAs) were investigated by SQUID magnetometry and X-ray magnetic circular dichroism (XMCD) at the three transition metal (TM) K-edges. In turn, the PBA trimetallic series was used as a tool in order to better understand the information contained in TM K-edge XMCD and particularly the chemical nature of the probed species (extended sub-lattice or localized entities). The results show that the magnetic behavior of the compounds is dictated by competing exchange interactions between the Co-Fe and Ni-Fe pairs, without spin frustration. They also show that XMCD at the TM K-edge is a local atomic probe of the element at the N side of the cyanide bridge and a local probe of the absorbing atom and its first magnetic neighbors on the C side of the bridge. At last, XMCD at the TM K-edge turns out to be highly sensitive to very small structural distortions.

Orbital Magnetic Moment and Single-Ion Magnetic Anisotropy of the S = 1/2 K3[Fe(CN)6] Compound: A Case Where the Orbital Magnetic Moment Dominates the Spin Magnetic Moment.

The potassium hexacyanoferrate(III), K3[FeIII(CN)6], is known for its exceptional magnetic anisotropy among the 3d transition metal series. The Fe(III) ions are in the S = 1/2 low spin state imposed by the strong crystal field of the cyanido ligands. A large orbital magnetic moment is expected from previous publications. In the present work, X-ray magnetic circular dichroism was recorded for a powder sample, allowing direct measurement of the Fe(III) orbital magnetic moment. A combination of molecular multiconfigurational ab initio and atomic ligand field multiplets calculations provides the spin and orbital magnetic moments for the [FeIII(CN)6]3- isolated cluster, the crystallographic unit cell, and the powder sample. The calculations of the angular dependencies of the spin and orbital magnetic moments with the external magnetic induction direction reveal easy magnetization axes for each S = 1/2 molecular entity and the crystal. It also shows that the orbital magnetic moment dominates the spin magnetic moment for all directions. Our measurements confirm that the orbital magnetic moment contributes to 60% of the total magnetization for the powder, which is in excellent agreement with our theoretical predictions. An orbital magnetic moment greater than the spin magnetic moment is exceptional for 3d transition metal ions. The impact of crystal field strength and distortion, π back-bonding, spin-orbit coupling, and external magnetic induction was analyzed, leading to a deeper understanding of the spin and orbital magnetic anisotropies.

Structure and Electronic Properties of Large Oligomeric Heterometallic 3d/CeIV Polyoxometalates.

Merging the rich chemistry of Ce(IV) polyoxometalates (POMs) with that of 3d polyanions remains a challenge due to the strong competition between these highly oxophilic lanthanide cations and 3d metallic ions for coordination to lacunary molecular metal oxides. We report herein the characterization of an unprecedented water stable hexameric CeIV/CoII POM (Ce12Co6) made of two {(SiW9)2Ce6} units connected to a {(SiW10)2Co6(PO4)2} core. In addition, the pentameric CeIV/NiII compound Ce6Ni8, where two {PW9Ni3W} and a {PW10Ni2} fragments are grafted on a {(PW9)2Ce6} moiety, has been obtained. Magnetic studies of Ce6Ni8 revealed ferromagnetic interactions between the NiII centers constituting the {Ni3PW10} fragments, in agreement with the geometry of such a trinuclear cluster. Related insoluble barium salts of Ce12Co6 and Ce6Ni8 were also prepared, allowing their solid-state electrochemical investigations and showing in particular that in Ce12Co6, both the cobalt, cerium, and silicotungstate moieties are electroactive. Finally, photophysical studies demonstrate the formation of long-lived reduced POMs photosensitized by [Ru(bpy)3]2+, suggesting that Ce12Co6 and Ce6Ni8 could be used as efficient reservoirs of reduction equivalents for photocatalytic reactions.

ON/OFF Photo(switching) along with Reversible Spin-State Change and Single-Crystal-to-Single-Crystal Transformation in a Mixed-Valence Fe(II)Fe(III) Molecular System.

A mixed-valence Fe(II)Fe(III) molecular system, {[Fe(pzTp)(CN)3]2[Fe(bik)2]2}·[Fe(pzTp)(CN)3]2·4MeOH (1·4MeOH) (bik = bis-(1-methylimidazolyl)-2-methanone, pzTp = tetrakis(pyrazolyl)borate), exhibits single-crystal-to-single-crystal (SC-SC) transformation while increasing the temperature and is converted into {[Fe(pzTp)(CN)3]2[Fe(bik)2]2}·[Fe(pzTp)(CN)3]2 (1). Both complexes exhibit thermo-induced spin-state switching behavior along with reversible SC-SC transformation, where the low-temperature [FeIIILSFeIILS]2 phase transforms into a high-temperature [FeIIILSFeIIHS]2 phase. 1·4MeOH exhibits an abrupt spin-state switching with T1/2 at 355 K, whereas 1 undergoes a gradual and reversible spin-state switching with a lower T1/2 at 338 K. Astonishingly, 1 exhibits ON/OFF photo-induced spin-state switching with TLIESST = 67 K, whereas 1·4MeOH does not show such an effect.

Interplay between Transition-Metal K-edge XMCD and Magnetism in Prussian Blue Analogs.

To disentangle the information contained in transition-metal K-edge X-ray magnetic circular dichroism (XMCD), two series of Prussian blue analogs (PBAs) were investigated as model compounds. The number of 3d electrons and the magnetic orbitals have been varied on both sites of the bimetallic cyanide polymer by combining with the hexacyanoferrate or the hexacyanochromate entities' various divalent metal ions A2+ (Mn2+, Fe2+, Co2+, Ni2+, and Cu2+). These PBA were studied by Fe and Cr X-ray absorption spectroscopy and XMCD. The results, compared to those obtained at the A K-edges in a previous work, show that transition-metal K-edge XMCD is very sensitive to orbital symmetry and can therefore give valuable information on the local structure of the magnetic centers. Expressions of the intensity of the main 1s → 4p contribution to the signal are proposed for all K-edges and all compounds. The results pave the way toward a new tool for molecular materials able to give access to valuable information on the local orientation of the magnetic moments or to better understand the role of 4p orbitals involved in their magnetic properties.

Toward Quantitative Magnetic Information from Transition Metal K-Edge XMCD of Prussian Blue Analogs.

Two series of Prussian blue analogs (PBA) were used as model compounds in order to disentangle the information contained in X-ray magnetic circular dichroism (XMCD) at the K-edges of transition metals. The number of 3d electrons on one site of the bimetallic cyanide polymer has been varied by associating to the [Fe(CN)6]3- or the [Cr(CN)6]3- precursors various divalent metal ions A2+ (Mn2+, Fe2+, Co2+, Ni2+, and Cu2+). The compounds were studied by X-ray diffraction and SQUID magnetometry, as well as by X-ray absorption spectroscopy and XMCD at the K-edges of the A2+ transition metal ion. The study shows that the 1s → 4p contribution to the A K-edge XMCD signal can be related to the electronic structure and the magnetic behavior of the probed A2+ ion: the shape of the signal to the filling of the 3d orbitals, the sign of the signal to the direction of the magnetic moment with respect to the applied magnetic field, the intensity of the signal to the total spin number SA, and the area under curve to the Curie constant CA. The whole study hence demonstrates that PBAs are particularly well-adapted for understanding the information contained in the transition metals K-edge XMCD signals. It also offers new perspectives toward the full disentangling of the information contained in these signals and access to new insights into materials magnetic properties.

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.

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.

Preparation, characterization and activity of CuZn and Cu2 superoxide dismutase mimics encapsulated in mesoporous silica.

Encapsulation of three superoxide dismutase (SOD) functional mimics, [CuZn(dien)2(µ-Im)(ClO4)2]ClO4 (1), [Cu2(dien)2(µ-Im)(ClO4)2]ClO4 (2) (Im = imidazolate, dien = diethylenetriamine), and [CuZn(salpn)Cl2] (3) (H2salpn = 1,3-bis(salicylideneamino)propane) in mesoporous MCM-41 silica afforded three hybrid catalysts 1@MCM-41, 2@MCM-41 and 3@MCM-41. Spectroscopic and magnetic analyses of these materials confirmed the metal centers of the complexes keep the coordination sphere after insertion into the MCM-41 silica matrix. For the imidazolate-bridged complexes the silica channels restraint the relative orientation of the two metal ions. While 3@MCM-41 shows SOD activity significantly lower than the host-free complex, insertion of the imidazolate-bridged CuZn or Cu2 complexes by ion exchange onto mesoporous MCM-41 silica affords durable and recoverable supported catalysts with much better SOD activity than the free complexes. For confined imidazolate-bridged complexes, 1@MCM-41 and 2@MCM-41, the small pore size of the silica matrix improves the SOD activity more than a host with larger pores. This high SOD activity is attributed to the close-fitting of the complexes into the nanochannels of MCM-41 silica that favors the Cu active site and HImZn(or Cu) group stay in close proximity during catalysis.

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.

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.

An unprecedented {Ni14SiW9} hybrid polyoxometalate with high photocatalytic hydrogen evolution activity.

A unique polyoxometalate complex made up of a tetradecanuclear nickel bisphosphonate cluster capping a {SiW9} unit has been characterized. This stable compound exhibits a high hydrogen evolution reaction photocatalytic activity under visible light irradiation via a reductive quenching mechanism.

Great Genetic Diversity but High Selfing Rates and Short-Distance Gene Flow Characterize Populations of a Tree (Foetidia; Lecythidaceae) in the Fragmented Tropical Dry Forest of the Mascarene Islands.

Following the global trend of deforestation and degradation, tropical dry forests in the Mascarenes archipelago on Reunion has undergone harsh reduction and fragmentation within 3 centuries of human occupation. We investigated the genetic diversity, mating system, and gene flow in fragmented populations of the native tree Foetidia mauritiana (Lecythidaceae) on Reunion, using microsatellite genotyping of adults (in- and ex situ) and seed progenies (in situ only). To test genetic isolation between the Mascarene islands, we also genotyped conspecific adults on Mauritius, and trees of Foetidia rodriguesiana on Rodrigues. We found a high genetic diversity among the trees on Reunion, but no population structure (G'ST: 0.039-0.090), and an increase of the fixation index (FIS) from adults to progenies. A subsequent analysis of mating systems from progeny arrays revealed selfing rates >50% in fragmented populations and close to 100% in lone trees. A paternity analysis revealed pollen flow ranging from 15.6 to 296.1 m within fragments. At broader scale, the populations of F. mauritiana on Reunion and Mauritius are genetically differentiated. The morphologically allied taxa F. rodriguesiana and F. mauritiana are clearly isolated. Therefore, this case study shows that genetic diversity may persist after deforestation, especially in long-lived tree species, but the reproductive features may be deeply altered during this process. This would explain the low seed production and the absence of recruitment in F. mauritiana. Restoration programs should take into account these features, as well as the importance that trees ex situ represent in restoring and conserving diversity.

A spin crossover porous hybrid architecture for potential sensing applications.

Spin crossover cations have been successfully synthesized in the pores of a mesoporous robust Metal-Organic Framework (MOF) MIL-100(Al) through sequential introduction of Fe(iii) cations and a sal2trien ligand. The MIL-100(Al)@Fe(sal2trien) hybrid material retains its crystallinity and partial porosity compared to the parent MOF. The spin state of the Fe(sal2trien)+ cations can be modulated at room temperature through sorption of guest molecules, paving the way to the design of a new generation of sensors based on MOF@spin crossover complex solids.

Evidence of the Core-Shell Structure of (Photo)magnetic CoFe Prussian Blue Analogue Nanoparticles and Peculiar Behavior of the Surface Species.

We report on a comparative study of 5.5 nm (embedded in an ordered mesoporous silica matrix) and 100 nm (free) (photo)magnetic CoFe Prussian blue analogue (PBA) particles. Co and Fe K-edge X-ray absorption spectroscopy, X-ray diffraction, infrared spectroscopy, and magnetic measurements point out a core-shell structure of the particles in their ground states. In the 5.5 nm particles, the 11.5 Šthick shell is made of Fe(CN)6 entities and CoII-NC-FeIII linkages departing from the geometry usually encountered in PBA, whatever the oxidation state (CoIIFeIII or CoIIIFeII) of the CoFe pairs in the core. In the photomagnetic particles, the photomagnetic effect in the core of the particles is due to the same photoinduced CoIII(LS)FeII → CoII(HS)FeIII electron transfer whatever the size of the particles. The shell of the nanoparticles exhibits a peculiar photoinduced structural rearrangement, and the nanoparticles in their photoexcited state exhibit a superparamagnetic behavior.

Bicapped Keggin polyoxomolybdates: discrete species and experimental and theoretical investigations on the electronic delocalization in a chain compound.

Three monomeric polyoxometalates [M(C10H8N2)3][α-PMoMoO40Zn2(C10H8N2)2]·2H2O (M-PMo12Zn2, M = Fe, Co, Ru) with {Zn(bpy)2}2+ units capped on reduced α-Keggin polyanions and [M(bpy)3]2+ counter-ions were synthesized under hydrothermal conditions. The 1D polymer [N(C4H9)4][Ru(C10H8N2)3][α-PMoMoO43] (Ru-PMo14) was prepared by a similar strategy, in the absence of 2,2'-bpy ligands. In this chain capped reduced Keggin anions are linked via Mo-O-Mo bridges and are surrounded by both tetrabutylammonium cations and [Ru(bpy)3]2+ counter-ions. The compounds were characterized in the solid state by single crystal and powder X-ray diffraction and IR spectroscopy and in solution by 31P NMR spectroscopy. 31P diffusion ordered NMR spectroscopy (DOSY) indicates that the diffusion coefficient of the dissolved species of Ru-PMo14 corresponds to a dimeric structure. Magnetic susceptibility measurements performed on Ru-PMo14 show the existence of antiferromagnetic interactions between the d1 electrons of the six MoV centers, with a singlet spin ground state. However, attempts to fit the data in the 2-300 K temperature range with Heisenberg Hamiltonians adapted for 0 or 1D systems suggest that these electrons are delocalized. Density Functional Theory (DFT) and Wave Function Theory (WFT) calculations indicate a migration of the electrons of the capping MoV centers into the PMo12 units at high temperature, allowing the rationalization of the experimental observations.

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.

Tuning the MnII2/MnIII2 redox cycle of a phenoxo-bridged diMn catalase mimic with terminal carboxylate donors.

A new phenoxo-bridged diMnIII complex, Na[Mn2L(OH)2(H2O)2]·5H2O (1), obtained with the ligand L5- = 5­methyl­2­hydroxo­1,3­xylene­α,α­diamine­N,N,N',N'­tetraacetato, has been prepared and characterized. Mass spectrometry, conductivity, UV-visible, EPR and 1H NMR spectroscopic studies showed that the complex exists in solution as a monoanionic diMnIII complex. Complex 1 catalyzes H2O2 disproportionation with second-order rate constant kcat = 305(9) M-1 min-1 and without a time-lag phase. Based on spectroscopic results, the catalase activity of complex 1 in methanol involves a MnIII2/MnII2 redox cycle, which distinguishes this catalyst from other phenoxo-bridged diMn complexes that cycle between MnIIMnIII/MnIIIMnIV species. Addition of base stabilizes the catalyst, restrains demetallation during catalysis and causes moderate enhancement of catalase activity. The terminal carboxylate donors of 1 not only contribute as internal bases to assist deprotonation of H2O2 but also favor the formation of active homovalent diMn species, just as observed for the enzyme.