Local force constants and charges of the nitrosyl ligand in photoinduced NO linkage isomers in a prototypical ruthenium nitrosyl complex.

Photoinduced linkage isomers (PLI) of the NO ligand in transition-metal nitrosyl compounds can be identified by vibrational spectroscopy due to the large shifts of the (NO) stretching vibration. We present a detailed experimental and theoretical study of the prototypical compound K2[RuCl5NO], where (NO) shifts by ≈150 cm-1 when going from the N-bound (κN) ground state (GS) to the oxygen-bound (κO) metastable linkage isomer MS1, and by ≈360 cm-1 when going to the side-on (κ2N,O) metastable linkage isomer MS2. We show that the experimentally observed N-O stretching modes of the GS, MS1, and MS2 exhibit strong coupling with the Ru-N and Ru-O stretching modes, which can be decoupled using the local mode vibrational theory formalism. From the resulting decoupled pure two-atomic harmonic oscillators the local force constants are determined, which all follow the same quadratic behavior on the wavenumber. A Bader charge analysis shows that the total charge on the NO ligand is not correlated to the observed frequency shift of (NO).

Photogeneration of Several Linkage Isomers and Investigation of Forward and Backward Nitro-Nitrito Isomerization Processes in a Palladium Complex.

Photoinduced linkage isomers (PLIs) of the nitro-ligand were generated and comprehensively characterized in a square planar unit [Pd(NH3)3NO2]+ of the complex salts [Pd(NH3)4][Pd(NH3)3NO2][MOx3]·yH2O (M = Cr (Cr), Rh (Rh), Co (Co), Ox = oxalate). Structural (XRD) and spectroscopic (IR, UV-vis) investigations at 10 and 150 K allowed determining the structures of several photoinduced linkage isomers, endo-ONO (PLI1, 2) and exo-ONO (PLI3, 4) isomers generated by irradiation with 365 nm from the initial NO2 (GS), along with the assignment of the infrared (IR) bands to each structural isomer. Based on a combination of these methods, the photo- and thermally induced interplay of PLIs was investigated. Irradiation in the temperature range of 10-80 K induces the formation of both endo- and exo-ONO isomers, while increasing the temperature up to 150 K results in the formation of only endo-ONO isomers. The structural arrangement of the endo-ONO and exo-ONO PLI is strongly influenced by intermolecular interactions due to the partial occupation of a neighboring site by water molecules. The investigation of thermal dynamics of PLIs revealed that the thermal decay of the exo-ONO isomer occurs via two steps exo-ONO → endo-ONO → NO2. The kinetic parameters (Ea, k0) of both decay processes were determined together with the characteristic decay temperatures (Td) by IR spectroscopy. According to the photoinduced dynamics measured by IR spectroscopy, the mechanism of PLI formation in [Pd(NH3)3NO2]+ could be described as NO2 → endo-ONO → exo-ONO.

Weak Coordinating Character of Organosulfonates in Oriented Silica Films: An Efficient Approach for Immobilizing Cationic Metal-Transition Complexes.

Iron (II) tris(2,2'-bipyridine) complexes, [Fe(bpy)3]2+, have been synthesized and immobilized in organosulfonate-functionalized nanostructured silica thin films taking advantage of the stabilization of [Fe(H2O)6]2+ species by hydrogen bonds to the anionic sulfonate moieties grafted to the silica nanopores. In a first step, thiol-based silica films have been electrochemically generated on indium tin oxide (ITO) substrates by co-condensation of 3-mercaptopropyltrimethoxysilane (MPTMS) and tetraethoxysilane (TEOS). Secondly, the thiol function has been modified to sulfonate by chemical oxidation using hydrogen peroxide in acidic medium as an oxidizing agent. The immobilization of [Fe(bpy)3]2+ complexes has been performed in situ in two consecutive steps: (i) impregnation of the sulfonate functionalized silica films in an aqueous solution of iron (II) sulfate heptahydrate; (ii) dipping of the iron-containing mesostructures in a solution of bipyridine ligands in acetonitrile. The in situ formation of the [Fe(bpy)3]2+ complex is evidenced by its characteristic optical absorption spectrum, and elemental composition analysis using X-ray photoelectron spectroscopy. The measured optical and electrochemical properties of immobilized [Fe(bpy)3]2+ complexes are not altered by confinement in the nanostructured silica thin film.

Pas de Deux of an NO Couple: Synchronous Photoswitching from a Double-Linear to a Double-Bent Ru(NO)2 Core under Nitrosyl Charge Conservation.

The {Ru(NO)2 }10 dinitrosylruthenium complex [Ru(NO)2 (PPh3 )2 ] (1) shows photo-induced linkage isomerism (PLI) of a special kind: the two NO ligands switch, on photo-excitation, synchronously from the ground state (GS) with two almost linear RuNO functions to a metastable state (MS) which persists up to 230 K and can be populated to ≈50 %. The MS was experimentally characterised by photo-crystallography, IR spectroscopy and DS-calorimetry as a double-bent variant of the double-linear GS. The experimental results are confirmed by computation which unravels the GS/MS transition as a disrotatory synchronous 50° turn of the two nitrosyl ligands. Although 1 shows the usual redshift of the N-O stretch on bending the MNO unit, there is no increased charge transfer from Ru to NO along the GS-to-MS path. In terms of the effective-oxidation-state (EOS) method, both isomers of 1 and the transition state are Ru-II (NO+ )2 species.

Multi-stimuli Photo and Redox-active Nanostructured Mesoporous Silica Films on Transparent Electrodes.

Silica matrices hosting transition metal guest complexes may offer remarkable platforms for the development of advanced functional devices. We report here the elaboration of ordered and vertically oriented mesoporous silica thin films containing covalently attached tris(bipyridine)iron derivatives using a combination of electrochemically assisted self-assembly (EASA) method and Huisgen cycloaddition reaction. Such a versatile approach is primarily used to bind nitrogen-based chelating ligands such as (4-[(2-propyn-1-yloxy)]4'-methyl-2,2'-bypiridine, bpy') inside the nanochannels. Further derivatization of the bpy'-functionalized silica thin films is then achieved via a subsequent in-situ complexation step to generate [Fe(bpy)2 (bpy')]2+ inside the mesopore channels. After giving spectroscopic evidences for the presence of such complexes in the functionalized film, electrochemistry is used to transform the confined diamagnetic (S=0) FeLSbpy2bpy'2+ species to paramagnetic (S=1/2) oxidized FeLSbpy2bpy'3+ species in a reversible way, while blue light irradiation (λ=470 nm) enables populating the short-lived paramagnetic (S=2) FeHSbpy2bpy'2+ excited state. [Fe(bpy)2 (bpy')]2+ -functionalized ordered films are therefore both electro- and photo-active through the manipulation of the oxidation state and spin state of the confined complexes, paving the way for their integration in optoelectronic devices.

Spin Crossover and High-Spin State in Fe(II) Anionic Polymorphs Based on Tripodal Ligands.

Two new mononuclear Fe(II) polymorphs, [(C2H5)4N]2[Fe(py3C-OEt)(NCS)3]2 (1) and [(C2H5)4N][Fe(py3C-OEt)(NCS)3] (2) (py3C-OEt = tris(pyridin-2-yl)ethoxymethane), have been synthesized and characterized by single-crystal X-ray diffraction, by magnetic and photomagnetic measurements, and by detailed variable-temperature infrared spectroscopy. The molecular structure, in both complexes, is composed of the same anionic [Fe(py3C-OEt)(NCS)3]- complex (two units for 1 and one unit for 2) generated by coordination to the Fe(II) metal center of one tridentate py3C-OEt tripodal ligand and three terminal κN-SCN coligands. Magnetic studies revealed that polymorph 2 displays a high-spin (HS) state over the entire studied temperature range (300-10 K), while complex 1 exhibits an abrupt and complete spin crossover (SCO) transition at ca. 132.3 K, the structural characterizations of which, performed at 295 and 100 K, show a strong modification, resulting from the thermal evolutions of the Fe-N bond lengths and of the distortion parameters (∑ and Θ) of the FeN6 coordination sphere, in agreement with the presence of HS and low-spin (LS) states at 295 and 100 K, respectively. This thermal transition has been also confirmed by the thermal evolution of the maximum absorbance for ν(NCS) vibrational bands recorded in the temperature range 200-10 K. In 1 the signature of a metastable photoinduced HS state has been observed using photomagnetic and photoinfrared spectroscopy, leading to a similar T(LIESST) relaxation temperature (LIESST = light-induced excited spin-state trapping) of 70 K.

Down and up conversion luminescence of the lead-free organic metal halide material: (C9H8NO)2SnCl6·2H2O.

The present work deals with the optical properties of hybrid organic metal halide material namely (C9H8NO)2SnCl6·2H2O. Its structure is built up from isolated [SnCl6]2- octahedral dianions surrounded by Hydroxyl quinolinium organic cations (C9H8NO)+, abbreviated as [HQ]+. Unlike the usual hybrid materials, where metal halide ions are luminescent semiconductors while the organic ones are optically inactive, [HQ]2SnCl6·2H2O contains two optically active entities: [HQ]+ organic cations and [SnCl6]2- dianions. The optical properties of the synthesized crystals were studied by optical absorption spectroscopy, photoluminescence measurements and DFT calculations of electronic density of states. These studies have shown that both organic and inorganic entities have very close HOMO-LUMO gaps and very similar band alignments favoring the resonant energy transfer process. In addition, measurements of luminescence under variable excitations reveal an intense green luminescence around 497 nm under UV excitation (down conversion) and infrared excitation (up conversion luminescence). The down conversion luminescence is assigned to the π-π* transition within the [HQ] + organic cations involving charge transfer between the organic and inorganic entities, whereas the up-conversion luminescence is based on the triplet-triplet annihilation mechanism (TTA).

Unprecedented Reverse Volume Expansion in Spin-Transition Crystals.

The current craze for research around the spin crossover phenomenon can be justified to some extent by the mechanical properties due to the decrease of volume associated with the transition of the metal ion from the HS state to the LS state. As demonstrated here, the molecular complex [Fe(PM-pBrA)2 (NCS)2 ] exhibits, on the contrary, an increase of the unit-cell volume from HS to LS. This counter-intuitive and unprecedented behavior that concerns both the thermal and the photoexcited spin conversions is revealed by a combination of single-crystal and powder X-ray diffraction complemented by magnetic measurements. Interestingly, this abnormal volume change appears concomitant with the wide rotation of a phenyl ring which induces a drastic modification, though reversible, of the structural packing within the crystal. In addition, the light-induced HS state obtained through the Light-Induced Excited Spin-State Trapping shows a remarkably high relaxation temperature, namely T(LIESST), of 109 K, one of the highest so far reported. The above set of quite unusual characteristics opens up new fields of possibilities within the development of spin crossover materials.

Sensitizer-free photon up conversion in (HQ)2ZnCl4 and HQCl crystals: systems involving resonant energy transfer and triplet-triplet annihilation.

This work deals with normal luminescence and up-conversion luminescence involving charge transfer and triplet-triplet annihilation in the lead free hybrid materials (HQ)2[ZnCl4] and HQCl salt; HQ is the hydroxyquinolate cation (HQ+ = C9H8NO+). The crystal structures were determined by X-ray diffraction and the optical properties were investigated by optical absorption and photoluminescence measurements and electronic band structure calculations. Under UV excitation, the normal luminescence is associated with π-π* transitions within the organic cation and involves energy and charge transfer between the inorganic ion and organic cation. Moreover, photoluminescence measurements under various excitation wavelengths performed on the hybrid (HQ)2[ZnCl4] and the salt HQCl have shown efficient up conversion of light from the near infrared (855 nm) to the visible region at 471 nm and 490 nm respectively. This behavior is described as sensitizer-free up-conversion luminescence based on the triplet-triplet annihilation process (TTA-UCL). These compounds are believed to be the first sensitizer-free TTA up-converting materials found in the organic metal halide family. Compared with the conventional TTA-UC solid systems based on precious and heavy metal organic complexes, the title compounds exhibit efficient photon up-conversion. Furthermore, they have extended the NIR conversion photons to a wide spectral interval of about 300 nm centred around 850 nm.

Photoinduced Mo-CN Bond Breakage in Octacyanomolybdate Leading to Spin Triplet Trapping.

The photoinduced properties of the octacoordinated complex K4 MoIV (CN)8 ⋅2 H2 O were studied by theoretical calculations, crystallography, and optical and magnetic measurements. The crystal structure recorded at 10 K after blue light irradiation reveals an heptacoordinated Mo(CN)7 species originating from the light-induced cleavage of one Mo-CN bond, concomitant with the photoinduced formation of a paramagnetic signal. When this complex is heated to 70 K, it returns to its original diamagnetic ground state, demonstrating full reversibility. The photomagnetic properties show a partial conversion into a triplet state possessing significant magnetic anisotropy, which is in agreement with theoretical studies. Inspired by these results, we isolated the new compound [K(crypt-222)]3 [MoIV (CN)7 ]⋅3 CH3 CN using a photochemical pathway, confirming that photodissociation leads to a stable heptacyanomolybdate(IV) species in solution.

Very Long-Lived Photogenerated High-Spin Phase of a Multistable Spin-Crossover Molecular Material.

The spin-crossover compound [Fe( n-Bu-im)3(tren)](PF6)2 shows an unusual long relaxation time of 20 h after light-induced excited spin state trapping when irradiating at 80 K. This is more than 40 times longer than when irradiating at 10 K. Optical absorption spectroscopy, magnetometry, and X-ray diffraction using synchrotron radiation were used to characterize and explain the different relaxation behaviors of this compound after irradiation below and above 70 K. Rearrangement of the butyl chains of the ligands occurring during the relaxation after irradiation above 70 K is thought to be responsible for the unusually long relaxation time at this temperature.

Conducting Anilate-Based Mixed-Valence Fe(II)Fe(III) Coordination Polymer: Small-Polaron Hopping Model for Oxalate-Type Fe(II)Fe(III) 2D Networks.

The mixed-valence FeIIFeIII 2D coordination polymer formulated as [TAG][FeIIFeIII(ClCNAn)3]·(solvate) 1 (TAG = tris(amino)-guanidinium, ClCNAn2- = chlorocyanoanilate dianionic ligand) crystallized in the polar trigonal space group P3. In the solid-state structure, determined both at 150 and at 10 K, anionic 2D honeycomb layers [FeIIFeIII(ClCNAn)3]- establish in the ab plane, with an intralayer metal-metal distance of 7.860 Å, alternating with cationic layers of TAG. The similar Fe-O distances suggest electron delocalization and an average oxidation state of +2.5 for each Fe center. The cation imposes its C3 symmetry to the structure and engages in intermolecular N-H···Cl hydrogen bonding with the ligand. Magnetic susceptibility characterization indicates magnetic ordering below 4 K and the presence of a hysteresis loop at 2 K with a coercive field of 60 Oe. Mössbauer measurements are in agreement with the existence of Fe(+2.5) ions at RT and statistic charge localization at 10 K. The compound shows semiconducting behavior with the in-plane conductivity of 2 × 10-3 S/cm, 3 orders of magnitude higher than the perpendicular one. A small-polaron hopping model has been applied to a series of oxalate-type FeIIFeIII 2D coordination polymers, providing a clear explanation on the much higher conductivity of the anilate-based systems than the oxalate ones.

Elastic Frustration Triggering Photoinduced Hidden Hysteresis and Multistability in a Two-Dimensional Photoswitchable Hofmann-Like Spin-Crossover Metal-Organic Framework.

We report a two-dimensional Hofmann-like spin-crossover (SCO) material, [Fe(trz-py)2{Pt(CN)4}]·3H2O, built from [FePt(CN)4] layers separated by interdigitated 4-(2-pyridyl)-1,2,4,4H-triazole (trz-py) ligands with two symmetrically inequivalent FeII sites. This compound exhibits an incomplete first-order spin transition at 153 K between fully high-spin (HS-HS) and intermediate high-spin low-spin (HS-LS) ordered states. At low temperature, it undergoes a bidirectional photoswitching to HS-HS and fully low-spin (LS-LS) states with green and near-IR light irradiation, respectively, with associated T(LIESST = Light-Induced Excited Spin-State Trapping) and T(reverse-LIESST) values of 52 and 85 K, respectively. Photomagnetic investigations show that the reverse-LIESST process, performed from either HS-HS or HS-LS states, enables access to a hidden stable LS-LS state, revealing the existence of a hidden thermal hysteresis. Crystallographic investigations allowed to identify that the strong metastability of the HS-LS state originates from the existence of a strong elastic frustration causing antiferroelastic interactions within the [FePt(CN)4] layers, through the rigid NC-Pt-CN bridges connecting the inequivalent FeII sites. The existence of the stable LS-LS state paves the way for a multidirectional photoswitching and allows potential applications for electronic devices based on ternary digits.

Giant Ising-type magnetic anisotropy in trigonal bipyramidal Ni(II) complexes: experiment and theory.

This paper reports the experimental and theoretical investigations of two trigonal bipyramidal Ni(II) complexes, [Ni(Me(6)tren)Cl](ClO(4)) (1) and [Ni(Me(6)tren)Br](Br) (2). High-field, high-frequency electron paramagnetic resonance spectroscopy performed on a single crystal of 1 shows a giant uniaxial magnetic anisotropy with an experimental D(expt) value (energy difference between the M(s) = ± 1 and M(s) = 0 components of the ground spin state S = 1) estimated to be between -120 and -180 cm(-1). The theoretical study shows that, for an ideally trigonal Ni(II) complex, the orbital degeneracy leads to a first-order spin-orbit coupling that results in a splitting of the M(s) = ± 1 and M(s) = 0 components of approximately -600 cm(-1). Despite the Jahn-Teller distortion that removes the ground term degeneracy and reduces the effects of the first-order spin-orbit interaction, the D value remains very large. A good agreement between theoretical and experimental results (theoretical D(theor) between -100 and -200 cm(-1)) is obtained.

Light-induced bistability in the 2 D coordination network {[Fe(bbtr)3][BF4]2}∞ : wavelength-selective addressing of molecular spin states.

Whereas the neat polymeric Fe(II) compound {[Fe(bbtr)3 ][ClO4 ]2 }∞ (bbtr=1,4-di(1,2,3-triazol-1-yl)butane) shows an abrupt spin transition centered at 107 K facilitated by a crystallographic symmetry breaking, in the covalently linked 2D coordination network of {[Fe(bbtr)3 ][BF4 ]2 }∞ , Fe(II) stays in the high-spin state down to 10 K. However, strong cooperative effects of elastic origin result in reversible, persistent, and wavelength-selective photoswitching between the low-spin and high-spin manifolds. This compound thus shows true light-induced bistability below 100 K. The persistent bidirectional optical switching behavior is discussed as a function of temperature, irradiation time, and intensity. Crystallographic studies reveal a photoinduced symmetry breaking and serve to establish the correlation between structure and cooperative effects. The static and kinetic behavior is explicated within the framework of the mean-field approximation.

Structural reinvestigation of the photoluminescent complex [NdCl2(H2O)6]Cl.

The structure of the photoluminescent compound hexaaquadichloridoneodymium(III) chloride has been redetermined from single-crystal X-ray diffraction data at 100 K, with the aim of providing an accurate structural model for the bulk crystalline material. The crystal structure may be described as a network of [NdCl2(H2O)6](+) cations with distorted square-antiprism geometry around the Nd(III) centre. The Nd(III) cation and the nonbonded Cl(-) anion are both located on twofold symmetry axes. The crystal packing consists of three different neodymium pairs linked by a three-dimensional network of O-H···Cl intermolecular interactions. The pair distribution function (PDF) calculated from the experimentally determined structure is used for the discussion of the local structure.

Properties of metastable linkage NO isomers in Na2[Fe(CN)5NO]·2H2O incorporated in mesopores of silica xerogels.

We study the properties of photoinduced metal-nitrosyl linkage isomers in sodium nitroprusside (SNP) as a function of particle size. By embedding the molecular complex at various concentrations into mesopores of silica xerogels the size of the particles can be adjusted. The ground state is characterized by X-ray diffraction, absorption and infrared spectroscopy. The physical properties of the photoswitched molecules were analysed by steady-state low-temperature absorption, infrared spectroscopy and by nanosecond transient absorption spectroscopy. The electronic structure as well as the activation energies of the metastable linkage isomers are independent of the particle size down to single isolated molecules, indicating that the SNP complexes are quasi-free inside the pores of the gel.

Probing the Spin Dimensionality in Single-Layer CrSBr Van Der Waals Heterostructures by Magneto-Transport Measurements.

2D magnetic materials offer unprecedented opportunities for fundamental and applied research in spintronics and magnonics. Beyond the pioneering studies on 2D CrI3 and Cr2 Ge2 Te6 , the field has expanded to 2D antiferromagnets exhibiting different spin anisotropies and textures. Of particular interest is the layered metamagnet CrSBr, a relatively air-stable semiconductor formed by antiferromagnetically-coupled ferromagnetic layers (Tc ∼150 K) that can be exfoliated down to the single-layer. It presents a complex magnetic behavior with a dynamic magnetic crossover, exhibiting a low-temperature hidden-order below T*∼40 K. Here, the magneto-transport properties of CrSBr vertical heterostructures in the 2D limit are inspected. The results demonstrate the marked low-dimensional character of the ferromagnetic monolayer, with short-range correlations above Tc and an Ising-type in-plane anisotropy, being the spins spontaneously aligned along the easy axis b below Tc . By applying moderate magnetic fields along a and c axes, a spin-reorientation occurs, leading to a magnetoresistance enhancement below T*. In multilayers, a spin-valve behavior is observed, with negative magnetoresistance strongly enhanced along the three directions below T*. These results show that CrSBr monolayer/bilayer provides an ideal platform for studying and controlling field-induced phenomena in two-dimensions, offering new insights regarding 2D magnets and their integration into vertical spintronic devices.

1-[3-(4-Nitro-phen-yl)propano-yl]urea acetic acid monosolvate.

The title compound, C(10)H(11)N(3)O(4)·C(2)H(4)O(2), was prepared by an electrochemical technique. In the crystal, acetic acid mol-ecules are involved in hydrogen bonding to two separate propano-ylurea mol-ecules, acting as a donor in an O-H⋯O inter-action and as an acceptor in two N-H⋯O inter-actions. The propano-ylurea mol-ecules inter-act with each other via N-H⋯O hydrogen bonds. C-H⋯O inter-actions also stabilize the crystal structure.

Cyanocarbanion-based spin-crossover materials: photocrystallographic and photomagnetic studies of a new iron(II) neutral chain.

A new iron(II) chain of formula [Fe(abpt)(2)(tcpd)] [1; (tcpd)(2-) = [C(10)N(6)](2-) = (C[C(CN)(2)](3))(2-) = 2-dicyanomethylene-1,1,3,3-tetracyanopropanediide anion, abpt = 4-amino-3,5-bis(pyridin-2-yl)-1,2,4-triazole] has been synthesized and characterized by IR spectroscopy, detailed variable-temperature single-crystal X-ray diffraction, magnetic and photomagnetic measurements. The crystal structure determination of 1 reveals a one-dimensional structural architecture in which the (tcpd)(2-) cyanocarbanion acts as a µ(2)-bridging ligand and the two abpt molecules act as chelating ligands. Detailed X-ray diffraction studies as a function of the temperature (293-10 K) showed a strong modification of the iron coordination sphere, whose characteristics are in agreement with the presence of a spin-crossover transition from high spin (HS) to low spin (LS) in 1. The average Fe-N distances at room temperature, at 10 K following a flash cooling, and at 10 K after subsequent HS-to-LS relaxation are in the range expected for 100%, 50%, and 25% fractions of HS Fe(II), respectively. These observations are consistent with the presence of ca. 25% residual HS species at low temperatures, as derived from the magnetic data. The signature of a photoinduced metastable HS state in 1 has been detected by performing coupled photomagnetic and photocrystallographic analyses. The limiting T(LIESST) value associated with the light-induced excited-spin-state trapping effect was derived as 35 K, in good agreement with the thermal dependence of the unit cell volume upon irradiation. Kinetic studies governing the photoinduced HS/LS process have been recorded at different temperatures; a reverse-LIESST effect has been evidenced at 10 K as a reduction of the residual HS fraction by irradiating the sample at 830 nm.