Tunable magnetic anisotropy in luminescent cyanido-bridged {Dy2Pt3} molecules incorporating heteroligand PtIV linkers.

The interest in the generation of photoluminescence in lanthanide(III) single-molecule magnets (SMMs) is driven by valuable magneto-optical correlations as well as perspectives toward magnetic switching of emission and opto-magnetic devices linking SMMs with optical thermometry. In the pursuit of enhanced magnetic anisotropy and optical features, the key role is played by suitable ligands attached to the 4f metal ion. In this context, cyanido complexes of d-block metal ions, serving as expanded metalloligands, are promising. We report two novel discrete coordination systems serving as emissive SMMs, {[DyIII(H2O)3(tmpo)3]2[PtIVBr2(CN)4]3}·2H2O (1) and {[DyIII(H2O)(tmpo)4]2[PtIVBr2(CN)4]3}·2CH3CN (2) (tmpo = trimethylphosphine oxide), obtained by combining DyIII complexes with uncommon dibromotetracyanidoplatinate(IV) ions, [PtIVBr2(CN)4]2-. They are built of analogous Z-shaped cyanido-bridged {Dy2Pt3} molecules but differ in the coordination number of DyIII (C.N. = 8 in 1, C.N. = 7 in 2) and the number of coordinated tmpo ligands (three in 1, four in 2) which is related to the applied solvents. As a result, both compounds reveal DyIII-centred slow magnetic relaxation but only 1 shows SMM character at zero dc field, while 2 is a field-induced SMM. The relaxation dynamics in both systems is governed by the Raman relaxation mechanism. These effects were analysed using ac magnetic data and the results of the ab initio calculations with the support of magneto-optical correlations based on low-temperature high-resolution emission spectra. Our findings indicate that heteroligand halogeno-cyanido PtIV complexes are promising precursors for emissive SMMs with the further potential of sensitivity to external stimuli that may be related to the lability of the axially positioned halogeno ligands.

Large breathing effect induced by water sorption in a remarkably stable nonporous cyanide-bridged coordination polymer.

While metal-organic frameworks (MOFs) are at the forefront of cutting-edge porous materials, extraordinary sorption properties can also be observed in Prussian Blue Analogs (PBAs) and related materials comprising extremely short bridging ligands. Herein, we present a bimetallic nonporous cyanide-bridged coordination polymer (CP) {[Mn(imH)]2[Mo(CN)8]} n (1Mn; imH = imidazole) that can efficiently and reversibly capture and release water molecules over tens of cycles without any fatigue despite being based on one of the shortest bridging ligands known - the cyanide. The sorption performance of {[Mn(imH)]2[Mo(CN)8]} n matches or even outperforms MOFs that are typically selected for water harvesting applications with perfect sorption reversibility and very low desorption temperatures. Water sorption in 1Mn is possible due to the breathing effect (accompanied by a dramatic cyanide-framework transformation) occurring in three well-defined steps between four different crystal phases studied structurally by X-ray diffraction structural analysis. Moreover, the capture of H2O by 1Mn switches the EPR signal intensity of the MnII centres, which has been demonstrated by in situ EPR measurements and enables monitoring of the hydration level of 1Mn by EPR. The sorption of water in 1Mn controls also its photomagnetic behavior at the cryogenic regime, thanks to the presence of the [MoIV(CN)8]4- photomagnetic chromophore in the structure. These observations demonstrate the extraordinary sorption potential of cyanide-bridged CPs and the possibility to merge it with the unique physical properties of this class of compounds arising from their bimetallic character (e.g. photomagnetism and long-range magnetic ordering).

Hepta-coordinated Ni(II) assemblies - structure and magnetic studies.

Two mononuclear complexes [Ni(dapsc)(H2O)2]Cl(NO3)·H2O (1) and [Ni(dapsc)(NCS)2] (2), and a bimetallic CN-bridged trinuclear molecule [NiII(dapsc)(H2O)]2[WIV(CN)8]·11H2O (3) (dapsc = 2,6-diacetylpyridine-bis(semicarbazone)) were synthesised and characterised in terms of structure and magnetic properties. All three compounds contain Ni(ii) ions in a pentagonal bipyramid coordination geometry afforded by the equatorial pentadentate ligand (dapsc) and two O- or N-donating axial ligands. The compounds differ in the relative arrangement of the complexes, intermolecular interactions and distortion from the ideal coordination geometry. The high-field EPR and magnetometric studies show large anisotropy of the Ni(ii) centres with the D parameters in the range of -10.5 to -21.2 cm-1 and negligible antiferromagnetic interactions. The easy-axis magnetic anisotropies of 1-3 were reproduced by ab initio CASSCF/NEVPT2 calculations. The ground states consist mainly of the |MS = |±1 states, which is consistent with the fact that no out-of-phase signal can be detected in the AC magnetic susceptibility measurements.

Tuning of magnetic properties of the 2D CN-bridged NiII-NbIV framework by incorporation of guest cations of alkali and alkaline earth metals.

The reaction between [Ni(cyclam)]2+ (cyclam = 1,4,8,11-tetraazacyclotetradecane) and [Nb(CN)8]4- in concentrated water solutions of different s-block metal salts leads to the formation of 2-dimensional honeycomb-like coordination networks of the formula Mx[Ni(cyclam)]3[Nb(CN)8]2·nH2O (x = 2: M = Li+, Na+; x = 1: M = Mg2+, Ca2+, Sr2+, Ba2+). The CN-bridged Ni-Nb coordination layers are intersected by channels filled with crystallisation water molecules and guest mono- or di-valent metal cations, which compensate the negative charge of the framework. The structural details and crystal symmetry vary between the networks, depending on the arrangement of the water molecules and the intermolecular interactions enforced by the guest cations. All compounds show long range magnetic order arising from superexchange interactions between paramagnetic NiII (s = 1) and NbIV (s = 1/2) centres through CN-bridges within the layers and weaker inter-layer interactions mediated by H-bonds. The ordering temperature as well as the coercive field of the magnetic hysteresis can be tuned by the type of guest cation, with the highest values achieved for Mg2+ and the lowest for Na+.

Solvent- and Temperature-Driven Photoluminescence Modulation in Porous Hofmann-Type SrII-ReV Metal-Organic Frameworks.

A unique family of three-dimensional (3D) luminescent SrII-ReV metal-organic frameworks (MOFs), {[SrII(MeOH)5][ReV(CN)4(N)(bpen)0.5]·MeOH}n [1·MeOH; N3- = nitrido ligand, bpen = 1,2-bis(4-pyridyl)ethane, and MeOH = methanol], {[SrII(MeOH)4][ReV(CN)4(N)(bpee)0.5]·2MeOH}n [2·MeOH; bpee = 1,2-bis(4-pyridyl)ethylene], and {[SrII(bpy)0.5(MeOH)2][ReV(CN)4(N)(bpy)0.5]}n (3·MeOH; bpy = 4,4'-bipyridine), is reported. They are obtained by the molecular self-assembly of Sr2+ ions with tetracyanidonitridorhenate(V) metalloligands, [ReV(CN)4(N)]2-, and pyridine-based organic spacers (L = bpen, bpee, bpy). Such a combination of molecular precursors results in bimetallic SrII-ReV cyanido-bridged layers further bonded by organic ligands into pillared Hofmann-type coordination skeletons. Because of the formation of {ReV-(L)-ReV} moieties providing emissive metal-to-ligand charge-transfer states, 1·MeOH-3·MeOH exhibit solid-state room-temperature photoluminescence tunable from green to orange by the applied organic ligand. The most stable MOF of 3·MeOH, based on the alternating {ReV-(bpy)-ReV} and {SrII-(bpy)-SrII} linkages, exhibits three interconvertible, variously solvated phases, methanol-solvated 3·MeOH, hydrated {[SrII(bpy)0.5(H2O)2][ReV(CN)4(N)(bpy)0.5]·0.6H2O}n (3·H2O), and desolvated {[SrII(bpy)0.5][ReV(CN)4(N)(bpy)0.5]}n (3). Their formation was correlated with water and methanol vapor sorption properties investigated for 3·H2O. The solvent content affects the luminescence mainly by tuning the emission energy within the series of 3·MeOH, 3·H2O, and 3. All of the obtained compounds exhibit temperature-driven modulation of luminescence, including the shift of the emission maximum and lifetime. The thermochromic luminescent response was found to be sensitive to the presence and type of solvent in the crystal lattice. This work shows that the construction of [ReV(CN)4(N)]2--based MOFs is an efficient route toward advanced solid luminophores tunable by external stimuli such as solvent or temperature.

Room-Temperature Bistability in a Ni-Fe Chain: Electron Transfer Controlled by Temperature, Pressure, Light, and Humidity.

Bistable and stimuli-responsive molecule-based materials are promising candidates for the development of molecular switches and sensors for future technologies. The CN-bridged {NH4 [Ni(cyclam)][Fe(CN)6 ]⋅5 H2 O}n chain exists in two valence states: NiII -FeIII (1HT ) and NiIII -FeII (1LT ) and shows unique multiresponsivity under ambient conditions to various stimuli, including temperature, pressure, light, and humidity, which generate measurable response in the form of significant changes in magnetic susceptibility and color. The electron-transfer phase transition 1LT ↔1HT shows room-temperature thermal hysteresis, can be induced by irradiation, and shows high sensitivity to small applied pressure, which shifts it to higher temperatures. Additionally, it can be reversibly turned off by dehydration to the {NH4 [NiII (cyclam)][FeIII (CN)6 ]}n (1 d) phase, which features the NiII -FeIII valence state over the whole temperature range, but responds to pressure by yielding NiIII -FeII above 1.06 GPa.

Guest-Dependent Pressure-Induced Spin Crossover in FeII 4 [MIV (CN)8 ]2 (M=Mo, W) Cluster-Based Material Showing Persistent Solvent-Driven Structural Transformations.

Discrete molecular species that can perform certain functions in response to multiple external stimuli constitute a special class of multifunctional molecular materials called smart molecules. Herein, cyanido-bridged coordination clusters {[FeII (2-pyrpy)2 ]4 [MIV (CN)8 ]2 }⋅4 MeOH⋅6 H2 O (M=Mo (1 solv), M=W (2 solv) and 2-pyrpy=2-(1-pyrazolyl)pyridine are presented, which show persistent solvent driven single-crystal-to-single-crystal transformations upon sorption/desorption of water and methanol molecules. Three full desolvation-resolvation cycles with the concomitant change of the host molecules do not damage the single crystals. More importantly, the Fe4 M2 molecules constitute a unique example where the presence of the guests directly affects the pressure-induced thermal spin crossover (SCO) phenomenon occurring at the FeII centres. The hydrated phases show a partial SCO with approximately two out-of-four FeII centres undergoing a gradual thermal SCO at 1 GPa, while in the anhydrous form the pressure-induced SCO effect is almost quenched with only 15 % of the FeII centres undergoing high-spin to low-spin transition at 1 GPa.

Proton-Conducting Humidity-Sensitive NiII-NbIV Magnetic Coordination Network.

The 2D coordination network (NH4)2[NiII(cyclam)]3[NbIV(CN)8]2·21H2O (1·21H2O) was obtained on a cation-assisted synthetic pathway. The reaction between [Ni(cyclam)]2+ and [Nb(CN)8]4- in the presence of excess of NH4Cl resulted in the formation of negatively charged coordination layers with the simultaneous incorporation of the NH4+ cations into the microporous channels of the structure. 1·21H2O network can be partly dehydrated in a single-crystal-to-single-crystal structural transformation to give (NH4)2[NiII(cyclam)]3[NbIV(CN)8]2·14H2O (1·14H2O). The dehydration-induced structural changes, in particular the deformation of CN--bridges and the disruption of interlayer interactions, give rise to the solvatomagnetic effect. Fully hydrated 1·21H2O phase is a ferrimagnet with a critical temperature of magnetic ordering of 7.6 K and a narrow magnetization hysteresis loop, while 1·14H2O hydrate is an antiferromagnet with Tc = 7.2 K and metamagnetic transition at 6.3 kOe. Thanks to the presence of the NH4+ ions in the structure, the proton conductivity of ∼4 × 10-5 S cm-1 (295 K, 100% relative humidity, RH) is observed with the activation energy of 0.80 eV.

Multi-colour uranyl emission efficiently tuned by hexacyanidometallates within hybrid coordination frameworks.

Unique hybrid organic-inorganic coordination networks, three-dimensional [(UO2)2(OH)(4,4'-bpdo)2][M(CN)6]·nH2O (M = Co, 1; Rh, 2; Ir, 3) and layered [(UO2)2(OH)2(4,4'-bpdo)2][Pt(CN)6]·H2O (4), employing cyanide, hydroxide and 4,4'-bpdo bridges, are reported. They exhibit vibronically coupled charge transfer emission of uranyl ions, whose colour is tunable from green to orange by the implemented hexacyanidometallates.

Connecting Visible Photoluminescence and Slow Magnetic Relaxation in Dysprosium(III) Octacyanidorhenate(V) Helices.

Functional crystalline materials based on bimetallic cyanido-bridged {[DyIII(4-Mephen)(dmf)4][MV(CN)8]}·0.5H2O (M = Re, 1; Mo, 2; W, 3; 4-Mephen = 4-methyl-1,10-phenanthroline) helices have been prepared. 1 is the first heterometallic coordination polymer incorporating an unexplored [ReV(CN)8]3- ion. Implementation of the ReV-based diamagnetic analogue of broadly investigated paramagnetic [MoV(CN)8]3- and [WV(CN)8]3- ions into the d-f coordination framework results in yellow photoluminescence originating from 4F9/2 → 6H J f-f electronic transitions of DyIII sensitized by 4-Mephen, and field-induced slow magnetic relaxation related to the single-ion anisotropy of the dysprosium(III) complexes. We prove that [ReV(CN)8]3- can work as a noninnocent metalloligand in the preparation of emissive 4f-metal-based single-molecule magnets.

Dehydration-Triggered Charge Transfer and High Proton Conductivity in (H3O)[NiIII(cyclam)][MII(CN)6] (M = Ru, Os) Cyanide-Bridged Chains.

The coexistence of dehydration-driven charge transfer, magnetic interactions, and high proton conductivity was found in two bimetallic alternating CN-bridged chains {(H3O)[NiIII(cyclam)][MII(CN)6]·5H2O} n (M = Ru (1), Os (2); cyclam = 1,4,8,11-tetraazacyclotetradecane). Dehydration of these materials causes structural transformation and triggers charge transfer between the metal centers: NiIII-NC-MII → NiII-NC-MIII. The CT process, whose extent is tuned by the change of the anionic building block, causes significant increase of magnetic moment, appearance of antiferromagnetic interactions, and noticeable changes in color. The high conductivity values of σ = 1.09 × 10-3 (1) and 1.12 × 10-3 S cm-1 (2) at 295 K and 100% relative humidity allow the classification of the materials as superionic conductors. The proton conduction occurs according to the Grotthuss mechanism as a hopping of protons between H-bonded water molecules due to the presence of the H3O+ ions, which compensate negative charge of the coordination chains.

A Photomagnetic Sponge: High-Temperature Light-Induced Ferrimagnet Controlled by Water Sorption.

"Converting" light energy to magnetization is the attribute of molecule-based compounds called photomagnets and is inaccessible for conventional magnetic solids. The design and synthesis of such compounds, however, is a formidable challenge, and only a few examples are known, all with rather low magnetic ordering temperatures well below the boiling point of liquid nitrogen. Herein, a cyanide-bridged coordination polymer, {[MnII(imidazole)]2[WIV(CN)8]} n, exhibiting the highest light-induced magnetic ordering temperature ever observed and a magnetic hysteresis loop up to 90 K is reported. The photomagnetic effect results from the blue light excitation (450 nm) of the constituent octacyanotungstate(IV) moiety, which then couples magnetically with manganese(II), resulting in light-induced ferrimagnetic ordering. The reported coordination framework shows also outstanding water sorption properties that are strongly correlated with the photomagnetic functionality. The photoswitching observed in the anhydrous state is completely quenched by the reversible capture of water, with the fully hydrated phase becoming practically non-photomagnetic.

Dehydration of Octacyanido-Bridged NiII-WIV Framework toward Negative Thermal Expansion and Magneto-Colorimetric Switching.

An inorganic three-dimensional [NiII(H2O)2]2[WIV(CN)8]·4H2O (1) framework undergoes a single-crystal-to-single-crystal transformation upon thermal dehydration, producing a fully anhydrous phase NiII2[WIV(CN)8] (1d). The dehydration process induces changes in optical, magnetic, and thermal expansion properties. While 1 reveals typical positive thermal expansion of the crystal lattice, greenish-yellow color, and paramagnetic behavior, 1d is the first ever reported octacyanido-based solid revealing negative thermal expansion, also exhibiting a deep red color and diamagnetism. Such drastic shift in the physical properties is explained by the removal of water molecules, leaving the exclusively cyanido-bridged bimetallic network, which is accompanied by the transformation of the octahedral paramagnetic [NiII(H2O)2(NC)4]2- to the square-planar diamagnetic [NiII(NC)4]2- moieties.

Ligand dependent topology and spontaneous resolution in high-spin cyano-bridged Ni3W2 clusters.

Two high-spin pentanuclear NiW clusters with diimine blocking ligands have been obtained: {[Ni(4,4'-MeObpy)2]3[W(CN)8]2}·12H2O (1) and {[Ni(phen)2(H2O)][Ni(phen)2]2[W(CN)8]2}·7H2O (2) (4,4'-MeObpy = 4,4'-dimethoxy-2,2'-bipyridine, phen = 1,10-phenanthroline). Despite the similarity of the building blocks and synthetic conditions the compounds show different topologies of the cluster core: 1 is a trigonal bipyramid while 2 is a decorated square. Both cluster structures are chiral with either ΔΔΔ or ΛΛΛ configuration around all three Ni centres. In 1 spontaneous resolution occurs and it crystallises in the P212121 space group forming a conglomerate containing both types of enantiomorphic crystals. 1Δ and 1Λ are the first pair of enantiomorphic structures of cyano-bridged clusters of trigonal bipyramidal topology obtained with achiral bidentate blocking ligands. 2 crystallises as a racemic compound in a centrosymmetric space group P1[combining macron] with both enantiomers present in the structure. 2 is an exceptional square-motif containing structure with an identical stereoconfiguration of all complex cations within one cluster. Ferromagnetic interactions are present in both clusters resulting in the ground spin state S = 4.

Hydration-switchable charge transfer in the first bimetallic assembly based on the [Ni(cyclam)](3+)--magnetic CN-bridged chain {(H3O)[Ni(III)(cyclam)][Fe(II)(CN)6]·5H2O}n.

An alternating bimetallic {(H3O)[Ni(III)(cyclam)][Fe(II)(CN)6]·5H2O}n chain undergoes reversible dehydration at 40 °C accompanied by electron transfer which leads to Ni(II)-Fe(III) in about 50% of metal centres. The hydrated dark blue form is a paramagnet while the dehydrated yellowish-green form shows ferromagnetic coupling between neighbouring Ni(II) and Fe(III).

New topology of CN-bridged clusters: dodecanuclear face-sharing defective cubes based on octacyanometallates(iv) and nickel(ii) with diimine ligands.

New dodecanuclear bimetallic Ni8M4 clusters were obtained in the reaction between octacyanometallates(IV), nickel(II) cations and diimine ligands. {[Ni(LL)(H2O)]2[Ni(LL)(H2O)2]6[M(CN)8]4} assemblies, where LL = 1,10-phenanthroline M = Mo, (1) or LL = 2,2'-bipyridine M = W (2) or Mo (3), are among the largest octacyanometallate-based clusters. They show the same compact topology of the cluster core, which can be described as defective face-sharing cubes with corners defined by alternating metal centres. The structures are stabilised by π­π interactions between aromatic rings of diimine ligands and hydrogen bonds connecting terminal CN groups and coordinated H2O molecules through a crystallisation solvent. Different decorating ligands cause different arrangements of clusters in the crystal structure. 1 crystallises in the triclinic system space group P, while 2 and 3 crystallise in the monoclinic system space group P21/n. The clusters show paramagnetic behaviour with weak antiferromagnetic interactions between the NiII centres through diamagnetic NC-MIV-CN linkages.

Multifunctionality in molecular magnetism.

Molecular magnetism draws from the fundamental ideas of structural chemistry and combines them with experimental physics resulting in one of the highest profile current topics, namely molecular materials that exhibit multifunctionality. Recent advances in the design of new generations of multifunctional molecular magnets that retain the functions of the building blocks and exhibit non-trivial magnetic properties at higher temperatures provide promising evidence that they may be useful for the future construction of nanoscale devices. This article is not a complete review but is rather an introduction into thefascinating world of multifunctional solids with magnetism as the leitmotif. We provide a subjective selection and discussion of the most inspiring examples of multifunctional molecular magnets: magnetic sponges, guest-responsive magnets, molecular magnets with ionic conductivity, photomagnets and non-centrosymmetric and chiral magnets.

A water sensitive ferromagnetic [Ni(cyclam)]2[Nb(CN)8] network.

Reaction between [Ni(cyclam)](2+) and [W(CN)(8)](4-) leads to the formation of a 3D diamond-like network [Ni(cyclam)](2)[W(CN)(8)]·3.5H(2)O (1). The structure is characterised by a network of intersecting channels of 3-4 Å in diameter, filled with crystallisation water, most of which is released upon drying in air, causing the crystals to collapse. Analogous compound [Ni(cyclam)](2)[Nb(CN)(8)]·3.5H(2)O (2), based on paramagnetic Nb(IV), could only be obtained as a powder, due to the decomposition of the [Nb(CN)(8)](4-) complex under slow diffusion conditions. It shows long-range magnetic ordering with T(C) = 11.8 K and magnetic hysteresis at 2 K. These properties are lost upon drying in air. After rehydration differently shaped hysteresis appears, which together with AC susceptibility measurements suggests the formation of a multiphase system. Subsequent dehydration-rehydration experiments show partial reversibility.