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Integration of spin crossover (SCO) properties in 3D frameworks made up of cyano-bimetallic layers connected through pillaring organic ligands, the so-called Hofmann-type coordination polymers (HCPs)- represents an important source of multifunctional advanced materials. Typically, these 3D structures are constituted by 4-substituted pyridine-based linear pillars which afford HCPs with regular pcu topology. Here, we have investigated the suitability of the 3-substituted pyridine and pyrimidine bis-monodentate ligands 2,5-di(pyridin-3-yl)aniline (3-dpyan) and 2,5-di(pyrimidin-5-yl)aniline (bpmdan) as alternative building blocks to explore new structural topologies and functionalities. In this context, we have prepared the compounds Fe(3-dpyan)[Ag(CN) 2 ] 2 ·2MeOH ( 1 Ag ·2MeOH ), Fe(3-dpyan)[Ag(CN) 2 ] 2 ···0.35NO 2 Bz·MeOH ( 1 Ag ·0.35NO 2 Bz·MeOH ), Fe(3-dpyan)[Au(CN) 2 ] 2 ·NO 2 Bz ( 1 Au ·NO 2 Bz ), and Fe(bpmdan)[Ag(CN) 2 ] 2 ·CH 3 Bz ( 2 Ag ·CH 3 Bz ) (MeOH = methanol, NO 2 Bz = nitrobenzene, CH 3 Bz = toluene). Our structural studies have revealed that 1 Ag ·2MeOH and 1 Ag ·0.35NO 2 Bz·MeOH exhibit isomorphous doubly interpenetrated 3D structures strongly differing from the unusual noninterpenetrated ones exhibited by 1 Au ·NO 2 Bz and 2 Ag ·CH 3 Bz . Temperature-dependent magnetic susceptibility measurements have shown that all the reported compounds exhibit thermal-induced SCO properties, and moreover, three of them display Light Induced Excited Spin State Trapping at low temperatures (LIESST effect). The studied compounds show a wide diversity of SCO behaviors, ranging from abrupt complete one-step SCO centered at 253 K ( 1 Au ·NO 2 Bz ) to gradual and incomplete multistepped SCO centered at 120 K ( 1 Ag ·0.35NO 2 Bz·MeOH ). This assorted SCO properties are discussed and correlated to the acquired chemical and structural information.

Spin transition (ST) compounds have been extensively studied because of the changes in rich physicochemical properties accompanying the ST process. The study of ST mainly focuses on the temperature-induced spin transition (TIST). To further understand the ST, we explore the pressure response behavior of TIST and pressure-induced spin transition (PIST) of the 2D Hofmann-type ST compounds [Fe(Isoq) 2 M(CN) 4 ] ( Isoq-M ) (M = Pt, Pd, Isoq = isoquinoline). The TISTs of both Isoq-Pt and Isoq-Pd compounds exhibit anomalous pressure response, where the transition temperature ( T 1/2 ) exhibits a nonlinear pressure dependence and the hysteresis width (Δ T 1/2 ) exhibits a nonmonotonic behavior with pressure, by the synergistic influence of the intermolecular interaction and the distortion of the octahedral coordination environment. And the distortion of the octahedra under critical pressures may be the common behavior of 2D Hofmann-type ST compounds. Moreover, Δ T 1/2 is increased compared with that before compression because of the partial irreversibility of structural distortion after decompression. At room temperature, both compounds exhibit completely reversible PIST. Because of the greater change in mechanical properties before and after ST, Isoq-Pt exhibits a more abrupt ST than Isoq-Pd . In addition, it is found that the hydrostatic properties of the pressure transfer medium (PTM) significantly affect the PIST due to their influence on spin-domain formation.

We report herein the synthesis and characterization of two unprecedented isomorphous spin-crossover two-dimensional coordination polymers of the Hofmann-type formulated {Fe II (Hdpyan) 2 (μ 2 -[M II (CN) 4 ]) 2 }, with M II = Pd, Pt and Hdpyan is the in situ partially protonated form of 2,5-(dipyridin-4-yl)aniline (dpyan). The Fe II is axially coordinated by the pyridine ring attached to the 2-position of the aniline ring, while it is equatorially surrounded by four [M II (CN) 4 ] 2- planar groups acting as trans μ 2 -bidentate ligands defining layers, which stack parallel to each other. The other pyridine group of Hdpyan, being protonated, remains peripheral but involved in a strong [M II -C≡N···Hpy + ] hydrogen bond between alternate layers. This provokes a nearly 90° rotation of the plane defined by the [M II (CN) 4 ] 2- groups, with respect to the average plane defined by the layers, forcing the observed uncommon bridging mode and the accumulation of negative charge around each Fe II , which is compensated by the axial [Hdpyan] + ligands. According to the magnetic and calorimetric data, both compounds undergo a strong cooperative spin transition featuring a 10-12 K wide hysteresis loop centered at 220 (Pt) and 211 K (Pd) accompanied by large entropy variations, 97.4 (Pt) and 102.9 (Pd) J/K mol. The breaking symmetry involving almost 90° rotation of one of the two coordinated pyridines together with the large unit-cell volume change per Fe II ( ca . 50 Å 3 ), and subsequent release of significantly short interlayer contacts upon the low-spin → high-spin event, accounts for the strong cooperativity.

Here we show that the porous metal-organic spin crossover (SCO) framework [Fe(tvp) 2 (NCS) 2 ]@4(CH 3 CN·H 2 O) [ 1@4(CH 3 CN·H 2 O) ] is an excellent precursor material for the systematic synthesis, via single-crystal to single-crystal transformation, of a series of halobenzene clathrates. Immersion of samples constituted of single crystals of 1@4(CH 3 CN·H 2 O) in the liquid halobenzenes PhX n , X = F ( n = 1-6), X = Cl ( n = 1, 2), and X = Br ( n = 1) at room temperature induces complete replacement of the guest molecules by PhX n to afford 1@2PhX n . Single-crystal analyses of the new clathrates confirm the integrity of the porous framework with the PhX n guests being organized by pairs via π-stacking filling the nanochannels. The magnetic and calorimetric data confirm the occurrence of practically complete SCO behavior in all of the clathrates. The characteristic SCO equilibrium temperatures, T 1/2 , seem to be the result of a subtle balance in the host-guest interactions, which are temperature- and spin-state-dependent. The radically distinct supramolecular organization of the PhCl 2 guests in 1@2PhCl 2 affords a rare example of four-step SCO behavior following the sequence [HS 1 :LS 0 ] ↔ [HS 2/3 :LS 1/3 ] ↔ [H S 1/2 :L S 1/2 ] ↔ [HS 1/4 :LS 3/4 ] ↔ [HS 0 :LS 1 ], which has been structurally characterized.

Controlled modulation of the spin-crossover (SCO) behavior through the sorption-desorption of invited molecules is an extensively exploited topic because of its potential applications in molecular sensing. For this purpose, understanding the mechanisms by which the spin-switching properties are altered by guest molecules is of paramount importance. Here, we show an experimental approach revealing a direct probe of how the interplay between SCO and host-guest chemistry is noticeably activated by chemically tuning the host structure. Thus, the axial ligand 4-phenylpyridine (4-PhPy) in the 2D Hofmann clathrates {Fe(4-PhPy) 2 [M(CN) 4 ]} ( PhPyM ; M = Pt, Pd) is replaced by 2,4-bipyridine (2,4-Bipy), resulting in the isomorphous compounds {Fe(2,4-Bipy) 2 [M(CN) 4 ]} ( BipyM ; M = Pt, Pd), which basically differ from the former in that they have a noncoordinated N heteroatom in the ancillary aromatic substituent, i.e., 2-pyridyl instead of phenyl. Our chemical, magnetic, calorimetric, and structural characterizations demonstrate that this subtle chemical composition change provokes outstanding modifications not only in the capability to adsorb small guests as water or methanol but also in the extent to which these guests affect the SCO characteristics.

Aiming at investigating the suitability of Hofmann-type two-dimensional (2D) coordination polymers {Fe II (L ax ) 2 [M II (CN) 4 ]} to be processed as single monolayers and probed as spin crossover (SCO) junctions in spintronic devices, the synthesis and characterization of the M II derivatives (M II = Pd and Pt) with sulfur-rich axial ligands (L ax = 4-methyl- and 4-ethyl-disulfanylpyridine) have been conducted. The thermal dependence of the magnetic and calorimetric properties confirmed the occurrence of strong cooperative SCO behavior in the temperature interval of 100-225 K, featuring hysteresis loops 44 and 32.5 K/21 K wide for Pt II -methyl and Pt II /Pd II -ethyl derivatives, while the Pd II -methyl derivative undergoes a much less cooperative multistep SCO. Excluding Pt II -methyl, the remaining compounds display light-induced excited spin-state trapping at 10 K with T LIESST temperatures in the range of 50-70 K. Single-crystal studies performed in the temperature interval 100-250 K confirmed the layered structure and the occurrence of complete transformation between the high- and low-spin states of the Fe II center for the four compounds. Strong positional disorder seems to be the source of elastic frustration driving the multistep SCO observed for the Pd II -methyl derivative. It is expected that the peripheral disulfanyl groups will favor anchoring and growing of the monolayer on gold substrates and optimal electron transport in the device.

Spin crossover (SCO) compounds are very attractive types of switchable materials due to their potential applications in memory devices, actuators or chemical sensors. Rational chemical tailoring of these switchable compounds is key for achieving new functionalities in synergy with the spin state change. However, the lack of precise structural information required to understand the chemical principles that control the SCO response with external stimuli may eventually hinder further development of spin switching-based applications. In this work, the functionalization with an amine group in the two-dimensional (2D) SCO compound {Fe(5-NH 2 Pym) 2 [M II (CN) 4 ]} ( 1M , 5-NH 2 Pym = 5-aminopyrimidine, M II = Pt ( 1Pt ), Pd ( 1Pd )) confers versatile host-guest chemistry and structural flexibility to the framework primarily driven by the generation of extensive H-bond interactions. Solvent free 1M species reversibly adsorb small protic molecules such as water, methanol or ethanol yielding the 1M·H2O , 1M·0.5MeOH or 1M·xEtOH ( x = 0.25-0.40) solvated derivatives. Our results demonstrate that the reversible structural rearrangements accompanying these adsorption/desorption processes ( 1M ↔ 1M·guest ) follow a gate-opening mechanism whose kinetics depend not only on the nature of the guest molecule and that of the host framework ( 1Pt or 1Pd ) but also on their reciprocal interactions. In addition, a predictable and reversible guest-induced SCO modulation has been observed and accurately correlated with the associated crystallographic transformations monitored in detail by single crystal X-ray diffraction., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

The spin crossover (SCO) phenomenon represents a source of multistability at the molecular level, and dilution into a nonactive host was originally key to understand its cooperative nature and the parameters governing it in the solid state. Here, we devise a molecular alloying approach in which all components are SCO-active, but with significantly different characteristic temperatures. Thus, the molecular material [Fe(Mebpp) 2 ](ClO 4 ) 2 ( 2 ) has been doped with increasing amounts of the ligand Me2bpp (Mebpp and Me2bpp = methyl- and bis-methyl-substituted bis-pyrazolylpyridine ligands), yielding molecular alloys with the formula [Fe(Mebpp) 2-2 x (Me2bpp) 2 x ](ClO 4 ) 2 ( 4 x ; 0.05 < x < 0.5). The effect of the composition on the SCO process is studied through single-crystal X-ray diffraction (SCXRD), magnetometry, and differential scanning calorimetry (DSC). While the attenuation of intermolecular interactions is shown to have a strong effect on the SCO cooperativity, the spin conversion was found to occur at intermediate temperatures and in one sole step for all components of the alloys, thus unveiling an unprecedented allosteric SCO process. This effect provides in turn a means of tuning the SCO temperature within a range of 42 K.

Integration of the ON-OFF cooperative spin crossover (SCO) properties of Fe II coordination polymers as components of electronic and/or spintronic devices is currently an area of great interest for potential applications. This requires the selection and growth of thin films of the appropriate material onto selected substrates. In this context, two new series of cooperative SCO two-dimensional Fe II coordination polymers of the Hofmann-type formulated {Fe II (Pym) 2 [M II (CN) 4 ]· x H 2 O} n and {Fe II (Isoq) 2 [M II (CN) 4 ]} n (Pym = pyrimidine, Isoq = isoquinoline; M II = Ni, Pd, Pt) have been synthesized, characterized, and the corresponding Pt derivatives selected for fabrication of thin films by liquid-phase epitaxy (LPE). At ambient pressure, variable-temperature single-crystal X-ray diffraction, magnetic, and calorimetric studies of the Pt and Pd microcrystalline materials of both series display strong cooperative thermal induced SCO properties. In contrast, this property is only observed for higher pressures in the Ni derivatives. The SCO behavior of the {Fe II (L) 2 [Pt II (CN) 4 ]} n thin films (L = Pym, Isoq) were monitored by magnetization measurements in a SQUID magnetometer and compared with the homologous samples of the previously reported isostructural {Fe II (Py) 2 [Pt II (CN) 4 ]} n (Py = pyridine). Application of the theory of regular solutions to the SCO of the three derivatives allowed us to evaluate the effect on the characteristic SCO temperatures and the hysteresis, as well as the associated thermodynamic parameters when moving from microcrystalline bulk solids to nanometric thin films.

Two new heteroleptic complexes [Fe(1bppCOOH)(3bpp-bph)](ClO 4 ) 2 ·solv ( 1·solv , solv = various solvents; 1bppCOOH = 2,6-bis(1 H -pyrazol-1-yl)isonicotinic acid; 3bpp-bph = 2,6-bis(5-([1,1'-biphenyl]-4-yl)-1 H -pyrazol-3-yl)pyridine) and [Fe(1bppCOOH)(1bppCOOEt)](ClO 4 ) 2 ·0.5Me 2 CO ( 2·0.5Me 2 CO , 1bppCOOEt = ethyl 2,6-bis(1 H -pyrazol-1-yl)isonicotinate) were designed and prepared. The heteroleptic compound 1·solv was obtained by the combination of stoichiometric amounts of Fe(ClO 4 ) 2 , 1bppCOOH, and 3bpp-bph, and it was designed to fine-tune the spin crossover (SCO) properties with respect to the previously reported homoleptic compound [Fe(1bppCOOH) 2 . Indeed, the introduction of a new substituted 3bpp ligand induces a weaker ligand field in addition to promoting the formation of π···π and C-H···π intermolecular interactions through the biphenyl groups. For the desolvated counterpart 4 ) 2 . Indeed, the introduction of a new substituted 3bpp ligand induces a weaker ligand field in addition to promoting the formation of π···π and C-H···π intermolecular interactions through the biphenyl groups. For the desolvated counterpart 1 , this results in a shift of the SCO curve toward room temperature and the observation of a 13 K hysteresis width. Besides, compound 2·0.5Me 2 CO , which represents the first example of a heteroleptic complex containing two 1bpp tridentate ligands, stabilizes the LS state at room temperature confirming the same trend observed for the corresponding homoleptic compounds. Interestingly, both 1 and 2·0.5Me 2 CO heteroleptic complexes exhibit photoswitchable properties when irradiating with a 523 nm laser at 10 K. Preliminary characterization of the deposited complexes on native SiO 2 by X-ray absorption measurements suggests oxidation and decomposition of the complexes.

The synthesis, structural characterization and magnetic properties of two new isostructural porous 3D compounds with the general formula {Fe II ( pina )[M I (CN) 2 ] 2 }· x MeOH ( x = 0-5; pina = N -(pyridin-4-yl)isonicotinamide; M I = Ag I and x ∼ 5 ( 1· x MeOH ); M I = Au I and x ∼ 5 ( 2· x MeOH )) are presented. The single-crystal X-ray diffraction analyses have revealed that the structure of 1· x MeOH (or 2· x MeOH ) presents two equivalent doubly interpenetrated 3D frameworks stabilized by both argentophilic (or aurophilic) interactions and interligand C═O···HC H-bonds. Despite the interpenetration of the networks, these compounds display accessible void volume capable of hosting up to five molecules of methanol which interact with the host pina ligand and establish an infinite lattice of hydrogen bonds along the structural channels. Interestingly, the magnetic studies have shown that solvated complexes 1· x MeOH and 2· x MeOH display two- and four-step hysteretic thermally driven spin transitions, respectively. However, when these compounds lose the methanol molecules, the magnetic behavior changes drastically giving place to gradual spin conversions evidencing the relevant influence of the guest molecules on the spin-crossover properties. Importantly, since the solvent desorption takes place following a single-crystal-to-single-crystal transformation, empty structures 1 and 2 ( x = 0) could be also determined allowing us to evaluate the correlation between the structural changes and the modification of the magnetic properties triggered by the loss of methanol molecules.

[This corrects the article DOI: 10.1039/C8SC04935A.].

A multistable spin crossover (SCO) molecular alloy system [Fe 1- x M x ( n Bu-im) 3 (tren)](P 1- y As y F 6 ) 2 (M = Zn II , Ni II ; ( n Bu-im) 3 (tren) = tris( n -butyl-imidazol(2-ethylamino))amine) has been synthesized and characterized. By controlling the composition of this isomorphous series, two cooperative thermally induced SCO events featuring distinct critical temperatures ( T c ) and hysteresis widths (Δ T c , memory) can be selected at will. The pristine derivative 100As ( x = 0, y = 1) displays a strong cooperative two-step SCO and two reversible structural phase transitions (PTs). The low temperature PT LT and the SCO occur synchronously involving conformational changes of the ligand's n -butyl arms and two different arrangements of the AsF 6 - anions [ T 1c = 174 K (Δ T 1c = 17 K), T 2c = 191 K (Δ T 2c = 23 K) (scan rate 2 K min -1 )]. The high-temperature PT HT takes place in the high-spin state domain and essentially involves rearrangement of the AsF 6 - anions [ T PTc = 275 K (Δ T PTc = 16 K)]. This behavior strongly contrasts with that of the homologous 100P [ x = 0, y = 0] derivative where two separate cooperative one-step SCO can be selected by controlling the kinetics of the coupled PT LT at ambient pressure: (i) one at low temperatures, T c = 122 K (Δ T c = 9 K), for temperature scan rates (>1 K min -1 ) (memory channel A) where the structural modifications associated with PT LS are inhibited; (ii) the other centered at T c = 155 K (Δ T c = 41 K) for slower temperature scan rates ≤0.1 K min -1 (memory channel B). These two SCO regimes of the 100P derivative transform reversibly into the two-step SCO of 100As upon application of hydrostatic pressure ( ca. 0.1 GPa) denoting the subtle effect of internal chemical pressure on the SCO behavior. Precise control of AsF 6 - ↔ PF 6 - substitution, and hence of the PT LT kinetics, selectively selects the memory channel B of 100P when x = 0 and y ≈ 0.7. Meanwhile, substitution of Fe II with Zn II or Ni II [ x ≈ 0.2, y = 0] favors the low temperature memory channel A at any scan rate. This intriguing interplay between PT, SCO and isomorphous substitution was monitored by single crystal and powder X-ray diffractometries, and magnetic and calorimetric measurements.

Mastering the nanostructuration of molecular materials onto solid surfaces and understanding how this process affects their properties are of utmost importance for their integration into solid-state electronic devices. This is even more important for spin crossover (SCO) systems, in which the spin transition is extremely sensitive to size reduction effects. These bi-stable materials have great potential for the development of nanotechnological applications provided their intrinsic properties can be successfully implemented in nanometric films, amenable to the fabrication of functional nanodevices. Here we report the fabrication of crystalline ultrathin films (<1-43 nm) of two-dimensional Hofmann-type coordination polymers by using an improved layer-by-layer strategy and a close examination of their SCO properties at the nanoscale. X-ray absorption spectroscopy data in combination with extensive atomic force microscopy analysis reveal critical dependence of the SCO transition on the number of layers and the microstructure of the films. This originates from the formation of segregated nanocrystals in early stages of the growth process that coalesce into a continuous film with an increasing number of growth cycles for an overall behaviour reminiscent of the bulk. As a result, the completeness of the high spin/low spin transition is dramatically hindered for films of less than 15 layers revealing serious limitations to the ultimate thickness that might be representative of the performance of the bulk when processing SCO materials as ultrathin films. This unprecedented exploration of the particularities of the growth of SCO thin films at the nanoscale should encourage researchers to put a spotlight on these issues when contemplating their integration into devices.

Fe II spin-crossover (SCO) coordination polymers of the Hofmann type have become an archetypal class of responsive materials. Almost invariably, the construction of their architectures has been based on the use of monotopic and linear ditopic pyridine-like ligands. In the search for new Hofmann-type architectures with SCO properties, here we analyze the possibilities of bridging ligands with higher connectivity degree. More precisely, the synthesis and structure of {Fe II (L N3 )[M I (CN) 2 ] 2 }·(Guest) (Guest = nitrobenzene, benzonitrile, o-dichlorobenzene; M I = Ag, Au) and {Fe II (L N4 )[Ag 2 (CN) 3 ][Ag(CN) 2 ]}·H 2 O are described, where L N3 and L N4 are the tritopic and tetratopic ligands 1,3,5-tris(pyridin-4-ylethynyl)benzene and 1,2,4,5-tetrakis(pyridin-4-ylethynyl)benzene. This new series of Hofmann clathrates displays thermo- and photoinduced SCO behaviors.

The search for bifunctional materials showing synergies between spin crossover (SCO) and luminescence has attracted substantial interest since they could be promising platforms for new switching electronic and optical technologies. In this context, we present the first three-dimensional Fe II Hofmann-type coordination polymer exhibiting SCO properties and luminescence. The complex {Fe II (bpben)[Au(CN) 2 ]}@pyr (bpben = 1,4-bis(4-pyridyl)benzene) functionalized with pyrene (pyr) guests undergoes a cooperative multi-step SCO, which has been investigated by single crystal X-ray diffraction, single crystal UV-Vis absorption spectroscopy, and magnetic and calorimetric measurements. The resulting fluorescence from pyrene and exciplex emissions are controlled by the thermal and light irradiation (LIESST effect) dependence of the high/low-spin state population of Fe II . Conversely, the SCO can be tracked by monitoring the fluorescence emission. This ON-OFF interplay between SCO and luminescence combined with the amenability of Hofmann-type materials to be processed at the nano-scale may be relevant for the generation of SCO-based sensors, actuators and spintronic devices.

Spin-crossover (SCO) molecular solids are valued switchable materials for their common abrupt and reversible thermal transitions, large thermal hysteresis, or guest-dependent effects. These properties usually involve crystallographic transitions coupled to the SCO events. These phenomena are of great value for the understanding of solid-state transformations and also for exploiting them. We present here a lattice of the complex [FeL(bbp)](ClO 4 ) 2 (1; L and bbp are tris-imine ligands) featuring an unprecedented rich succession of SCO and crystallographic phase transformations. Magnetometry measurements unveil a thermally irreversible sequence of spin conversions that delineate four different thermal pathways. All of these are single-crystal-to-single-crystal processes and can thus be monitored by single crystal X-ray diffraction using one unique specimen. Fresh crystals of 1 contain one molecule of acetone per Fe center (1·ac) that abandons the lattice upon warming at the same time that a SCO from an ordered mixed spin state (1:1 high spin/low spin; HS/LS) to a fully HS state, 1 α , occurs. This crystallographic phase, accessed through a template effect by the solvent, converts into another one, 1 β , upon cooling, as triggered by a HS to LS SCO. Warming of 1 β induces a new SCO (LS to ordered HS/LS) coupled to another crystallographic phase transition, 1 β → 1 γ . The fully HS state of 1 γ can not be reached before decomposition of the compound. Instead, this phase cycles between the HS/LS and the LS states through superimposable pathways, different from that of the prerequired 1 β → 1 γ phase change. Analysis of the thermal variation of the free energy, G, through density functional theory methods provides trends in agreement with the observation of these transformations and clarifies the possible metastable nature of the various phases identified. This unique behavior allows the access to four different magnetic responses depending on the thermal history of the sample, within a given range of temperatures near the ambient conditions.

We report an unprecedented series of two-dimensional (2D) spin-crossover (SCO) heterobimetallic coordination polymers generically formulated as {Fe II [(Hg II (SCN) 3 ) 2 ](L) x }·Solv, where x = 2 for L = tvp (trans-(4,4'-vinylenedipyridine)) (1tvp), bpmh ((1E,2E)-1,2-bis(pyridin-4-ylmethylene)hydrazine) (1bpmh·nCH 3 OH; n = 0, 1), bpeh ((1E,2E)-1,2-bis(1-(pyridin-4-yl)ethylidene)hydrazine) (1bpeh·nH 2 O; n = 0, 1) and x = 2.33 for L = bpbz (1,4-bis(pyridin-4-yl)benzene) (1bpbz·nH 2 O; n = 0, 2/3). The results confirm that self-assembly of Fe II , [Hg II (SCN) 4 ] 2- , and ditopic rodlike bridging ligands L containing 4-pyridyl moieties favors the formation of linear [Fe(μ-L)] n 2n+ chains and in situ generated binuclear units {[Hg II (SCN) 3 ] 2 (μ-L)} 2- . The latter act as bridges between adjacent chains generating robust 2D layers. The [Fe II N 6 ] centers are equatorially surrounded by four NCS - groups and two axial N atoms of the organic ligand L. The compound 1tvp and the unsolvated form of 1bpmh undergo complete SCO centered at T 1/2 = 177 and 226 K, characterized by the enthalpy and entropy variations ΔH = 12.3 and 10.5 kJ mol -1 and ΔS = 69.4 and 48 J K -1 mol -1 , respectively. The almost complete SCO of the unsolvated form of 1bpeh occurs at ca. T 1/2 = 119 K and exhibits a complete LIESST effect. Regardless of the degree of solvation, a half-spin conversion at T 1/2 < 100 K occurs for 1bpbz·nH 2 O, which becomes almost complete at p = 0.65 GPa. The labile solvent molecules present in 1bpmh·CH 3 OH and 1bpeh·H 2 O have a dramatic influence on the corresponding SCO behavior.

Understanding the origin of cooperativity and the equilibrium temperature of transition (T 1/2 ) displayed by the spin-crossover (SCO) compounds as well as controlling these parameters are of paramount importance for future applications. For this task, the occurrence of polymorphism, presented by a number of SCO complexes, may provide deep insight into the influence of the supramolecular organization on the SCO behavior. In this context, herein we present a novel family of mononuclear octahedral Fe II complexes with formula cis-[Fe(bqen)(NCX) 2 ], where bqen is the chelating tetradentate ligand N,N'-bis(8-quinolyl)ethane-1,2-diamine and X = S, Se. Depending on the preparation method, these compounds crystallize in either the orthorhombic or the trigonal symmetry systems. While the orthorhombic phase is composed of a racemic mixture of mononuclear complexes (polymorph I), the trigonal phase contains only one of the two possible enantiomers (Λ or Δ), thereby generating a chiral crystal (polymorph II). The four derivatives undergo SCO behavior with well-differentiated T 1/2 values occurring in the interval 90-233 K. On one hand, T 1/2 is about 110 K (polymorph I) and 87 K (polymorph II) higher for the selenocyanate derivatives in comparison to those for their thiocyanate counterparts. These differences in T 1/2 are ascribed not only to the higher ligand field induced by the selenocyanate anion but also to a remarkable difference in the structural reorganization of the [FeN 6 ] coordination core upon SCO. Likewise, the higher cooperativity observed for the thiocyanate derivatives seems to be related to their stronger intermolecular interactions within the crystal. On the other hand, T 1/2 is about 53 K (thiocyanate) and 29 K (selenocyanate) higher for the trigonal polymorph II in comparison to those for the orthorhombic polymorph I. These differences, and the small changes observed in cooperativity, stem from the slightly different hetero- and homochiral crystal packing generated by the cis-[Fe(bqen)(NCX) 2 ] molecules, which determines subtle adaptations in the intermolecular contacts and the Fe II coordination core.

Two polymorphs of the spin crossover (SCO) compound [Fe(1,3-bpp)2 ](ClO4 )2 (1 and 2; 1,3-bpp=2-(pyrazol-1-yl)-6-(pyrazol-3-yl)pyridine) were prepared using a novel, stepwise procedure. Crystals of 1 deposit from dry solvents, while 2 is obtained from a solid-state procedure, by sequentially removing lattice H2 O molecules from the solvatomorph [Fe(1,3-bpp)2 ](ClO4 )2 ⋅2 H2 O (2⋅2 H2 O), using single-crystal-to-single-crystal (SCSC) transformations. Hydrate 2⋅2 H2 O is obtained through the same reaction as 1, now with 2.5 % of water added. Compounds 2 and 2⋅2 H2 O are unstable in the atmosphere and absorb or lose one equivalent of water, respectively, to both yield the stable solvatomorph [Fe(1,3-bpp)2 ](ClO4 )2 ⋅H2 O (2⋅H2 O), also following SCSC processes. The four derivatives have been characterised by single-crystal X-ray diffraction (SCXRD). Furthermore, the homogeneity of the various compounds as well as their SCSC interconversions have been confirmed by powder X-ray diffraction (PXRD). Polymorphs 1 and 2 exhibit abrupt SCO behaviour near room temperature with T1/2↑ =279/316 K and T1/2↓ =276/314 K (near 40 K of shift) and different cooperativity., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

We show a marked tendency of Fe(II) to form heteroleptic [Fe(L)(L')](ClO4)2 complexes from pairs of chelating tris-imine 3bpp, tpy, or 2bbp ligands. New synthetic avenues for spin crossover research become thus available, here illustrated with three new heteroleptic compounds with differing magnetic behaviors: [Fe(H4L1)(Cl-tpy)](ClO4)2·C3H6O (1), [Fe(H2L3)(Me3bpp)](ClO4)2·C3H6O (2), [Fe(H4L1)(2bbp)](ClO4)2·3C3H6O (3). Structural studies demonstrate that 1 is in the low-spin (LS) state up to 350 K, while complexes 2 and 3 are, by contrast, in the high-spin (HS) state down to 2 K, as corroborated through magnetic susceptibility measurements. Upon exposure to the atmosphere, the latter exhibits the release of three molecules of acetone per complex, turning into the solvent-free analogue [Fe(H4L1)(2bbp)](ClO4)2 (3a), through a single-crystal-to-single-crystal transformation. This guest extrusion process is accompanied by a spin switch, from HS to LS.

Surface-relief photonic gratings of the spin-crossover metal-organic framework {Fe(bpac)[Pt(CN)4]} (bpac = bis(4-pyridyl)acetylene) were elaborated by the combination of a sequential assembly process and lithographic methods. Optical diffraction, surface plasmon resonance spectroscopy and Raman micro-spectroscopy were used to investigate the temperature dependence of the spin state of the iron(II) ions and the concomitant change of the refractive index of the grating material. The refractive index change associated with the high spin ((5)T) to low spin ((1)A) transition was found to be as high as Δn = 0.08 ± 0.005, which was attributed to the pronounced mass density difference between the two spin states. While the grating thickness (15-90 nm) had no influence on the spin-crossover properties of the gratings, the adsorption of aromatic guest molecules was found to have a substantial effect both on the spin transition temperature and the completeness of the transition.

A study of the spin-crossover (SCO) behavior of the tridimensional porous coordination polymer {Fe(bpac)[Pt(CN)4]} (bpac=bis(4-pyridyl)acetylene) on adsorption of different mono- and polyhalobenzene guest molecules is presented. The resolution of the crystal structure of {Fe(bpac)[Pt(CN)4]}⋅G (G=1,2,4-trichlorobenzene) shows preferential guest sites establishing π⋅⋅⋅π stacking interactions with the host framework. These host-guest interactions may explain the relationship between the modification of the SCO behavior and both the chemical nature of the guest molecule (electronic factors) and the number of adsorbed molecules (steric factors)., (Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

We report on atomic force microscopy (AFM) and near-field scanning optical microscopy (NSOM) investigations of single crystals of the spin crossover complex {Fe(pyrazine)[Pt(CN)4]} across the first-order thermal spin transition. We demonstrate for the first time that the change in spin state can be probed with sub-micrometer spatial resolution through various topographic features extracted from AFM data. This original approach based on surface topography analysis should be easy to implement to any phase change material exhibiting sizeable electron-lattice coupling. In addition, AFM images revealed specific topographic features in the crystals, which were correlated with the spatiotemporal evolution of the transition observed by far-field and near-field optical microscopies.

Plasmonic resonance properties of a series of lithographically patterned gold nanorod arrays, spin coated by thin films of an iron(II)-triazole type spin crossover complex, were investigated upon heating/cooling and also under 633 nm laser irradiation. In both cases a reversible shift of the localised surface plasmon resonance wavelength was observed and quantitatively linked to the refractive index change accompanying the spin transition. These results show that molecular spin state switching can be very efficiently triggered by the photo-thermal effect, which - in turn - allows for an active tuning of the plasmon resonance.

The synthesis and characterization of a series of three-dimensional (3D) Hofmann-like clathrate porous metal-organic framework (MOF) materials [Fe(bpac)M(CN)(4)] (M=Pt, Pd, and Ni; bpac=bis(4-pyridyl)acetylene) that exhibit spin-crossover behavior is reported. The rigid bpac ligand is longer than the previously used azopyridine and pyrazine and has been selected with the aim to improve both the spin-crossover properties and the porosity of the corresponding porous coordination polymers (PCPs). The 3D network is composed of successive {Fe[M(CN)(4)]}(n) planar layers bridged by the bis-monodentate bpac ligand linked in the apical positions of the iron center. The large void between the layers, which represents 41.7% of the unit cell, can accommodate solvent molecules or free bpac ligand. Different synthetic strategies were used to obtain a range of spin-crossover behaviors with hysteresis loops around room temperature; the samples were characterized by magnetic susceptibility, calorimetric, Mössbauer, and Raman measurements. The complete physical study reveals a clear relationship between the quantity of included bpac molecules and the completeness of the spin transition, thereby underlining the key role of the π-π stacking interactions operating between the host and guest bpac molecules within the network. Although the inclusion of the bpac molecules tends to increase the amount of active iron centers, no variation of the transition temperature was measured. We have also investigated the ability of the network to accommodate the inclusion of molecules other than water and bpac and studied the synergy between the host-guest interaction and the spin-crossover behavior. In fact, the clathration of various aromatic molecules revealed specific modifications of the transition temperature. Finally, the transition temperature and the completeness of the transition are related to the nature of the metal associated with the iron center (Ni, Pt, or Pd) and also to the nature and the amount of guest molecules in the lattice., (Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Nanopatterned thin films of the metal-organic framework {Fe(bpac)[Pt(CN)4]} (bpac=bis(4-pyridyl)acetylene) are elaborated by the combination of a sequential assembly process and a lithographic method. Raman microspectroscopy is used to probe the temperature dependence of the spin state of the iron(II) ions in the films (40-90 nm in thickness), and reveals an incomplete but cooperative spin transition comparable to that of the bulk material. Adsorption/desorption of pyridine guest molecules is found to have a substantial influence on the spin-crossover properties of the thin layers. This interplay between host-guest and spin-crossover properties in thin films and nanopatterns demonstrates the potential ability of using this kind of material as a microsensor., (Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)