David
Aguilà
*ab,
Yoann
Prado
ab,
Evangelia S.
Koumousi
abcd,
Corine
Mathonière
*cd and
Rodolphe
Clérac
*ab
aCNRS, CRPP, UPR 8641, F-33600 Pessac, France. E-mail: clerac@crpp-bordeaux.cnrs.fr; aguila@crpp-bordeaux.cnrs.fr; Tel: +33 5 56 84 56 50
bUniv. Bordeaux, CRPP, UPR 8641, F-33000 Pessac, France
cCNRS, ICMCB, UPR 9048, F-33600 Pessac, France. E-mail: Corine.Mathoniere@icmcb.cnrs.fr; Tel: +33 5 40 00 26 82
dUniv. Bordeaux, ICMCB, UPR 9048, F-33600 Pessac, France
First published on 10th November 2015
With the long term objective to build the next generation of devices from the molecular scale, scientists have explored extensively in the past two decades the Prussian blue derivatives and their remarkable physico-chemical properties. In particular, the exquisite Fe/Co system displays tuneable optical and magnetic behaviours associated with thermally and photo-induced metal-to-metal electron transfer processes. Recently, numerous research groups have been involved in the transfer of these electronic properties to new Fe/Co coordination networks of lower dimensionality as well as soluble molecular analogues in order to facilitate their manipulation and integration into devices. In this review, the most representative examples of tridimensional Fe/Co Prussian blue compounds are described, focusing on the techniques used to understand their photomagnetic properties. Subsequently, the different strategies employed toward the design of new low dimensional Prussian blue analogues based on a rational molecular building block approach are discussed emphasizing the advantages of these functional molecular systems.
In this review article, the most representative examples of tridimensional AxCoy[Fe(CN)6]·nH2O Prussian blue compounds are described, focusing on their photomagnetic switchable properties and how those are influenced by their chemical composition. Subsequently, the different strategies employed toward the design of new low dimensional Prussian blue systems based on a rational molecular building block approach are discussed emphasizing the advantages and potential applications of these functional molecular analogues.
The Fe/Co Prussian blue materials have a general formula AxCoy[Fe(CN)6]·nH2O (A: Na+, K+, Cs+, Rb+) and form a neutral tridimensional network (Fig. 1) obtained from the reaction of hexacyanidoferrate(III) ([FeIII(CN)6]3−) with cobalt(II) centres in water ([CoII(OH2)6]2+), in presence of alkaline ions A+. These coordination networks adopt a face-centred cubic (fcc) structure in the Fm3m space group, with a cell parameter close to 10 Å depending on the oxidation state of the metallic ions and the nature of alkaline ions.22–24 The vertices and the centres of the faces of the cubic unit cell are occupied by the FeIII ions, while CoII ions are located at the octahedral sites (Fig. 1). Both metal centres are linked by cyanide bridges with FeIII and CoII being coordinated by carbon and nitrogen, respectively. The corresponding ligand field of both donor atoms leads to low spin FeIIILS and high spin CoIIHS configurations. Zeolitic water molecules form a hydrogen-bonded network in the interstitial sites, where alkaline ions are also inserted. Depending on the amount of alkaline ions introduced, the stoichiometry of the compound can vary. The electro-neutrality of the network is ensured by adjusting the number of [FeIII(CN)6]3− vacancies (□), and the coordination sphere of the neighbouring CoII sites is completed by water molecules (as shown on the right bottom corner of structure in Fig. 1; note that each missing [FeIII(CN)6]3− unit is leading to the coordination of six additional water molecules). Hence, in the crystal, such vacancies (inhomogeneously distributed through the network) are responsible for a variety of coordination environments around the CoII ions leading to an average CoN6−pOp coordination sphere. These different environments around the CoII site are of particular importance for the electron transfer properties, which are correlated to the redox potential of the two metal centres.25 The replacement of a nitrogen atom from the cyanide ligand by a water molecule increases the redox potential of the cobalt centre. Therefore depending on the amount of water on the Co site, the Co redox potential can be significantly lower or higher than the Fe one, stabilizing FeII/CoIII or FeIII/CoII states respectively. This is only when the redox potential of the Co site is slightly lower than the Fe one, that the FeIII/CoII paramagnetic excited state becomes thermally and optically accessible above the FeII/CoIII ground state.25 Hence, the electron transfer phenomena in this Fe/Co Prussian blue analogue can be easily tuned through modification of the vacancies, directly in link with the quantity of alkaline ions inserted in the network.
Compound (number in text) | % Vacancies [□] | CoN6−pOp |
![]() |
ET with temperature | ET with light | EXAFS | XANES | Ref. |
---|---|---|---|---|---|---|---|---|
a The highest intensity bands observed at room temperature are reported. | ||||||||
Co1.5[Fe(CN)6]·6H2O (3) | 33 | CoN4O2 | 2163 | Non active | Non active | Yes | Yes | 31 and 43 |
K0.04Co1.48[Fe(CN)6]·6.8H2O (4) | 33 | CoN4.1O1.9 | 2156, 2090 | Non active | Non active | — | — | 23 |
K0.2Co1.4[Fe(CN)6]·6.9H2O (1) | 29 | CoN4.3O1.7 | 2162, 2116 | Non active | Active | — | — | 22 |
K0.4Co1.3[Fe(CN)6]·4.2H2O (10) | 23 | CoN4.6O1.4 | — | Active (280 K) | — | Yes | Yes | 43 |
K0.4Co1.3[Fe(CN)6]·5H2O (8) | 23 | CoN4.6O1.4 | 2135 | Non active | Active | Yes | Yes | 29 and 43 |
Na0.07Co1.5[Fe(CN)6]·6.3H2O | 33 | CoN4O2 | 2155, 2089 | Non active | Non active | — | — | 11 |
Na0.37Co1.37[Fe(CN)6]·4.8H2O | 27 | CoN4.4O1.6 | 2155, 2089 | Active (180/220 K) | Active | — | — | 11 |
Na0.4Co1.3[Fe(CN)6]·5H2O (9) | 23 | CoN4.6O1.4 | 2160 | Active (260 K) | — | Yes | Yes | 29 and 43 |
Na0.43Co1.35[Fe(CN)6]·4.6H2O (7) | 26 | CoN4.4O1.6 | — | Active (213/232 K) | Active | — | — | 40 and 41 |
Na0.53Co1.32[Fe(CN)6]·4.4H2O | 24 | CoN4.5O1.5 | 2155, 2089 | Active (230/270 K) | Active | — | — | 11 |
Na0.60Co1.26[Fe(CN)6]·3.9H2O | 21 | CoN4.8O1.2 | 2155, 2122 | Active (260/300 K) | Active | — | — | 11 |
Na0.94Co1.15[Fe(CN)6]·3H2O | 13 | CoN5.2O0.8 | 2122 | Non active | Non active | — | — | 11 |
Na1.4Co1.3[Fe(CN)6]·5H2O (11) | 23 | CoN4.6O1.4 | 2100 | Non active | — | Yes | Yes | 29 and 43 |
Rb0.55Co1.2[Fe(CN)6]·3.9H2O (5) | 17 | CoN5O1 | 2125 | Non active | Active | — | — | 23 |
Rb0.66Co1.25[Fe(CN)6]·4.3H2O (2) | 20 | CoN4.8O1.2 | 2133 | Non active | Active | Yes | Yes | 31 and 43 |
Cs0.1Co1.43[Fe(CN)6]·6.4H2O | 30 | CoN4.2O1.8 | 2160, 2090 | Non active | Weak | — | Yes | 24 |
Cs0.24Co1.38[Fe(CN)6]·5.5H2O | 28 | CoN4.3O1.7 | 2160, 2090 | Active (170–280 K) | Active | Yes | Yes | 24 and 44 |
Cs0.38Co1.25[Fe(CN)6]·5H2O | 20 | CoN4.8O1.2 | 2105 | Active (170–280 K) | Active | — | Yes | 24 |
Cs0.68Co1.18[Fe(CN)6]·4.1H2O | 15 | CoN5.1O0.9 | 2100 | Non active | Non active | — | Yes | 24 |
CsCo1.03[Fe(CN)6]·3.3H2O (6) | 3 | CoN5.8O0.2 | 2120 | Non active | Weak | — | — | 23 |
One of the most relevant compounds studied by Hashimoto and co-workers was obtained by replacing potassium by rubidium: Rb0.66Co1.25[Fe(CN)6]·4.3H2O (2).31 To understand its photo-induced long-range magnetic order, the authors first characterized the compound by infrared and Mössbauer spectroscopy, and the results were compared with alkaline free analogue, Co1.5[Fe(CN)6]·6H2O (3). Compound 2 was found to be composed mainly of FeII–CN–CoIII pairs, while clear evidence for a FeIII–CN–CoII configuration was found for 3. Indeed, elemental analysis suggested the following stoichiometries, Rb0.66Co0.25Co[Fe(CN)6][□]0.25·4.3H2O for 2 and Co0.5Co[Fe(CN)6][□]0.5·6H2O for 3, which implies CoN4.8O1.2 and CoN4O2 average cobalt coordination spheres for 2 and 3, respectively (note that the oxygen atoms originate from the six water molecules, which are present for each vacancy). Since the ligand field for the N atom from the cyanide ligand is higher than the O atom from the water molecule, the electronic structure of both compounds turns out to be substantially different.26 Thus, for a CoN4O2 environment (3), the ligand field of the cobalt is weak enough to stabilize the FeIIILS–CN–CoIIHS configuration. In contrast, for 2, where the average amount of nitrogen around the cobalt is higher (CoN4.8O1.2) due to fewer vacancies, the ligand field is stronger, thus stabilizing the diamagnetic FeIILS–CN–CoIIILS state. It is worth mentioning that these conclusions drawn from the ligand field theory are also perfectly in line with the discussion of the redox potentials reported by Bleuzen and co-workers in 2010 (vide supra).25 The magnetic properties of both compounds further confirmed this scenario. For 3, the ferrimagnetic order was observed below a Curie temperature of 16 K. In contrast, the χT values for 2 were much smaller, as the material is mostly composed by diamagnetic FeIILS–CN–CoIIILS pairs, and only a small amount of CoII and FeIII centres are responsible for the observed paramagnetism in the whole temperature range. Nevertheless when a sample of 2 was irradiated at 5 K, a remarkable increase of the magnetization was observed (Fig. 2).31 This enhancement associated with a long-range magnetic order at 22 K confirmed the first studies on 122 and the effect of the light illumination. When the sample was further heated to 150 K, the original value of the magnetization (before irradiation) was recovered. The same conclusions were obtained by infrared and Mössbauer spectroscopies after photo-excitation at 5 K and 25 K, respectively. Interestingly, no change in the infrared spectra after irradiation was observed in the thermal treatment until 70 K, demonstrating that the metastable photo-induced FeIIILS–CN–CoIIHS configuration was kinetically trapped below this temperature. The recovery of the FeIILS–CN–CoIIILS configuration was observed only around 80 K, and the original spectrum was completely restored at ca. 120 K. Taking into account these results, the authors proposed a possible mechanism for the light induced electron-transfer based on the CTIST process, which can explain the long-life time of the metastable state.31 Since the change from the FeIILS–CN–CoIIILS to FeIIILS–CN–CoIIHS implies a spin-forbidden transition, a possible alternative pathway was contemplated considering an intermediate FeIIILS–CN–CoIILS state. The transition between FeIILS–CN–CoIIILS and FeIIILS–CN–CoIILS is spin-allowed and could enable the following decay to FeIIILS–CN–CoIIHS due to the large stability of CoIIHS. Recovering the original FeIILS–CN–CoIIILS state turns out to be slow due to the large change in the bond distances and the spin-forbidden character of such transition. This mechanism suggests a high energy barrier, which would afford a long-lived metastable state. From these results, Hashimoto and co-workers demonstrated the importance of the presence of diamagnetic FeIILS–CN–CoIIILS pairs in the compound to allow the photo-induced magnetization.31 At the same time, they observed that this diamagnetic motif was favoured when the number of nitrogen atoms was sufficient to guarantee a sufficiently strong ligand field around the cobalt ion.
![]() | ||
Fig. 2 Dependence of field-cooled magnetization of compound 2 with temperature under an applied field H = 0.5 mT before (empty dots) and after (black dots) light irradiation, and after the thermal treatment at 150 K (crosses). Reprinted with permission from ref. 31. Copyright 1999 American Chemical Society. |
Subsequently to Hashimoto's work, an extensive study was performed by Bleuzen, Verdaguer and co-workers through the study of three different compounds featuring different cobalt environment: K0.04Co1.48[Fe(CN)6]·6.8H2O (4), Rb0.55Co1.2[Fe(CN)6]·13H2O (5), and CsCo1.03[Fe(CN)6]·3.3H2O (6), displaying average coordination spheres close to CoN4O2, CoN5O and CoN6 respectively.23 These environments correspond to different amount of vacancies in the material from 33% for 4, 17% for 5, to almost none for 6 (see Table 1). Comparing the behaviour of these three compounds, the authors demonstrated that the enhancement of the ligand field produced by five nitrogen and one oxygen atom in 5 was enough to induce a spontaneous electron transfer during the synthesis and thus to produce diamagnetic pairs in the material. Due to the existence of these diamagnetic pairs, a considerable increase of the magnetization was observed after irradiation as a signature of a photo-induced ferrimagnetic phase. However, when compound 6 (with six nitrogen atoms around the cobalt and thus a maximum of diamagnetic pairs) was measured, the effect of the light was found to be very weak. Thus, the authors confirmed that the presence of diamagnetic pairs in the Prussian blue analogues was necessary to observe a photo-induced magnetization, but an excess of such diamagnetic pairs precludes the phenomena.23 The hypothesis given by the authors to explain this result relies on the flexibility of the inorganic network that seems to be required to allow the necessary increase of the bond lengths during the photo-generation of the FeIIILS–CN–CoIIHS pairs. When the number of diamagnetic units is too high (6), almost no [Fe(CN)6]3− vacancies are present in the network, and thus the number of water molecules coordinated to the Co metal ions is very low. In these conditions, the network is probably relatively rigid and the photo-generation of the FeIIILS–CN–CoIIHS phase is difficult to take place. This study was further complemented one year later by the same authors, who demonstrated that it was possible to induce and eventually tune the photo-induced magnetization of 6 by carefully controlling the amount of Cs+ inserted in the structure.24 Compounds with general formula CsxCoy[Fe(CN)6][□]z·nH2O were synthesized with different x values from 0.1 to 0.68 (see Table 1). Elemental analysis showed an increase of the nitrogen amount, corresponding to a mean environment of the cobalt centre from CoN4.2O1.8 (x = 0.1, y = 1.43, z = 0.43) to CoN5.1O0.9 (x = 0.68, y = 1.18, z = 0.18), due to the decrease of z (the number of vacancies [□]). Infrared spectroscopy, powder X-ray diffraction and X-ray absorption spectroscopy (see below, Section 2.3) demonstrated the enhancement of the amount of diamagnetic FeIILS–CN–CoIIILS units with the increase of Cs+ amount. This evidence was corroborated by measuring the magnetic susceptibility of the samples at room temperature, which was progressively reduced by the increase of Cs+ quantity. When the Cs+ content ranged in between x = 0.24 and 0.38, the required ligand field at the cobalt ion was empirically achieved resulting in the presence of a thermally induced electron transfer when decreasing the temperature. In contrast, when the samples were irradiated with light, the highest efficiency for the photo-induced process was observed for x between 0.38 and 0.68. Thus, this range turned out to be the best compromise between the amount of FeIILS–CN–CoIIILS diamagnetic pairs and the number of vacancies [□], providing the adequate network flexibility to allow the trapping of the photo-induced metastable state. Similar conclusions were obtained by Hashimoto and co-workers by studying the effect of the Na+ content in the NaxCoy[Fe(CN)6][□]z·nH2O Prussian blue analogues from x = 0.07 to 0.94.11 The infrared and UV-Vis spectra of the different compounds within this series showed that lower contents of sodium imposed a main FeIIILS–CN–CoIIHS phase, while an increase of the Na+ content rather stabilized the FeIILS–CN–CoIIILS configuration. For intermediate doping of Na+, the average ligand field around the cobalt ion allows the occurrence of a thermal electron transfer, as well as a photo-induced ferrimagnetic state at low temperature. It should be noticed that these compounds were the first Prussian blue analogues exhibiting a thermal hysteresis associated with the thermally induced electron-transfer phenomenon (i.e. a first order phase transition). This phase transition was shifted towards high temperatures by increasing the amount of alkali metal ion. Additionally, it is worth mentioning that the relaxation of the thermally quenched state was studied in details for one related compound of this series, Na0.4Co1.4[Fe(CN)6]·3.4H2O (7).40,41 This system was found to show a quasi-complete trapping of the high-temperature phase (when the sample was cooled down extremely fast), with a thermal decay of the quenched phase around 160 K. The mean-field analysis of the relaxation curves led to a relaxation time following a thermally activated behaviour (Arrhenius) with an energy barrier to electron transfer (Δ/kB) of 3110(60) K and τ0 = 6.7 × 10−7 s. This work represents the first evaluation of the relaxation time (τ) in a Fe/Co PBA, with a τ value of ca. 33 hours at 120 K.40,41 Similarly, the relaxation properties of the photo-induced state from other systems of this family have also been explored. As an example, the lifetime of the photo-induced state in Na0.6Co1.21[Fe(CN)6]·4.2H2O was found to be about 3 hours at 120 K.42
![]() | ||
Fig. 3 Fe K-edge (left) and Co K-edge (right) XANES spectra for compounds 2, 8, 9, 10, 11 and 3 at 30 K (solid lines) and 296 K (dashed lines). Spectra for K3FeIII(CN)6 and K4FeII(CN)6 (Fe K-edge) and for K3CoIII(CN)6 and Co(NO3)2 hydrate (Co K-edge) were added for comparison. Adapted with permission from ref. 43. Copyrighted by the American Physical Society. |
Analyses of the EXAFS data were used to obtain specific structural information, such as the coordination geometry or interatomic distances around the metal ions. Interestingly, it was observed that FeII–C bond length distances are slightly shorter than in systems with FeIIILS–C bonds. This effect was attributed to the presence of an additional electron in the t2g bonding orbital for FeIILS site, that induces a slight shortening of the Fe–C bond compared to those involving FeIIILS. On the other hand, the EXAFS analysis for the CoIIHS–N,O and CoIIILS–N,O systems showed that the differences in the bond lengths were more similar to the ones found in Co/radical complexes showing valence tautomerism than in CoII spin-crossover compounds. This study proved the change of Co valence within the studied materials and thus the electron transfer phenomena. In 1999, Hashimoto and co-workers went one step further and used XANES and EXAFS spectroscopies to study the local Fe and Co environments in the photo-excited state of Na0.4Co1.3Fe(CN)6·5H2O (9).47 This system was found to exhibit photo-induced electron transfer at low temperatures,29 with a metastable state possessing lifetimes large enough around 40 K to be studied by these spectroscopic techniques. The features observed in the Co K-edge and Fe K-edge XANES spectra after irradiating the sample with visible light at 36 K were similar to those at 300 K, showing that the dominant Co and Fe species were in the oxidation state +2 and +3, respectively. After heating the sample to 150 K, the Co K-edge spectra turned back to the low temperature one (for CoIIILS), implying that the trapped excited state was thermally relaxed to the ground state at this temperature. A further increase of the temperature until 300 K confirmed the presence of the FeIIILS–CoIIHS phase and thus that the thermally induced electron-transfer was still present as for the non irradiated sample. By comparing the estimated CoIII/CoII composition ratio, it was found that the amount of CoII site was larger in the irradiated sample at 36 K than in the sample at 300 K, which evidenced the larger number of paramagnetic FeIIILS–CoIIHS units in the photo-induced phase. Nevertheless, EXAFS spectroscopy showed that the local structure of the photo-induced state was very close to that of the high-temperature phase.
The influence of the alkali-metal ion in the thermally induced electron transfer phenomenon was also assessed by EXAFS spectroscopy. As an example, Bleuzen and co-workers studied Cs0.24Co1.38[Fe(CN)6]·5.5H2O not only at the Fe and Co K-edges but also at the Cs L3-edge.44 The different EXAFS signals obtained at 300 and 20 K at Fe and Co K-edges were used to evidence the thermally induced electron transfer in this compound (see Table 1). On the other hand, the analysis of EXAFS data at the Cs L3-edge demonstrated that at 300 K the Cs ion is not centred on the Td site of the Prussian blue network, inducing a bend of the Co–CN–Fe motifs. This structural feature, that implies a less efficient orbital overlap than in the linear conformation, imposes a weaker ligand field around the cobalt centre and thus stabilizes the CoIIHS state. In contrast, the EXAFS experiments carried out at 20 K showed that the Cs ion is localized on the Td site, inducing a linear Co–CN–Fe conformation in its neighbourhood. The stronger orbital interaction promoted by such linearity produces a stronger ligand field around the cobalt ion, and thus stabilizes its CoIIILS configuration. With these instructive results, the authors showed that the cobalt ions surrounding the Cs ions are the ones involved in the thermal electron transfer phenomenon, thus proving the crucial role of the alkali metal ions in this process.
In order to study further the light-induced electron transfer process, Cartier dit Moulin, Bleuzen, Verdaguer and co-workers investigated the electronic and local structures of the ground and excited states of Rb0.55Co1.2[Fe(CN)6]·3.9H2O (5) by XANES and EXAFS.45 The comparison between the XANES spectra before and after irradiation below 30 K confirmed a decrease of the CoIIILS and FeIILS signals subsequent to the photo-induced conversion of some CoIIILS–FeIILS units into CoIIHS–FeIIILS ones. However, it was estimated that about 46% of diamagnetic pairs remained unaffected by the irradiation. Therefore, two types of diamagnetic CoIIILS–FeIILS pairs were described: (i) active ones, which are located in a more flexible network (close to iron vacancies [□]) and can be easily converted into the paramagnetic CoIIHS–FeIIILS configuration through light irradiation; and (ii) inactive ones, which are thought to have less or a lack of vacancies [□] in their neighbourhood, being trapped in a more rigid network that precludes the light-induced electron transfer. These two kinds of FeIILS–CN–CoIIILS moiety are naturally induced by the inhomogeneous repartition of the vacancies in the material, which implies a variety of environments around the cobalt centres (vide supra). Interestingly, the authors tried to de-excite the photo-induced state with a blue light as seen before by Hashimoto and co-workers for 1.22 Against expectations, the effect was found to be inversed, resulting in a further increase of the paramagnetic CoIIHS–FeIIILS pair population. This observation illustrates the complexity of the materials with the presence of a distribution of geometries for the FeIILS–CN–CoIIILS moiety that display different photo-activities.45 These EXAFS experiments also evidenced that the photo-induced electron-transfer was associated to a local structure rearrangement of the coordination sphere of the cobalt ions with a bond increase of about 0.17 Å. This large modification needs to be absorbed by the tridimensional network, and thus the efficiency of the photo-conversion of the FeIILS–CN–CoIIILS pairs depends on a subtle compromise between the number of diamagnetic pairs and vacancies [□] in the material.
One of the remaining questions concerning the photo-induced phase of Fe/Co PBAs was the nature of the exchange interaction between the magnetic CoIIHS and FeIIILS sites. Even if it was assumed that antiferromagnetic interactions between the centres led to ferrimagnetic ground state,22–24,31 no macroscopic characterization of this photo-induced metastable state could be carried out. The main difficulties were (i) to know the amount of the photo-transformed phase45 (as the photo-conversion of the sample is never complete; vide supra), (ii) the possible partial relaxation to the diamagnetic state at low temperatures, and (iii) the fact that two configurations (antiferromagnetic CoII(HS,3/2)/FeIII(LS,1/2) or ferromagnetic CoII(LS,1/2)/FeIII(LS,1/2)) cannot be easily discriminated as they generate a very similar resulting magnetic moment (around 2 μB).46 However, Cartier dit Moulin, Bleuzen and co-workers showed that X-Ray Magnetic Circular Dichroism experiments (XMCD) were able to probe the relative orientation of the magnetic moments of the metal ions, and thus to determine the sign of the magnetic interaction. With this technique, they characterized the magnetic interaction within the photo-induced metastable state of compound 5 (Rb0.55Co1.2[Fe(CN)6]·3.9H2O),46 that was compared to K0.04Co1.48[Fe(CN)6]·6.8H2O (4), known to exhibit antiferromagnetic interactions between Co and Fe ions.23 For both compounds, a weak dichroic signal was obtained at the Co and Fe K-edges, with positive and negative signs, respectively. Since the antiferromagnetic coupling between magnetic CoII(HS,3/2) and FeIII(LS,1/2) centres in 4 was shown already by macroscopic magnetization data, it was concluded that the inversion of dichroic signal from cobalt to iron was a local evidence of the antiferromagnetic interaction in 4. With this assumption, and taking into account that the same XMCD signature was observed for 5, the authors evidenced for the first time the ferrimagnetic ground state of the photo-induced phase in Fe/Co PBAs.
![]() | ||
Fig. 4 (top) Representation of the molecular structure of {[Co(tmphen)2]3[Fe(CN)6]2} (12) at T = 220 K. Hydrogen atoms are omitted for clarity. Fe, Co, N and C atoms are indicated in orange, dark blue, light blue and light grey, respectively. (bottom) χT versus T data of 12 at a constant magnetic field of 0.1 T for the three solid-state phases obtained (red crystals, red and blue powders). Reprinted with permission from ref. 55. Copyright 2005 American Chemical Society. |
A few years later in 2011, the photomagnetic properties of 12 were reported by Dunbar, Clérac, Mathonière and co-workers by measuring the temperature dependence of the magnetic susceptibility of compound 12 after exposure to the humidity (blue powder phase) before and after irradiation.56 As expected54,55 the magnetic properties agreed with a [CoIICoIII2FeII2] configuration at low temperatures (vide supra) that appeared to be photo-active as indicated by a fast increase of the magnetic response after irradiation at 10 K with white light. This effect was attributed to a partial photo-conversion (about 30%) of the [CoIICoIII2FeII2] state to the [CoII3FeIII2] one. The authors related the incomplete nature of the photomagnetic effect to the dark colour of the sample (which likely impeded the light penetration) or to the difficulty to access to the [CoII3FeIII2] configuration from the blue solid phase. Above 50 K, the photo-excited state relaxed to the thermodynamic [CoIICoIII2FeII2] phase, that reproducibly exhibits the same magnetic properties observed before irradiation.56
![]() | ||
Fig. 5 (top) Representation of the molecular structure of {[(pzTp)FeIII(CN)3]4[CoII((pz)3CCH2OH)]4}[ClO4]4·13DMF·4H2O (13) at T = 260 K. Hydrogen atoms, perchlorate and lattice-solvent molecules are omitted for clarity. Fe, Co, N, C, O and B atoms are indicated in orange, dark blue, light blue, light grey, red and pink, respectively. (bottom) χT versus T data of 13 at 0.4 K min−1 and a constant magnetic field of 1 T before (black dots) and after (red dots) white light irradiation, and after thermal quenching (blue dots). Reprinted with permission from ref. 57. Copyright 2008 American Chemical Society. |
The magnetic properties as a function of temperature and light irradiation were carried out to further study the physical properties of compound 13. Magnetic susceptibility measurements revealed a constant χT product of 12.7 cm3 K mol−1 from 300 to 265 K, in a good agreement with non interacting FeIIILS and CoIIHS magnetic centres in a 4:
4 ratio (Fig. 5, bottom). An abrupt and reproducible decrease of the χT value down to 0.57 cm3 K mol−1 was observed when the sample was cooled below 255 K, evidencing the intramolecular electron transfer from the paramagnetic [FeIIILSCoIIHS]4 configuration into the diamagnetic [FeIILSCoIIILS]4 one. Moreover, the authors demonstrated that the high temperature [FeIIILSCoIIHS]4 phase can be thermally trapped by rapidly cooling the sample, or photo-generated at 30 K after 20 hours of white light irradiation. A gradual increase of the temperature (at 0.4 K min−1) allowed the complete relaxation of the metastable state toward the thermodynamic [FeIILSCoIIILS]4 phase at about 180 K. This remarkably high relaxation temperature clearly evidenced the long lifetime of the metastable state, which was further studied as a function of the temperature. For both thermally and photo-induced metastable states, the characteristic relaxation time (τ) followed the same Arrhenius law with an extremely large activation energy barrier of 4455 K and τ0 = 2.6 × 10−8 s. In comparison to tridimensional PBAs, 7 or Na0.6Co1.21[Fe(CN)6]·4.2H2O, which possess τ values at 120 K of ca. 33 or 3 hours respectively,40–42 this [Fe4Co4] molecular cube possesses an exceptionally long relaxation time estimated at 10 years at 120 K.57
![]() | ||
Fig. 6 (top) Representation of the molecular structure of {[(Tp*)FeIII(CN)3]2[CoII(bpy)2]2}[OTf]2·4DMF·2H2O (14) at T = 230 K. Hydrogen atoms, triflate and lattice-solvent molecules are omitted for clarity. Fe, Co, N, C, and B atoms are indicated in orange, dark blue, light blue, light grey, and pink, respectively. (bottom) χT versus T data of 14 at 0.4 K min−1 before (black dots, 0.1 T) and after (green dots, 1 T) white light irradiation, and after thermal quenching (purple dots, 0.1 T). Reprinted with permission from ref. 61. Copyright 2010 Wiley-VCH. |
After the discovery of 14, several other Fe/Co molecular square complexes featuring thermally and/or photo-induced electron transfer have been reported.62 Using a similar building block approach, different groups have obtained these new square complexes by the modification of the ligands capping the metal centres or by looking at the influence of the counter-ion or the synthesis/crystallization solvent mixture. Indeed, the functionalization of the 2,2′-bipyridine ligand (bpy) has been one of the main approaches to develop new tetranuclear [Fe2Co2] square compounds. For example, the addition of alkyl R groups on bpy (bpyR) tunes the electronic properties of the final complex, but also its solubility. The first related complexes were reported by Oshio and co-workers who synthesized and studied {[(Tp*)FeIII(CN)3]2[CoII(bpy)2]2}[PF6]2·2MeOH (15) and {[(Tp*)FeIII(CN)3]2[CoII(dtbbpy)2]2}[PF6]2·2MeOH (16, dtbbpy: 4,4′-di-tert-butyl-2,2′-bipyridine).63,64 The former analogue was found to exhibit a paramagnetic [FeIIILSCoIIHS]2 state independently of the temperature. The absence of electron-transfer properties was attributed by the authors to the lack of donating group on the bpy ligand, which results in an increase of the redox potential at the cobalt site. This hypothesis, that was proposed by comparing the redox properties of both 15 and 16 (vide infra),64a contrasts completely with the results observed for 14,61 which rather suggest a strong influence of the counter-ion within these systems and more generally the importance of the crystal packing on the electron transfer properties. Remarkably, complex 16 showed a two-step thermally induced electron transfer behaviour, with diamagnetic [FeIILSCoIIILS]2 and paramagnetic [FeIIILSCoIIHS]2 configurations at low and high temperatures, respectively. In between at intermediate temperatures, the nature of the phase is still controversial. While infrared spectroscopy and X-ray diffraction studies suggest a 1:
1 mixture of both [FeIILSCoIIILS]2 and [FeIIILSCoIIHS]2 squares, DFT calculations support the stabilization of a one-electron transfer species with a [FeIILSCoIIILSFeIIILSCoIIHS] configuration.64b The photo-generation of the paramagnetic phase was successfully carried out by irradiating the compound with an 808 nm laser at 5 K. The light-induced metastable state was found to relax to the [FeIILSCoIIILS]2 state around 80 K when increasing the temperature, as well as by irradiating the sample with green light (532 nm) at 5 K.65 The same authors have also recently characterized compound 16 before and after irradiation using X-ray diffraction and X-ray absorption spectroscopy.65,66 Interestingly, the X-ray beam itself was also found to produce the paramagnetic [FeIIILSCoIIHS]2 state, since accumulating XAS measurements on the diamagnetic [FeIILSCoIIILS]2 state at 15 K induced gradual changes in the XAS spectra with time toward the one observed at high temperature.66
Another important result was reported by Oshio and co-workers, who used compound 16 to demonstrate for the first time the possibility of transferring the electron transfer phenomenon and the associated properties from solid state to solution.64 When 16 was dissolved in butyronitrile, significant changes were observed in temperature by UV-Vis spectroscopy. Reducing the temperature, the intensity of the UV-Vis band associated with the [FeIIILSCoIIHS]2 state described a S-shape variation and the signature of the [FeIILSCoIIILS]2 state was observed below 200 K. Remarkably, the thermal equilibrium between the two [FeIILSCoIIILS]2 and [FeIIILSCoIIHS]2 states and their respective populations in solution were determined for the first time in temperature by UV-Vis spectroscopy. It is also important to mention that the intermediate state detected in solid state was absent in solution likely due to the lack of intermolecular interactions in solution.64 Furthermore, UV-Vis spectroscopy was also used to monitor the electron transfer process upon addition of trifluoroacetic acid at fixed temperature. This remarkable result demonstrated for the first time the possibility of inducing an electron transfer in these molecular Fe/Co PBAs by protonation. The same authors also explored the possibility of changing the ligand capping the iron centre by using the Tp ligand (Tp: hydrotris(pyrazol-1-yl)borate) to synthesize the related compound {[(Tp)FeIII(CN)3]2[CoII(dtbbpy)2]2}[PF6]2·4H2O (17).64 The absence of methyl groups on the Tp ligand stabilizes the FeII low spin state, thus leading to a diamagnetic [FeIILSCoIIILS]2 electronic configuration for 17 in the whole temperature range. The good solubility of these [Fe2Co2] systems permitted the study of their electron transfer by electrochemical measurements. Four redox processes attributed to the [Fe2Co2]2+ moiety were observed by cyclic voltammetry experiments permitting (i) the simple comparison of the redox potentials of each metal centre for complexes 15, 16 and 17, and (ii) to probe the influence of the ligand functionalization by alkyl groups. The authors concluded that the addition of electron donating groups on the bpy and Tp* ligand offers a control of the redox potential at the Co and Fe sites, respectively, allowing the stabilisation of a thermally induced electron transfer phenomenon in 16.
The influence of the bpy functionalization was also studied by Clérac, Mathonière, and co-workers in particular with complex 18, {[(Tp*)FeIII(CN)3]2[CoII(bpyMe)2]2}[OTf]2·DMF·H2O, for which the bpy ligand of complex 14 is replaced by bpyMe (bpyMe: 4,4′-dimethyl-2,2′-bipyridine).67 This simple modification influenced dramatically the thermally induced electron transfer mechanism and the associated properties. While complex 14 exhibited a first order transition with a significant thermal hysteresis associated with the electron transfer process (vide supra; Fig. 6), a thermal conversion (i.e. a thermal equilibrium between the two [FeIILSCoIIILS]2 and [FeIIILSCoIIHS]2 states) was observed for 18. Similarly to spin-crossover systems, the electron transfer transition in 14 is converted in an electron transfer conversion in 18 by decreasing the elastic interactions between the molecules (i.e. decreasing the cooperativity) thanks to weaker π–π interactions between bpyMe moieties in 18 than between bpy ligands in 14.67
Combined UV-Vis spectroscopy and magnetic measurements of 14 and 18 in the different solvents were used to confirm that the occurrence of the intramolecular electron transfer was preserved in solution.67 While the electron transfer process was detected only in methanol and acetonitrile for 14, the physical properties of 18 were transferred to dilute solutions using a larger number of solvents. Interestingly, the thermally induced electron transfer conversion was found to be strongly influenced by the nature of the used solvent. For example, a shift of about 60 K was observed when comparing T1/2 (temperature where the ratio between the paramagnetic and diamagnetic configurations is 1:
1) for 18 in CH3OH (240 K) and CH2Cl2 (180 K). A general tendency showed that T1/2 values increased with the solvent polarity, allowing a fine tuning of the electron transfer properties simply by a judicious choice of the solvent or adjusting the composition of a solvent mixture. For comparison, the authors also reported the solution properties of the related compound 19, {[(Tp*)FeIII(CN)3]2[CoII(DMF)4]2}[OTf]2·2DMF, possessing cobalt ions capped by only coordinating DMF molecules and not bpy type ligands like in the analogues described above.61,67,68 In this case, the complex stays paramagnetic in solid state68 but also in all the solvents tested,67 confirming the influence of the ligand environment on the redox potential of the Co site and thus the occurrence of an intramolecular electron transfer process. Recently, Oshio and co-workers obtained a similar complex {[(Tp*)FeIII(CN)3]2[CoII(dmbpy)2]2}[PF6]2·4MeCN (20, dmbpy: 5,5′-dimethyl-2,2′-bipyridine), by changing the position of the methyl group on the bpy ligand in comparison to complex 18.69 Like for 19, X-ray diffraction and magnetic measurements in the solid state evidenced that 20 is stabilised in its paramagnetic [FeIIILSCoIIHS]2 configuration independently of the temperature. These results highlight how sensitive is the electron transfer process for these [Fe2Co2] square complexes in the solid state and solutions, regarding the functionalization of the bpy ligand, as well as the choice of the counter-anions and the solvent molecules surrounding the complex.60–69 The effect of the crystallisation solvent molecules was also illustrated by the appearance of both thermally and photo-induced electron transfer phenomena when 20 is desolvated.69
The influence of the ancillary ligands and the effect of the intermolecular interactions within these kinds of Fe/Co molecular squares were also recently studied by Holmes, Clérac, Mathonière and co-workers.70 Two new complexes of this family, {[(TpMe)FeIII(CN)3]2[CoII(bpy)2]2}[(TpMe)FeIII(CN)3]2·12H2O (21, TpMe: hydrotris(3-methylpyrazol-1-yl)borate) and {[(TpMe)FeIII(CN)3]2[CoII(bpy)2]2}[BPh4]2·6MeCN (22) were synthesized using [NEt4][(TpMe)FeIII(CN)3]·9H2O as a new iron building block. As their analogues, these [Fe2Co2] systems show thermally and photo-induced electron transfer properties with a metastable paramagnetic state relaxing at 90 K and 120 K for 21 and 22, respectively. The obtained T1/2 values were 244 K for 21, and 230 K for 22. These values are higher than those observed for the related Tp*-based complexes (i.e., 177 K for 14, 174 K for 18), demonstrating that the weaker σ donor character of the TpMe ligand stabilizes the low spin state of the FeII sites. This conclusion is corroborated by the properties of the related Tp-based complexes such as 17 (vide supra), which is diamagnetic due to an even weaker σ donor character of Fe capping ligand.64 With this study, the authors demonstrated how the functionalization of the Tp ligand can also tune the electron transfer properties of the Fe/Co molecular squares. In contrast, no clear influence on T1/2 was observed from the different intermolecular interactions detected in 21 and 22. On the other hand, Li and co-workers synthesized and studied another example of a Fe/Co molecular square using the Tp ligand to chelate the iron sites and 4,4′-bis(ethoxycarbonyl)-2,2′-bipyridine (4,4′-bcbpy) as capping ligand for the cobalt centres: {[(Tp)Fe(CN)3]2[Co(4,4′-bcbpy)2]2}[ClO4]2·2MeOH (23·2MeOH).71a Accordingly, only the diamagnetic [FeIILSCoIIILS]2 configuration was observed up to 300 K for 23·2MeOH. However when the methanol molecules were removed from the lattice, complex 23 exhibited an incomplete thermally induced electron transfer to the paramagnetic [FeIIILSCoIIHS]2 state around 200 K. The authors attributed this effect to the loss of the hydrogen bonding network present between these molecular squares that is supposed to induce a negative shift of the redox potentials of the iron ions, thus promoting the electron transfer.71a Under external pressure (up to 8.35 kbar), the T1/2 value increased slightly and the electron transfer process became almost complete. Remarkably when the crystals of 23 were soaked in methanol, the diamagnetic state was fully recovered, and this “crystal-to-crystal” transformation was found to be reversible. Interestingly, the same group recently published a related compound featuring similar ligands for both metal centres: {[(MeTp)Fe(CN)3]2[Co(4,4′-bmbpy)2]2}[PF6]2·2MeOH (24·2MeOH, MeTp: methyltris(pyrazolyl)borate, 4,4′-bmbpy: 4,4′-bis(methoxycarbonyl)-2,2′-bipyridine).71b While the metal ion precursors exhibit similar redox potentials to the ones in 23·2MeOH, both thermal and photo-induced electron transfer processes were observed for compound 24·2MeOH. The authors justified these contrasted behaviours by the significant distortion of the molecular square's core and the highly bent Co–N–C angles in 24·2MeOH, which induce a decrease of the characteristic temperature of the electron transfer process.71b In this respect, Li's work introduces the influence of the square distortion and demonstrates once more the importance of the lattice environment in the electron transfer properties of these [Fe2Co2] compounds.
Lescouëzec and co-workers also reported a Fe/Co cyanido-based square complex using the pzTp iron derivative and the bis(1-methylimidazol-2-yl)ketone (bik) ligand to coordinate at the cobalt centres: {[(pzTp)Fe(CN)3]2[Co(bik)2]2}[ClO4]2·2H2O (25).72 While the magnetic measurements clearly indicates the diamagnetic nature of 25 between 2 and 300 K, the irradiation of the [FeIILSCoIIILS]2 state (with white light at 20 K) led to a photo-induced electron transfer engendering paramagnetic [FeIIILSCoIIHS]2 species. In 2013, the same authors demonstrated that this metastable paramagnetic state in 25 could also be photo-generated using laser sources, with a high efficiency at 808 nm.73 Interestingly, this photo-excited state was found to photo-relax to the diamagnetic one after irradiation at 532 nm, showing for the first time a bidirectional photomagnetic effect for a Fe/Co molecular PBA at a fixed temperature.
For comparison, the previously discussed [Fe2Co2] systems are gathered in Table 2, mentioning the ligands occupying the iron (LFe) and cobalt (LCo) coordination spheres, the used anion, the state of the compound for the study, the temperature at which the thermally induced electron transfer occurs and the temperature at which the system relaxes after a photo-induced electron transfer.
Compound | LFe | LCo | Anion | T 1/2 (K) of the ET or magnetic state | T relax (K) of the photo-induced state | State studied | Ref. |
---|---|---|---|---|---|---|---|
a Data obtained from the desolvated form of the compound.
b Temperature where the ratio between the paramagnetic and diamagnetic configurations is 1![]() ![]() |
|||||||
14 | Tp* | bpy | OTf− | 168/186 | 120 | Solid/solution | 61 and 67 |
15 | Tp* | bpy | PF6− | Paramagnetic | — | Solid | 64 |
16 | Tp* | dtbbpy | PF6− | 275 and 310 (two steps) | 80 | Solid/solution | 63 and 64 |
17 | Tp | dtbbpy | PF6− | Diamagnetic | — | Solid/solution | 64 |
18 | Tp* | bpyMe | OTf− | 174 | 120 | Solid/solution | 67 |
19 | Tp* | (DMF)4 | OTf− | Paramagnetic | — | Solid/solution | 67 |
20 | Tp* | dmbpy | PF6− | 240 | 100 | Solid | 69 |
21 | TpMe | bpy | [(TpMe)Fe(CN)3]− | 244 | 100 | Solid | 70 |
22 | TpMe | bpy | BPh4− | 230 | 120 | Solid | 70 |
23 | Tp | 4,4′-bcbpy | ClO4− | 120 | — | Solid | 71a |
24 | MeTp | 4,4′-bmbpy | PF6− | 177/184 | 100 | Solid | 71b |
25 | pzTp | bik | ClO4− | Diamagnetic | 100 | Solid | 72 and 73 |
![]() | ||
Fig. 7 (top) Representation of the molecular structure of [(bbp)Fe(CN)3Co(PY5Me2)]·2.5MeOH (26) at T = 370 K. Hydrogen atoms and lattice-solvent molecules are omitted for clarity. Fe, Co, N and C atoms are indicated in orange, dark blue, light blue and light grey, respectively. (bottom) Evolution of the UV-Vis spectra upon TFA (TFA: trifluoroacetic acid) addition to a solution of 26 in DMSO, showing the colour change from dark green (paramagnetic, [FeIIILSCoIIHS]) to purple (diamagnetic, [FeIILSCoIIILS]). Reproduced from ref. 76 with permission from The Royal Society of Chemistry. |
Unexpectedly, 26 exhibits a spin-crossover process occurring at the cobalt site in the solid state.76 Nevertheless when 26 was studied in solution, different physical properties were observed. DMSO solutions of 26 were studied by magnetic susceptibility measurements to show that the spin-crossover behaviour is lost and only the paramagnetic [FeIIILSCoIIHS] configuration is observed above 1.8 K. However, when DMSO solutions were treated with an acid (trifluoroacetic or trifluoromethanesulfonic acids), their colour changed from dark green to purple. This proton-induced evolution was proven to be associated with a change of the [FeCo] pair electronic configuration by UV-vis spectroscopy, following the concomitant disappearance of the ligand-to-metal charge transfer band and the appearance of the metal-to-ligand charge transfer absorption centred on the iron moiety upon acid addition (Fig. 7, bottom). Moreover, the 1H NMR spectra measured before and after acidifying the solution demonstrated the conversion of the paramagnetic [FeIIILSCoIIHS] complexes into diamagnetic species which can only be [FeIILSCoIIILS] pairs. Using combined cyclic voltammetry and UV-vis spectroscopy on 26 and its molecular precursors, it was shown that the proton addition only affects the iron redox properties, shifting its potential toward the unaffected Co one and thus promoting the electron transfer mechanism. By crystallizing the iron precursor after protonation ([Fe(H2bbp)(CN)3]·2H2O), the authors revealed that added protons were indeed doubly protonating the bpp ligand affecting only the redox properties of the Fe site. Remarkably, complex 26 is the first dinuclear [FeCo] PBA to exhibit a metal-to-metal electron transfer, and this process is not triggered by temperature or light but by protonation.76
The detailed study of the redox properties of 26 under protonation76 was the key to obtain the first dinuclear Fe/Co complex exhibiting a thermally and light-induced electron transfer in the solid state. Clérac, Mathonière, Li and co-workers77 replaced the [Fe(bbp)(CN)3]2− building-block used in the synthesis of 26 by the [(Tp)FeIII(CN)3]− precursor that displays a redox potential in between those of [Fe(bbp)(CN)3]2− and [Fe(H2bbp)(CN)3], which combined with [Co(PY5Me2)]2+ afforded paramagnetic and diamagnetic dinuclear species respectively (vide supra).76 This rational synthetic strategy successfully affords [(Tp)Fe(CN)3Co(PY5Me2)][OTf]·2DMF, (27·2DMF, Fig. 8, top) for which magnetic susceptibility and X-ray diffraction measurements demonstrated the presence of a partial (50%) thermally induced electron transfer in the solid state at 165 K. When 27·2DMF was treated at high temperature and under vacuum, a quasi-complete electron transfer transition was observed at 170 K exhibiting a thermal hysteresis of about 5 K (with a sweep rate of 0.4 K min−1; Fig. 8, bottom). As shown by IR spectroscopy, the heating/vacuum treatment of 27·2DMF leads to a complete removal of the interstitial DMF molecules highlighting the crucial influence of the crystal packing on the electron transfer phenomenon. Solid-state optical reflectivity measurements and photomagnetic studies showed that the paramagnetic [FeIIILSCoIIHS] configuration can be photo-induced at 10 K with a white light irradiation of the diamagnetic sample. This metastable phase relaxes to the thermodynamic [FeIILSCoIIILS] state after heating above 45 K (with a sweep rate of 0.4 K min−1; Fig. 8, bottom). It is worth mentioning that this temperature is the lowest relaxation temperature observed for any molecular PBAs and it seems to decrease with the miniaturization of the complex. From these results, complex 27 can be then considered as the first dinuclear Fe/Co PBA exhibiting both thermally and photo-induced electron transfer processes in the solid state.77
![]() | ||
Fig. 8 (top) Representation of the molecular structure of [(Tp)Fe(CN)3Co(PY5Me2)](OTf)·2DMF (27·2DMF) at T = 180 K. Hydrogen atoms, triflate and lattice-solvent molecules are omitted for clarity. Fe, Co, N and C atoms are indicated in orange, dark blue, light blue and light grey, respectively. (bottom) χT versus time (blue circles) of the desolvated compound, 27, at 1 T and 10 K under white light irradiation (3 mW cm−2), and χT versus temperature before (black dots) and after (red dots) white light irradiation with a sweep rate of 0.4 K min−1. Reprinted with permission from ref. 77. Copyright 2014 American Chemical Society. |
Oshio and co-workers reported a tetradecanuclear [Fe8Co6] complex [Fe8Co6(μ-CN)14(CN)10(Tp)8(HL)10(CH3CN)2][PF6]4·14CH3CN·5H2O (28·14CH3CN·5H2O, HL: 3-(2-pyridyl)-5-[4-(diphenylamino)phenyl]-1H-pyrazole),78 by reacting [NBu4][(Tp)Fe(CN)3] with Co(BF4)2·6H2O in the presence of HL and [NBu4]PF6. A crown-like complex was obtained, exhibiting a twelve-membered ring with alternated Fe and Co metal ions decorated with two dangling [(Tp)Fe(CN)3]− moieties. Independently of the temperature, coordination bond lengths, magnetic measurements and Mössbauer spectroscopy revealed the paramagnetic [(FeIIILS)8(CoIIHS)6] configuration of 28·14CH3CN·5H2O. However, when this compound was left at ambient temperature for several days, the magnetic properties changed drastically. Elemental analysis and TGA data established the total loss of the acetonitrile solvated molecules leading to formulate this compound as 28·5H2O. In this “aged” sample, a decrease of the χT product was observed from 250 to 150 K before levelling to a value of about 9.4 cm3 K mol−1. From these magnetic measurements, the authors concluded to the presence of a [(FeIIILS)5(FeIILS)3(CoIIHS)3(CoIIILS)3] configuration below 150 K in 28·5H2O. This low temperature phase was stabilized by a CoII to FeIII electron transfer in three FeIII–CN–CoII pairs from the high temperature [(FeIIILS)8(CoIIHS)6] state. Remarkably, this compound in its [(FeIIILS)5(FeIILS)3(CoIIHS)3(CoIIILS)3] configuration at 20 K was efficiently converted (at about 76%) in its fully paramagnetic [(FeIIILS)8(CoIIHS)6] state using laser irradiations (at 405 or 808 nm). Increasing the temperature, the photo-generated phase relaxed to its thermodynamic state above 150 K.78
Recently, the same group synthesized a new decanuclear Fe/Co complex containing six cobalt ions and four iron centres: [NEt4]2{[Co(LR)]6[Fe(CN)6]4}[BF4]·17CH3OH·12H2O (29, Fig. 9 top).79 For its synthesis, the authors used the LR ligand that was obtained in situ by reacting 2-pyridinecarbaldehyde and R-(+)-phenylethylamine, together with the metal ion precursors (Co(BF4)2·6H2O and [NEt4]3[Fe(CN)6]). This serendipitous synthetic strategy led to a cage-type species, featuring six [Co(LR)2] and four hexacyanoferrate units, encapsulating one tetraethylammonium cation (Fig. 9, top). Structural studies and Mössbauer spectroscopy evidenced the presence of a thermally induced electron transfer in 29 from a [(CoIIHS)5CoIIILS(FeIILS)2(FeIIILS)2] configuration at high temperatures to a [(CoIIHS)3(CoIIILS)3(FeIILS)4] state at 100 K. This conclusion was corroborated by magnetic susceptibility studies (Fig. 9, bottom) which detected a characteristic thermal variation of the χT product from 12.4 cm3 K mol−1 at 300 K (close to the expected value for five CoIIHS and two FeIIILS centres) down to 6.8 cm3 K mol−1 below 180 K (in agreement with the value expected for three CoIIHS ions) clearly associated with the metal-to-metal electron transfer process. As already observed for other compounds of this family, the desolvated version of 29 led to different physical properties with, in this case, a loss of the thermally induced electron transfer.79
![]() | ||
Fig. 9 (top) Representation of the molecular structure of [NEt4]2{[Co(LR)]6[Fe(CN)6]4}[BF4]·17CH3OH·12H2O (29) at T = 100 K. Hydrogen atoms, tetrafluoroborate and lattice-solvent molecules are omitted for clarity. Fe(II), Co(III), Co(II), N and C atoms are indicated in brown, green, dark blue, light blue and light grey, respectively. (bottom) χT versus T data cooling (blue dots) and heating (red dots) the sample, together with the diagrams of the spin state of each metal ion. Reprinted with permission from ref. 79. Copyright (2014) American Chemical Society. |
![]() | ||
Fig. 10 (top) Representation of the molecular structure of [Co2Fe4(bimpy)2(CN)6(μ-CN)6(pzTp)4]·2(1-PrOH)·4H2O (30) at T = 100 K. Hydrogen atoms and lattice-solvent molecules are omitted for clarity. Fe, Co, N, C, and B atoms are indicated in orange, dark blue, light blue, light grey, and pink, respectively. (bottom) χ′ versus T (a) and χ′′ versus T (b) data for compound 30 after light irradiation (Hac = 3 Oe oscillating at 10–1500 Hz and Hext = 500 Oe) demonstrating the slow relaxation of the magnetization in the light-induced paramagnetic phase. Reprinted with permission from ref. 81. Copyright 2012 Wiley-VCH. |
Another interesting example of multifunctional molecular cyanido-bridged Fe/Co complex exhibiting an electron transfer phenomenon was reported by Liu, Sato, Duan and coworkers.82 In this case, the authors described a linear trinuclear compound, {[(Tp)Fe(CN)3]2Co(Meim)4}·6H2O (31, Meim: N-methylimidazole), with the aim of controlling concomitantly the dielectric and the magnetic properties of the system. The reaction of [NBu4][(Tp)Fe(CN)3] with Co(NO3)2·6H2O in the presence of Meim led to 31, where a cobalt centre is inserted between two iron metal ions in a linear cyanido-bridged skeleton. At 240 K, the bond lengths around the metal ions observed in the crystal structure agreed well with a [FeIIILSCoIIHSFeIIILS] configuration. After cooling the sample at 150 K, a significant decrease of the bond distances around the Co site suggested a thermally induced electron transfer from the cobalt metal ion to one of the two iron centres (likely occurring randomly between the two iron sites) leading to a low temperature [FeIILSCoIIILSFeIIILS] state. This conclusion was also supported by infrared and 57Fe Mössbauer spectroscopies, from which the characteristics of the two iron configurations, FeIILS and FeIIILS, were clearly observed. The thermal dependence of the magnetic susceptibility confirmed a reversible electron transfer transition (i.e. a first order phase transition) centred around 225 K with a small thermal hysteresis of about 10 K at 0.5 K min−1. The χT values at high and low temperatures were found to be in good agreement with the expected electronic configurations. The possibility to photo-induce the electron transfer process was also demonstrated at 5 K by irradiating the sample with a laser source at 535 nm. This effect was found to be relatively inefficient in 31 with only about 20% of photo-conversion. The magnetic susceptibility measurements showed that this photo-induced [FeIIILSCoIIHSFeIIILS] fraction of the sample relaxed completely to the [FeIIILSCoIIILSFeIILS] phase upon heating above 90 K.82 In both thermally or photo-induced electron transfer processes for 31, one electron from the single CoIIHS site was transferred to one of the two FeIIILS centres. This phenomenon was thus imposing a change from a centrosymmetric nonpolar [FeIIILSCoIIHSFeIIILS] molecule into an asymmetric [FeIIILSCoIIILSFeIILS] polar one, demonstrating the possibility to switch the polarity of a given complex by a “directional” electron transfer mechanism. Based on the X-ray crystal structures, DFT calculations were used to estimate the permanent electric dipole moment of the low temperature phase (18.4 D), and to demonstrate the absence of dipole moment for the high temperature configuration. With this example, the authors demonstrated for the first time that it is possible to trigger a polar/nonpolar conversion of a molecular system by a thermally and photo-induced electron transfer mechanism.82
The first example, {[(Tp)Fe(CN)3]2Co(bpe)}·5H2O (32·5H2O), was described by Sato and co-workers in 2010.83 This compound was synthesized by reacting Li[(Tp)Fe(CN)3] with Co(NO3)2 and 1,2-bis(4-pyridyl)ethane (bpe). This compound contains cyanido-bridged Fe/Co double zigzag chains (Fig. 11, top) with each cobalt centre linked to four [(Tp)Fe(CN)3]− moieties which themselves act as a bidentate metallo-ligand between Co ions (Fig. 11, top). In the crystal structure, these chains are interconnected by the bpe ligands to form a two-dimensional framework. In addition, uncoordinated water molecules are located between the cyanido-bridged Fe/Co layers, interacting with them by significant hydrogen bonding interactions. At 223 K, the red crystals of 32·5H2O exhibit a structure with metal–ligand bond distances indicating only paramagnetic CoIIHS and FeIIILS sites. Lowering the temperature to 123 K, the structure of the thermochromic dark green crystals revealed the presence of randomly distributed FeIILS, FeIIILS, CoIIHS and CoIIILS metal ions. This conclusion based on the metal–ligand bond distances was attributed to a partial intramolecular electron transfer as also supported by temperature-dependent IR spectroscopy, that showed reversibly the expected νCN bands at the different temperatures. The metal-to-metal electron transfer process was further confirmed by magnetic susceptibility studies. Above 220 K, the obtained χT value agreed well with only FeIIILS (two sites) and CoIIHS (one site) magnetic centres (5.1 cm3 K mol−1; Fig. 11, bottom). Lowering the temperature, the χT product experienced a marked decrease around 180 K, before stabilizing down to about 1.9 cm3 K mol−1 below 120 K. This low temperature value suggested that only two-thirds of the CoIIHS metal ions are transformed into CoIIILS sites. In addition to the thermally induced electron transfer phenomenon, the authors demonstrated that the high-temperature configuration can also be photo-generated at 5 K. After 12 hours of 532 nm light irradiation, the χT product raised notably. The resulting photo-induced phase was shown to relax to the original thermodynamic state upon heating the sample above 150 K. Interestingly, these thermally and photo-induced electron transfer phenomena exhibited by 32·5H2O vanished after dehydrating the sample (Fig. 11, bottom). In both materials, 32·5H2O and 32, the magnetic properties revealed the occurrence of dominant ferromagnetic interactions between the paramagnetic metal ions (Fig. 11, bottom) as observed in 30,81 and again in contrast with the three dimensional PBAs.23,24,31 Based on the crystal structure of 32 that established the complete removal of the water molecules observed in 32·5H2O, the authors attributed the absence of electron transfer properties in 32 to the lack of the water hydrogen bonding interactions toward terminal cyanido groups. This scenario suggests that the hydrogen bond network produced by the water molecules in 32·5H2O, pushes the redox potentials of the two metal ion sites to be close enough to favour the metal-to-metal electron transfer.83 This “water-switchable” electron transfer system highlights once more the extreme sensitivity of the electron transfer process likely in link with redox potentials of the metal centres.
![]() | ||
Fig. 11 (top) Representation of the molecular structure of {[(Tp)Fe(CN)3]2Co(bpe)}·5H2O (32·5H2O) at T = 123 K. Hydrogen atoms and lattice-solvent molecules are omitted for clarity. Fe, Co, N, C, and B atoms are indicated in orange, dark blue, light blue, light grey, and pink, respectively. (bottom) χT versus T data of the hydrated (blue line), dehydrated (red line) and rehydrated (squares) of 32. Reprinted with permission from ref. 83. Copyright 2010 Wiley-VCH. |
By changing the environment of the iron centre, the same group reported another two-dimensional compound 33, {[Fe(bpy)(CN)4]2Co(4,4′-bipyridine)}·4H2O, exhibiting thermally and photo-induced electron transfer properties.84 In this case, the authors used Li[Fe(bpy)(CN)4] as the iron precursor, while Co(ClO4)2 and 4,4′-bipyridine were chosen to assemble the cobalt counterpart. As in 32·5H2O (Fig. 11, top), the crystal structure shows a double zigzag chain conformation, with the cobalt metal ions connected by four cyanide groups to four [Fe(bpy)(CN)4] moieties. Two 4,4′-bipyridine ligands complete the Co coordination sphere and connect the chains into a 2D network. As already observed in 32·5H2O, water molecules are intercalated between the cyanido/bpy-bridged Fe/Co layers. Partial thermally (around 215 K) and light-induced electron transfer phenomena were characterized by X-ray diffraction, infrared spectroscopy, magnetic measurements and recently by X-ray absorption spectroscopy.84b Interestingly, strong frequency dependence of the ac susceptibility (for both in-phase and out-of-phase components) was observed in the photo-induced metastable state of 33. The relaxation time of the dynamics was shown to follow an Arrhenius law with an energy barrier of 29 K and a pre-exponential factor of 1.4 × 10−9 s. Based on a qualitative analysis of the magnetic data, the authors attributed the observed slow dynamics of the magnetization to the intrinsic Single-Chain Magnet (SCM)85 properties of the chains in the antiferromagnetically ordered phase (TN = 3.8 K).
In order to minimize the inter-chain magnetic interactions and obtain a SCM system, the authors recently proposed to use other ligands able to separate more efficiently the {Fe2Co}∞ chains. This strategy is well illustrated by complex 34, {[(pzTp)Fe(CN)3]2Co(4-styrylpyridine)2}·2H2O·2CH3OH.86 In this case, Liu, Sato, Duan and co-workers used a bulkier pzTp ligand to block the iron centre, while a monodentate ligand (4-styrylpyridine) was chosen to complete the coordination of the cobalt ion. Consequently, 34 exhibits an one-dimensional structural organization with double zigzag chains (similar to 32·5H2O in Fig. 11, top), which are not connected (in contrast to 32·5H2O and 33) but just separated by uncoordinated water molecules. In this case, crystallographic, spectroscopic and magnetic techniques confirmed a full thermally induced electron transfer around 230 K from FeIIILS–CN–CoIIHS pairs to FeIILS–CN–CoIIILS ones while decreasing the temperature. As the stoichiometry of compound 34 is one cobalt for two Fe centres, only half of the iron metal ions are involved in the electron transfer process with all Co sites. Surprisingly, this phenomenon engaged specifically one of the two iron sites instead of randomly involving both iron centres as described for example in the trinuclear complex 31.82 The authors attributed this ordered electron transfer to the presence of different hydrogen bonding interactions around the two [(pzTp)Fe(CN)3]2− units with the solvent molecules in the crystal packing. The photo-induced electron transfer was first shown in 34 by infrared spectroscopy and the decrease of the bridging νCN absorption peaks from the FeII/IIILS–CN–CoIIILS units after a 532 nm laser irradiation of the sample. Magnetic measurements further confirmed the photoactivity of the sample. After an irradiation of 12 hours at 5 K, the χT product was significantly increased as expected for the photoconversion of a material composed essentially of isolated paramagnetic FeIIILS centres to an one-dimensional magnetically correlated {(FeIIILS)2CoIIHS}∞ system. The magnetization dynamics of these metastable photo-induced chains was studied by ac magnetic susceptibility measurements, which revealed a thermally activated relaxation time with an energy barrier of 27 K (τ0 = 1.4 × 10−10 s). Based solely on the study of the magnetization dynamics, the authors concluded to the photo-induced SCM properties of 34. In addition, the thermal relaxation of the metastable photo-induced state was studied by monitoring the time decay of the magnetization at different temperatures. Above 40 K, the photo-generated phase relaxed with an Arrhenius behaviour and an energy barrier of 1348 ± 200 cm−1 (1926 ± 286 K) (τ0 = 8.4 × 10−12 s). In contrast at lower temperatures (<40 K), a temperature independent tunnelling relaxation of the excited paramagnetic {(FeIIILS)2CoIIHS}∞ state to the {FeIIILSFeIILSCoIIILS}∞ ground state was observed. Overall, this remarkable compound constitutes the first evidence of the possibility to design photo-switchable single-chain magnets from one-dimensional cyanido-bridged Fe/Co Prussian blue analogues based on a metal-to-metal electron transfer mechanism.86
In 2012, Oshio and co-workers reported another type of one dimensional cyanido-bridged Fe/Co compound with a chiral square-wave chain topology: {[CoII((R)-pabn)][(Tp)FeIII(CN)3]}(BF4)·MeOH·2H2O (35R·MeOH·2H2O; (R)-pabn: (R)-N(2),N(2′)-bis(pyridine-2-ylmethyl)-1,1′-binaphtyl-2,2′-diamine), and {[CoII((S)-pabn)][(Tp)FeIII(CN)3]}(BF4)·2H2O (35S·2H2O).87 By reacting [NBu4][(Tp)Fe(CN)3] with the corresponding cobalt building block ([CoII((R)-pabn)]2+ or [CoII((S)-pabn)]2+), the authors were able to synthesize both enantiomerically pure materials. These cyanido-bridged Fe/Co chain systems crystalized in the chiral P212121 space group, with the cobalt metal ions chelated by four N atoms from the pabn ligand and linked to two cyanide N atoms from the iron [(Tp)Fe(CN)3]− units (Fig. 12, top). Compound 35R·MeOH·2H2O was found to lose the solvated methanol molecules and evolves to 35R·H2O (when dried under N2) or to 35R·3H2O (when dried in air). While the magnetic properties of both R and S enantiomers were found, as expected, to be the same, the different solvated systems showed a thermally induced electron transfer phenomenon with a thermal hysteretic behaviour differing only by the T1/2 values (above 250 K). These materials appeared to be fully diamagnetic at low temperatures in agreement with the {FeIILSCoIIILS}∞ ground state and exhibited χT values (ca. 3.4 cm3 K mol−1) coherent with the paramagnetic {FeIIILSCoIIHS}∞ phase above the thermal hysteresis.87 These metal-to-metal electron transfer properties were also confirmed by Mössbauer spectroscopy and single-crystal X-ray diffraction experiments. In addition, the temperature dependence of the electrical properties of 35R·H2O was probed. Below 250 K, the value of the electrical conductivity was found to be around 10−12 S m−1, suggesting an insulating state. By increasing the temperature above the electron transfer temperature, the conductivity raised to about 10−9 S m−1 with semiconducting properties in the paramagnetic phase. Similarly to the magnetic properties, conductivity measurements exhibited a thermal hysteresis associated to the electron transfer process, thus demonstrating that 35R·H2O possessed not only magnetic but also electric bistability (Fig. 12, bottom). As well, the photomagnetic properties of 35R·H2O were studied by irradiating the sample with an 808 nm laser at 5 K. Under light, a fast increase of the χT values (up to ca. 300 cm3 K mol−1) was detected suggesting the photo-generation of the metastable paramagnetic {FeIIILSCoIIHS}∞ state. The χT vs. T data revealed the presence of ferromagnetic interactions between FeIIILS and CoIIHS magnetic sites within the photo-induced state, which relaxed to the diamagnetic ground state when the temperature exceeded 72 K. Furthermore, the characterization of the photo-generated {FeIIILSCoIIHS}∞ state was carried out by ac susceptibility measurements showing a strong frequency-dependence of both in-phase and out-of-phase signals. Two thermally activated relaxation processes of the magnetization were identified with energy barriers of 65.5 K (τ0 = 3.1 × 10−10 s−1) and 33.3 K (τ0 = 1.1 × 10−8 s−1). Without further analysis of the static magnetic susceptibility, the authors concluded from this dynamic study that the photo-induced state displayed single-chain magnet properties. Thanks to thermally and light-induced electron transfer processes, this multifunctional material displays above 250 K both magnetic and conductivity bistabilities in temperature, while below 10 K, a photo-induced “tristability” (from the diamagnetic state and the field-induced ±M states from the SCM properties) is also described.87
![]() | ||
Fig. 12 (top) Representation of the one-dimensional structure of [CoII((R)-pabn)][(Tp)FeIII(CN)3](BF4)·MeOH·2H2O (35R·MeOH·2H2O) shown at 360 K. Hydrogen atoms, tetrafluoroborate and lattice-solvent molecules are omitted for clarity. Fe, Co, N, C, and B atoms are indicated in orange, dark blue, light blue, light grey, and pink, respectively. (bottom) Temperature dependence of the χT product (blue dots) and the dc conductivity (red dots) of 35R·H2O. Reprinted with permission from ref. 87. Copyright (2012) Nature Chemistry, McMillan Publishers Ltd. |
Recently, Nojiri, Oshio and co-workers showed that the solid state grinding of 35R·MeOH·2H2O could also provoked an electron transfer and thus switched its diamagnetic state to the paramagnetic phase.88 This new way of inducing the metal-to-metal electron transfer was indeed associated to the partial dehydration of the sample (i.e. the loss of only one water molecule) as deduced by thermogravimetric experiments. L-edge XAS and XMCD measurements were performed to characterize the different phases before and after grinding the sample and confirmed the observed effect. This study highlighted once more the key role of the interstitial solvent molecules on the metal-to-metal electron transfer process.
This journal is © The Royal Society of Chemistry 2016 |