Manuel
Boniolo
a,
Petko
Chernev
a,
Mun Hon
Cheah
a,
Philipp A.
Heizmann
b,
Ping
Huang
a,
Sergii I.
Shylin
a,
Nessima
Salhi
ac,
Md Kamal
Hossain
b,
Arvind K.
Gupta
b,
Johannes
Messinger
*ad,
Anders
Thapper
*b and
Marcus
Lundberg
*ac
aMolecular Biomimetics, Department of Chemistry – Ångström Laboratory, Uppsala University, 75120 Uppsala, Sweden. E-mail: johannes.messinger@kemi.uu.se; marcus.lundberg@kemi.uu.se
bSynthetic Molecular Chemistry, Department of Chemistry – Ångström Laboratory, Uppsala University, 75120 Uppsala, Sweden. E-mail: anders.thapper@kemi.uu.se
cTheoretical Chemistry, Department of Chemistry – Ångström Laboratory, Uppsala University, 75120 Uppsala, Sweden
dDepartment of Chemistry, Chemical Biological Centre, Umeå University, 90187 Umeå, Sweden
First published on 9th December 2020
Developing new transition metal catalysts requires understanding of how both metal and ligand properties determine reactivity. Since metal complexes bearing ligands of the Py5 family (2,6-bis-[(2-pyridyl)methyl]pyridine) have been employed in many fields in the past 20 years, we set out here to understand their redox properties by studying a series of base metal ions (M = Mn, Fe, Co, and Ni) within the Py5OH (pyridine-2,6-diylbis[di-(pyridin-2-yl)methanol]) variant. Both reduced (MII) and the one-electron oxidized (MIII) species were carefully characterized using a combination of X-ray crystallography, X-ray absorption spectroscopy, cyclic voltammetry, and density-functional theory calculations. The observed metal–ligand interactions and electrochemical properties do not always follow consistent trends along the periodic table. We demonstrate that this observation cannot be explained by only considering orbital and geometric relaxation, and that spin multiplicity changes needed to be included into the DFT calculations to reproduce and understand these trends. In addition, exchange reactions of the sixth ligand coordinated to the metal, were analysed. Finally, by including published data of the extensively characterised Py5OMe (pyridine-2,6-diylbis[di-(pyridin-2-yl)methoxymethane])complexes, the special characteristics of the less common Py5OH ligand were extracted. This comparison highlights the non-innocent effect of the distal OH functionalization on the geometry, and consequently on the electronic structure of the metal complexes. Together, this gives a complete analysis of metal and ligand degrees of freedom for these base metal complexes, while also providing general insights into how to control electrochemical processes of transition metal complexes.
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Fig. 1 General structure of the pentapyridyl family of metal complexes (M = metal centre, R = ligand substituent, X = apical ligand). |
The family of pentapyridyl ligands stemming from Py5, (2,6-bis-[(2-pyridyl)methyl]pyridine) has been extensively adopted in the past two decades to complex different first-row transition metals.5 Feringa et al. reported the first example of FeII and MnII complexes with the methoxy-substituted ligand (Py5OMe), highlighting how the apical coordination site is particularly prone to ligand substitution and therefore can reversibly bind possible substrate candidates for catalytic reactions.6 Simultaneously, Stack et al. studied catalytic applications of the same complexes for the oxidation of organic substrates as they mimic the cofactor of lipoxygenases.7–9 This team also reported structural parameters, magnetic susceptibility, electrochemical behaviour, and optical properties of the series of [M(Py5OMe)Cl]+ (M = Mn, Fe, Co, Ni, Cu and Zn) complexes, but only in their reduced MII oxidation state.4 During the following two decades, Py5 complexes have also been applied as anti-tumour agents,10,11 redox mediators for dye-sensitized solar cells,12,13 and materials with tunable magnetic properties.14–16 In the field of the artificial photosynthesis, Py5-type ligands have been reported to be a suitable scaffold for synthesizing both proton reduction17–20 and water oxidation catalysts.21–24
With the idea of creating a starting point for further functionalization, our group introduced the Py5OH ligand and employed it in homogeneous water oxidation catalysis using either CoII or FeII as the metal centre.25,26 Our recent study on the [FeII(Py5OH)Cl]+ complex showed that, unlike [FeII(Py5OMe)Cl]+, it undergoes a spin-crossover from a high spin (HS) to low spin (LS) configuration, even in the presence of a weak-field ligand like Cl.15 This infers that the peripheral R-groups of the ligand can affect the electronic structure of the metal centre.
Using the Py5OH ligand framework (Fig. 1; R = OH) we synthesized here a series of metal complexes with the general formula [MII(Py5OH)Cl](PF6) (abbreviated as [MII–Cl]), where M = Mn, Fe, Co and Ni. Their one-electron redox potentials were then determined by cyclic voltammetry, and the geometric and electronic structures of both the reduced [MII–Cl] and oxidized [MIII–Cl] species were investigated in powder and/or dissolved form by employing a combination of single-crystal X-ray diffraction (XRD), synchrotron X-ray absorption spectroscopy (XAS) and density-functional theory (DFT) calculations.
The effect of the ligand sphere on the redox potential was then studied by exchange of the apical chloride ligand. This is especially interesting with regard to catalytic reactions as its exchangeability is likely important for substrate activation. To facilitate this, we also prepared the Cl-free [FeII(Py5OH)MeOH](ClO4)2 complex, which upon dissolving in dimethylformamide or acetonitrile resulted in two additional set of complexes: [FeII–DMF] and [FeII–MeCN]. Finally, the electrochemical properties of the [MII–Cl] complexes were compared to those reported previously for [MII(Py5OMe)Cl]+, abbreviated [MII–Cl]OMe. Together, this work represents a consistent set of modifications for the pentapyridyl complexes in Fig. 1, varying metal (M), apical ligand (X) and pentapyridyl substituent (R). Combined with the careful experimental and theoretical analysis of a well-defined one-electron redox event, this provides fundamental insight into the electrochemical processes of transition metal complexes.
Fig. 3 shows that all the metal–nitrogen bond distances (average of the equatorial M–Neq., blue; axial M–Naxial, red) decreased following the order of the periodic table, for M–Naxial from 2.249 Å in [MnII–Cl] to 2.065 Å in [NiII–Cl]. This was not the case for the metal–chlorine bond distance: although the Mn–Cl bond (2.458 Å) was longer than the Fe–Cl bond (2.419 Å), it increased again for the subsequent Co (2.432 Å) and Ni (2.431 Å) complexes, see Fig. 3 (green). These comparatively long metal–ligand distances are consistent with a high-spin (HS) configuration for all four [MII–Cl] complexes.
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Fig. 3 Comparison of distances from single-crystal X-ray diffraction collected at 150 K (full triangle, solid line) and calculated distances using DFT; (half-filled triangle, dotted line). M–Eq. plane, metal displacement from the equatorial plane, which is defined by the four nitrogen atoms: N2, N2i, N3 and N3i (see Fig. 2). |
Finally, the metal displacement from the equatorial plane followed a linear trend from 0.281 Å to 0.081 Å in the order Mn > Fe > Co > Ni (Fig. 3, black).
The solid [MII–Cl] complexes were further characterized in powder form (see Experimental section for elemental analyses) by X-ray absorption spectroscopy (XAS) at 20 K. All the complexes exhibited K-edge XANES energy positions that matched the values of divalent reference metal complexes, see Fig. S3–S6.† The simulated distances, obtained from the EXAFS measurements at 20 K of the solid [MnII–Cl], [CoII–Cl] and [NiII–Cl] samples, did not deviate significantly from those determined by XRD at 150 K. However, the EXAFS spectrum of [FeII–Cl] indicated a significantly shorter Fe–Neq. distances, by approximately 0.2 Å. As we reported recently, this is due to a spin-state change (spin-crossover, SCO) from quintet 5[FeII–Cl] to singlet 1[FeII–Cl] that occurs at a temperature below 80 K in the microcrystalline powder sample.15
To get closer to the conditions of the CV experiments, the XAS parameters were also obtained after dissolving the four samples in acetonitrile with electrolyte. The XAS spectra of the [MnII–Cl], [CoII–Cl] and [NiII–Cl] complexes remained unchanged as compared to the spectra recorded for the powder samples (see Fig. S3–S6†). By contrast, large differences in the XAS spectra were observed for [FeII–Cl] under the two conditions. A reasonable XAS fit of the dissolved Fe-complex at 20 K could be obtained with three components: (i) 40% of the chloride-bound LS form that was also observed for the powder, (ii) 40% of a HS form with long metal–ligand bonds, and (iii) 20% of a LS structure where the chloride ligand had exchanged with a solvent molecule. This was supported by a good EXAFS fit at 150 K where only two components, 80% of (ii) and 20% (iii), were necessary (see Fig. S8 and S9†). Dissolving the sample in an electrolyte solution thus led to partial ligand exchange and incomplete SCO down to 20 K.
The electronic and geometric structures of the [MII–Cl] complexes were calculated for all spin multiplicities consistent with 3dn configurations (n = 5–8). Correct spin-state energetics are in general challenging to calculate with DFT due to strong functional dependence.27–30 The results are especially sensitive to the amount of HF exchange, but as the functional dependence varies with the type of bonding it is difficult to get accurate results for a wide range of complexes.29 To address this challenge, we used the SCO in [FeII–Cl] as a reference point for selecting the functional.15
For [FeII–Cl] the B3LYP* functional (15% HF exchange) gave good results. It favoured the quintet over the singlet by 5.3 kcal mol−1 at room temperature, see Fig. 4. This value was 2.2 kcal mol−1 higher than what can be expected from the determined spin-transition temperature of the powder sample at 80 K.15 As the solvated chloride-coordinated sample had remaining HS species down to 20 K, the B3LYP* calculations with 15% HF exchange should thus represent the complex in solution with relatively high accuracy. Calculations of the other complexes showed that they all favour high-spin states, even more so than iron, see Fig. 4 (blue bars) and Table S2.† At RT, the spin-state energetics for [CoII–Cl] was very close to that of [FeII–Cl], but compared to [FeII–Cl] the LS form of the Co-complex was less well-stabilized at low temperatures, so that the calculations did not predict this to be a spin-crossover complex, see Table S5.†
The corresponding DFT geometric structures were, in general, in good agreement with XRD data, see Fig. 3 and Table 1. The Fe–Neq. distances had absolute deviations of less than 0.02 Å, which meant that trends in bond distances were also well reproduced. The agreement is poorer for the axial bonds, with too short M–Cl bonds (−0.1 Å on average) and much too long for M–Naxial bonds (+0.2 Å on average). This led to calculated metal centre positions that were further displaced from the equatorial plane than measured by XRD (by 0.1 Å). However, the structural trends were still very well reproduced, with all M–N distances (M–Neq. and M–Naxial) decreasing following the order in the periodic table, while the M–Cl distances showed the above-described deviation for Co and Ni.
Complex | Ox. state | M–Neq. | M–Naxial | M–Xa | ||||||
---|---|---|---|---|---|---|---|---|---|---|
XRD | EXAFSb | DFT | XRD | EXAFSb | DFT | XRD | EXAFS | DFT | ||
a For XRD, the apical ligand X is chloride for all [MII–Cl] complexes and the oxygen of DMF for the [FeII–Solv] complex. For EXAFS and DFT of [FeII–Solv] the apical ligand is the nitrogen of an acetonitrile molecule. b Average of all M–N distances modelled as one shell. c Distorted 5[MnIII–Cl] after a least-squares EXAFS fit that allows for the distances to the three closest N atoms and the Cl− to be optimized (5[MnIII–Cl]′). d Calculated distances for 5[MnIII–Cl]′ structure. e Fe–N distance: single shell Fe–N distance obtained in the best EXAFS fits employing a sample composition of 40% HS, 40% LS, and 20% chloride substituted LS complex; Fe–Cl distance: average of 50% HS and 50% LS complexes. | ||||||||||
[Mn–Cl] | II | 2.251 | 2.25 | 2.260 | 2.249 | 2.25 | 2.389 | 2.458 | 2.43 | 2.421 |
III | — | 2.14c | 2.158d | — | 2.14c | 2.116d | — | 2.22c | 2.264d | |
[Fe–Cl] | II | 2.189 | 1.99e | 2.206 | 2.171 | 1.99e | 2.292 | 2.419 | 2.38e | 2.357 |
III | — | 1.99 | 2.034 | — | 1.99 | 2.049 | — | 2.22 | 2.249 | |
[Co–Cl] | II | 2.151 | 2.14 | 2.168 | 2.121 | 2.14 | 2.222 | 2.432 | 2.40 | 2.392 |
III | — | 1.97 | 2.009 | — | 1.97 | 2.020 | — | 2.20 | 2.263 | |
[Ni–Cl] | II | 2.111 | 2.09 | 2.131 | 2.065 | 2.09 | 2.150 | 2.431 | 2.42 | 2.409 |
III | — | — | 1.993 | — | — | 2.193 | — | — | 2.420 | |
[Fe–Solv] | II | 2.017 | 1.98 | 2.040 | 1.952 | 1.98 | 2.032 | 1.989 | 1.98 | 1.933 |
III | — | 1.97 | 2.015 | — | 1.97 | 2.026 | — | 1.97 | 1.945 |
The choice of functional and basis set size did not affect the calculated distances by more than 0.02 Å, see Table S3,† and the very long Fe–Naxial bond is present also with the local BP86 functional. Despite the deviations of the axial bond distances, the HS structures still give the best agreement with experiment. Structures with lower spin multiplicities all have significantly shorter Fe–Neq. bonds, which led to an underestimation by 0.2 Å, with no significant improvement in the Fe–Naxial distance, see Table S2.†
Given the observation of the irreversible Cl2/Cl− redox wave, the most likely candidate was the complex where the Cl− ligand was replaced by a solvent molecule, which was also observed in the EXAFS data. This possibility will be analysed in detail in a later section.
We note that due to the difference in temperature between the experiments, the LS 1[FeII–Cl] species observed with EXAFS at 20 K was not present in the room temperature CV experiment. Thus, we estimate that the room temperature composition was 75% HS 5[FeII–Cl] and 25% 1[FeII–MeCN], in good agreement with the CV peak analysis.
Oxidation of the [MnII–Cl] complex shortened the average Mn–N distance by about 0.11 Å and the Mn–Cl distance by 0.21 Å (Table 1). A direct EXAFS fit of the oxidized form requires a large Debye–Waller factor when a single Mn–N shell is used (0.085 Å, compared to around 0.065 Å for the other complexes, see Table S4†), indicating a large Jahn–Teller distortion. DFT calculations of the oxidized Mn complex give the lowest energy for a quintet 5[MnIII–Cl] structure (Fig. 4), with the triplet 3[MnIII–Cl] 6.7 kcal mol−1 higher in energy (Table S2†). Compared to the reduced complex, the calculations on the 5[MnIII–Cl] reproduced qualitatively the shorter average Mn–N distances, but maintained a long Mn–Cl distance (2.40 Å, Table S2†), in poor agreement with EXAFS data, see Fig. S12.† The 3[MnIII–Cl] has similar calculated average Mn–N distances and a much shorter Mn–Cl bond length (2.24 Å, Table S2†) as compared to the quintet, which gives better agreement with EXAFS distances (Fig. 6). However, the fit to the EXAFS spectrum was not significantly improved (Fig. S12†). Instead, an alternative quintet structure 5[MnIII–Cl]′ with a shorter Mn–Cl bond of 2.26 Å (Table 1 and Fig. 6) and elongated bonds in the equatorial plane, lies only 0.6 kcal mol−1 above the most stable quintet and gives a much better fit to EXAFS (Fig. S12†). Considering the small energy difference and the good structural match, this alternative quintet structure will also be considered in further comparisons and analyses.
For [CoIII–Cl], EXAFS fitting suggests that upon oxidation the average Co–N distance shortens from 2.14 Å to 1.97 Å, and the average Co–Cl distance from 2.40 Å to 2.20 Å. The majority of reported CoIII complexes exist in a LS singlet configuration,31 and the distances found here for [CoIII–Cl] were also consistent with such an assignment. DFT calculations also prefer 1[CoIII–Cl] over 5[CoIII–Cl] by a large margin (26.4 kcal mol−1), see Fig. 4, and 3[CoIII–Cl] is also much higher in energy, see Table S2.† The calculations reproduce the short metal–ligand bonds of the EXAFS structure, although they are overestimated by approx. 0.04 Å.
In contrast to the Mn and Co complexes, the oxidation of [FeII–Cl] to [FeIII–Cl] did not lead to a similar shortening of the bonds and connected EXAFS changes. While the EXAFS spectrum of [FeII–Cl] required three components to be fitted at 20 K, the EXAFS data obtained with the oxidized complex, [FeIII–Cl], could be simulated well with a single species that had a short Fe–Cl distance (2.22 Å) and short average Fe–N distance (1.99 Å), see Table 1. This suggests the oxidation to a LS 2[FeIII–Cl] structure. Unlike the reduced complexes, there was thus no equilibrium between different spin multiplicities or axial ligands (Cl−vs. solvent) after oxidation. Energetically, DFT calculations favour the low-spin over the high-spin 6[FeIII–Cl] structure by 1.1 kcal mol−1 already at 298 K, and this tendency increases with decreasing temperature (Table S5†). The calculated average Fe–N bonds (2.04 Å) in the 2[FeIII–Cl] structure are 0.05 Å longer than predicted by experiment (Fig. 6), but still a much better fit than the 2.17 Å of the average Fe–N bond distance obtained for the 6[FeIII–Cl] complex, see Table S2.†
While no oxidized [NiIII–Cl] suitable for EXAFS analysis could be obtained, DFT calculations indicate a preference for LS 2[NiIII–Cl] over the alternative HS 4[NiIII–Cl] by 16.7 kcal mol−1, see Fig. 4. The LS structure gave short equatorial Ni–N bonds of 1.99 Å, and a much longer axial bond of 2.19 Å, for an average Ni–N bond of 2.03 Å. The calculated NiIII–Cl distance is 2.42 Å, see Fig. 6. The HS structure had much longer Ni–N distances (2.15 Å) and a shorter Ni–Cl distance (2.23 Å).
The results of our DFT calculations are shown as vertical lines in the CVs plotted in Fig. 5, and are also reported in Table S6.† In agreement with our experiments, the lowest redox potential was found for [CoII–Cl]. The theoretical value of 0.18 V, is +0.10 V higher than the experimental value (0.08 V). This deviation is well within the expected accuracy of the calculations, and is likely due to error cancellation. For [FeII–Cl], the calculated value was 0.37 V, which is in even better agreement with the experiment (0.33 V). Experimentally, [MnII–Cl] had a higher redox potential (0.58 V) than both [FeII–Cl] and [CoII–Cl]. Calculations with the lowest energy structure, 5[MnIII–Cl], gave a value of 0.34 V (−0.24 V vs. exp.), which placed it at the same level as that of the iron complex. Using the alternative 5[MnIII–Cl]′ structure would instead give a redox potential of 0.37 V, which is a minor improvement compared to the experiment. Finally, the calculated redox potential of [NiII–Cl] was 1.19 V, much higher than the other complexes, and in excellent agreement with the experiment (1.17 V).
Preparing the chloride-free complex in methanol yielded a solid material where MeOH is in the apical coordination site. When this product was dissolved in acetonitrile, methanol was replaced by an acetonitrile molecule ([FeII–MeCN]), as observed in a HR-MS conducted at low ionization energy (Fig. S13†). Taken together, these data suggest that the solvent molecule at the apical coordination site was weakly bound and could be easily exchanged. The EXAFS data of [FeII–MeCN] shown in Fig. 7 could be fitted using a short metal–nitrogen bond length of 1.98 Å (Table 1), consistent with a LS FeII centre. The LS configuration was further supported by a 1H-NMR spectrum of [FeII–MeCN] that showed the presence of a diamagnetic metal complex (Fig. S14†). DFT calculations also favoured the LS form (by 3.2 kcal mol−1) at 298 K and gave metal–ligand distances within 0.02 Å of the EXAFS analysis.
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Fig. 7 EXAFS spectra weighted by k3 (a) and their Fourier transforms (b) of the [M–X] complexes (1 mM) dissolved in acetonitrile with the addition of TBAPF6 (0.1 M). Spectra were recorded at 20 K and are offset for clarity. Divalent [MII–X], blue; oxidized [MIII–X] samples, red. Simulations of the experimental data are shown as thin lines and the parameters are given in Table S4.† |
In contrast to the cyclic voltammogram of [FeII–Cl] in acetonitrile that showed two reversible redox waves (E1/2 = 0.33 V and 0.83 V), the CV of [FeII–MeCN] showed only one reversible redox wave with a potential that matched the position of the second wave of the CV labelled [FeII–Cl] (Fig. 5 and S15†). Fig. 8 shows that addition of Cl− into a solution of [FeII–MeCN] in electrolyte led to the appearance of a reversible redox wave at +0.33 V that coincided with the first reversible couple of [FeII–Cl], suggesting that [FeII–Cl] and [FeII–MeCN] interchanged easily in solution. An electrochemical contribution to this ligand exchange can be excluded as we observed the same shift in the equilibrium by monitoring the Cl-titration by UV-Vis spectroscopy in pure acetonitrile (Fig. S16†). The UV-Vis data obtained in presence of TBAPF6 revealed that the supporting electrolyte partially shifted this equilibrium in favour of the [FeII–MeCN] species (Fig. S17†). This effect was probably due to the increased ionic strength of the medium, which stabilized free chloride in the solvent. This explains, why even after addition of two equivalents of Cl− a mixture of [FeII–Cl] and [FeII–MeCN] was still observed (Fig. 8 and S16a†). In addition, the Cl2/Cl− redox couple was also observed at Ep = 0.72 V in the oxidative scan in Fig. 8.
In contrast to the [MII–Cl] complexes, the oxidation of the [FeII–MeCN] complex occurred without significant structural changes (Fig. 7 and Table 1), although the oxidation was witnessed by the edge shift in the XANES region (Fig. S7†). The near-constant metal–ligand distances (Table 1) suggested a transition between two LS species, i.e. from 1[FeII–MeCN] to 2[FeIII–MeCN], which was supported by DFT energy and structure calculations (Table S2†). DFT calculations of the redox potential of [FeII–MeCN] gave a value of 0.76 V, which was in good agreement with the experimental value of 0.83 V (Fig. S15†).
The introducing an apical ligand (X) to a hypothetical complex with six equivalent ligands (Oh point group) decreases its symmetry. As shown by our experiments and DFT calculations, this includes for the [MII–Cl] complexes a displacement of the central metal ion from the equatorial plane along the C4-axis. Thus. a C4v symmetry is a fair assignment of the local metal environment. In reality, the symmetry deviates from C4v to a certain extent since there is no authentic C4 rotational axis giving the Py5OH ligand. This deviation, however, does not change the principles in the following section.
The calculated electronic structure of the Py5 complexes are consistent with a previous analysis that described the pyridine rings as being predominantly σ-donor and π-acceptor ligands,5 while Cl− as σ and π donor. In a C4v symmetry, the orbital degeneracy from the well-known cubic environment is lifted. Consequently, the metal 3d-dominated t2g and eg orbitals in a virtual Oh symmetry transform to b2 + e and a1 + b1 respectively, see Fig. 9. The lowest b2 level is related to a dxy orbital (equatorial pyridines π-bonding), above which is two-fold degenerated e level related to dxz and dyz orbitals (pyridine π-bonding and Cl− π-antibonding). These three orbitals will be labelled as π-type orbitals. Higher in the energy are a1 and b1 levels, both σ-type orbitals related to dz2 (Cl−/pyridine σ-antibonding) and dx2−y2 (pyridine σ-antibonding), respectively. The ordering of these two levels will be discussed in more detail below.
Going from left to right in the periodic table lowers the energy level of the metal orbitals because the additional nuclear charge is only partially screened by the extra electron. This lowering is even more pronounced when increasing the formal oxidation state. For ligand-donor bonding, lowering the metal level leads to smaller energy differences between metal and ligand orbitals, and thus a stronger interaction. For ligand-acceptor binding, it instead leads to a larger energy difference between metal and empty ligand energy levels and weaker interactions. In general, the energy difference between the π-levels and the antibonding σ-levels increases, which corresponds to a larger ligand-field splitting. These general principles can now be used to rationalize trends in geometric structure, spin-state energetics, and electrochemical behaviour.
The results are more interesting when going from Fe to Co. In 4[CoII–Cl] the extra electron goes into the dxz/dyz level, which is bonding with respect to the pyridines and anti-bonding with respect to Cl−. The added electron leads to shorter M–N bonds and longer M–Cl bonds. At the same time, increased donor bonding should have an overall contracting effect. Still, for the metal–chlorine bond, the anti-bonding effect dominates, and the bond length increases. Finally, going from 4[CoII–Cl] to 3[NiII–Cl] puts another electron into the dxz/dyz orbitals, which leads to similar changes as seen when going from Fe to Co. The molecular orbital analysis can thus fully explain the bond length trends for the reduced complexes.
The metal–ligand distances of the oxidized complexes show a complex behaviour upon exchange of the metal (Fig. 6). The computational analysis of the [MnIII–Cl] compound is complicated because of the deviations between the experiment and the lowest-energy 5[MnIII–Cl] (π3σ1) structure. The short Mn–Cl bond from EXAFS (2.22 Å) suggests that an electron is removed from the anti-bonding σ-type dz2 orbital upon oxidation, but the calculations instead give for 5[MnIII–Cl] a long Mn–Cl and shorter Mn–Neq. bonds, see Table S2,† consistent with an electron taken from the dx2−y2 orbital. The alternative 5[MnIII–Cl]′ structure, which with shorter axial and longer Mn–Neq. bonds, gives a better EXAFS match (Fig. 6), is more consistent with an empty dz2 orbital. It is thus possible that the calculations remove the electron from the wrong σ orbitals in this oxidation process.
As the octahedral HS MnIII complex shows a Jahn–Teller distortion, the difference between the two calculated structures can also be viewed as a change in distortion axis.
As the calculations consistently overestimate the axial Mn–N bond distances, it is possible that they artificially favour the 5[MnIII–Cl] structure with a Jahn–Teller-like elongation in this direction. Overestimations of the MnIII JT distortion have also been previously observed in DFT calculations.42
For 2[FeIII–Cl] theory and experiment largely agree, see Fig. 6. The 2[FeIII–Cl] complex has a LS (π5σ0) electron configuration and compared to 5[MnIII–Cl] this means extra electrons in dxy and one of the dxz, dyz orbitals while removing the final σ electron. This leads to short axial as well as equatorial bonds. Going further from 2[FeIII–Cl] to LS 1[CoIII–Cl] (π6σ0) adds an electron to dxz/dyz, and as these are antibonding with respect to Cl−, together with the general contraction with larger Z there should be small changes in the M–Cl distance while the M–N distances decrease when going from Fe to Co (Fig. 6). Incidentally, the extra electron is here added to the same orbital level as for the comparison of the reduced iron and cobalt complexes. Finally, the trend when going from 1[CoIII–Cl] to 2[NiIII–Cl] (π6σ1) can only be derived from calculations as the oxidized nickel complex could not be obtained. They show a significant increase in M–Cl bond length and a slight increase in the average M–N bond length. The increase in bond distances is expected as the added electron is placed in an σ antibonding orbital. As the bond distances increase more along the C4-axis, the calculations suggest that the electron ends up in the dz2 rather than the dx2−y2 orbital. LS NiIII complex is expected to show a similar Jahn–Teller-like distortion as HS MnIII, and the long M–Cl distance is similar to that of the 5[MnIII–Cl] structure. However, as seen from the [MnIII–Cl] calculations, it is possible that the structure instead would have a distortion along the equatorial M–N plane.
The spin-state energetics are governed by two major factors, the ligand-field strengths and the differences in exchange stabilization between electron configurations. If the former is sufficiently large, the benefit of being at the lower orbital levels competes with and overcomes the loss of exchange stabilization and the electrons fill lower b2 and e orbitals, resulting in LS configurations. The exception is NiII where both spin configurations have two electrons in the upper two levels. In general, both ligand-field strengths and the exchange interactions increase along the periodic table. However, with changing d-electron count, the difference in the number of ligand-field excitations and exchange interactions change between LS and HS states. The resulting spin-state energetics in Fig. 4, therefore, do not follow any linear trend but are rather consistent with the spectrochemical series of metals.
Taking the reduced complexes as an example, [MnII–Cl], it has a relatively weak ligand field and the sextet has all electrons with the same spin orientation, leading to a highly stable configuration as seen in Fig. 4. Going to d6 FeII and d7 CoIII, all electrons can no longer have the same spin orientation, and the ligand-field splitting increases, resulting in the lower relative stability of the HS configurations. As mentioned above, for d8[NiII–Cl] b2 and e orbitals (b22e4) are filled in all configurations, and the high spin is favoured because it allows for a1 and b1 to be half-filled with electrons in the same spin-orientation.
From Fig. 5 it is clear that the redox potentials of all complexes except [MnII–Cl] are well described by the calculations, not only in terms of relative but also absolute potentials. The main discrepancy is that manganese is too easy to oxidize according to the calculations. However, the deviation, −0.24 eV, is within the expected accuracy of the method, and the calculations reproduce the overall experimental trend well enough to be used to rationalize the trends in redox potential.
The oxidation process will be analysed in three schematic steps. The first step is the removal of an electron from the highest occupied molecular orbital, which in all cases is the σ-type dx2−y2 orbital, and the subsequent orbital relaxation. This is followed by geometry relaxation to the minimum energy geometry of the oxidized species. Finally, in cases where a more stable spin multiplicity existed, spin change was allowed.
The description of [MnII–Cl] oxidation is straightforward: removing an electron is equivalent to going from 6[MnII–Cl] (π3σ2) to 5[MnIII–Cl] (π3σ1). Including only orbital relaxation would lead to a hypothetical redox potential of 1.11 V, see Fig. 10. This is followed by geometric relaxation of the oxidized complex to its minimum energy, which leads to a drop in the potential to 0.34 V. As the quintet is also the lowest energy of [MnIII–Cl], this is also the final calculated redox potential. Using instead the alternative 5[MnIII–Cl]′ structure, which would be consistent with the removal of a dz2 electron, would give a very similar analysis, although with a slightly higher final potential (0.37 V). The relative order of dz2 and dx2−y2 might thus not be correctly predicted, but this does not seem to have a significant effect on the analysis.
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Fig. 10 Theoretically calculated half potentials for the [MIII–Cl]/[MII–Cl] redox couples. Allowing only for orbital relaxation after removal of an electron from the same orbital in all complexes, orange bars; allowing for geometric relaxation, green bars; allowing for spin multiplicity change, purple bars. The experimental redox potentials are shown as a line. [FeII–Cl]OMe represents the [FeII(Py5OMe)Cl]+ complex with the experimental value reported by Stack et al.4 |
For [FeII–Cl], the oxidation is a 5[FeII–Cl] (π4σ2) to 2[FeIII–Cl] (π5σ0) transition. Taking an electron from a σ-type orbital leads initially to a 4[FeIII–Cl] π4σ1 configuration at 1.20 V, which then drops to 0.73 V upon geometry relaxation, see Fig. 10. However, for iron, there is an additional change in spin multiplicity from a quartet to a doublet, which gives the final calculated potential of 0.37 V. The analysis for the 4[CoII–Cl] (π5σ2) to 1[CoIII–Cl] (π6σ0) transition is similar to the case for iron. The oxidation to 3[CoIII–Cl] (π5σ1) gives potentials of 1.48 and 0.98 V after orbital and geometric relaxation, respectively. For [CoIII–Cl], the singlet is much more stable than the triplet, which leads to a drop in the potential down to 0.19 V. Finally, for [NiII–Cl] the electron is also taken from a σ-type orbital as it goes from 3[NiII–Cl] (π6σ2) to 2[NiIII–Cl] (π6σ1). As expected, the removal of a σ electron is more difficult in [NiII–Cl] than in the other complexes, leading to a potential of 1.19 V after geometric relaxation. As there is no further change in spin multiplicity, this is also the final redox potential, which is then much higher than for any other complex in the series. From the trends in Fig. 10 it is thus clear that if only orbital and geometry relaxation would occur, the potentials of all our Py5OH complexes would follow the order in the periodic table, i.e. show a higher redox potentials with higher Z. It is thus the difference in energy stabilization from potential changes in spin multiplicity that determines the final order of the redox potentials. The calculations can thus be used to rationalize the changes in electrochemical properties between different base metals.
The ligand exchange equilibrium is instead determined by the energy costs for solvating the Cl− ion and the binding energy of the acetonitrile ligand, which binds stronger to Fe and Ni compared to Mn and Co. Compared to the chloride complex, acetonitrile favours the singlet state by 8.5 kcal mol−1, which makes [FeII–MeCN] a low-spin complex.
However, the rest of the [MII–MeCN] complexes remain HS, even though the energy difference is only 1.8 kcal mol−1 for [CoII–MeCN]. That means all complexes except iron have electrons in the anti-bonding dz2 orbitals. The reason for stronger bonding in Ni compared to Co could be a combination of improved overlap and the fact that the extra electron now appears in a dxz/dyz orbital that is bonding between metal and MeCN.
Taken together, the calculations show that the exchange energy, which is the difference between the two binding energies, is close to zero for [FeII–Cl] and [NiII–Cl], while it is slightly positive for [MnII–Cl] and [CoII–Cl], see Fig. 11. For [MnII–Cl], [FeII–Cl] and [CoII–Cl] this reproduces the trend observed in the experiments, as we observed the exchange of the apical ligand only for the [FeII–Cl] complex. By contrast, for [NiII–Cl] the thermodynamically expected ligand exchange was not observed, which may indicate a kinetic limitation of this process. Interestingly, for the related [NiII(Py5Me)Cl]+ complex the chloride was recently reported to exchange with the solvent.23
Calculations of [FeIII–Cl] show that in the oxidized state, the corresponding exchange reaction for a neutral solvent molecule is unfavourable, which is consistent with the EXAFS observations of [FeIII–Cl] described above. The difference in calculated redox potential between [FeII–Cl] and [FeII–MeCN] can also be attributed to the difference in charge, with the anionic ligand favouring lower redox potentials.
Electrochemically, the Py5OMe complexes have redox potentials that are 0.08 V higher than the Py5OH complexes, see Table S6.† The exception is Ni, where the reported redox potential of the Py5OMe complex is 0.78 V lower.4 Based on the good agreement between calculated and measured half potentials for the [NiIII–Cl]/[NiII–Cl] redox couple in this study, we assume that the reported values for [NiII(Py5OMe)Cl]+ are not reflecting the same redox couple.
To analyse the differences between the two versions of the ligand, the redox potential of the [FeII(Py5OMe)Cl]+ complex was calculated using the same protocol as for [FeII–Cl]. With this ligand, the ferric complex is also LS, although by a very small margin at 298 K (0.7 kcal mol−1). The calculated redox potential is 0.11 V higher than for the [FeII–Cl] complex, in good agreement with the experimental difference of 0.07 V. Breaking down the process into the different steps shows that the main contribution is the increased energy required to remove the σ electron (+0.18 V), while geometric relaxation and changes in spin multiplicity work in the opposite direction ([FeII–Cl]OMe in Fig. 10). In the calculations, the electron is taken from the antibonding dx2−y2 orbital, and the structural distortion with the Py5OMe ligand lowers the dx2−y2 level because of poorer overlap. This effect is also visible from the longer equatorial bond distances, by 0.08 Å, in [FeII–Cl]OMe. If the observed differences in redox potential could be directly translated into differences in barrier heights, a 0.1 eV difference corresponds to a hundred-fold effect on reaction rates. This shows the potential of modifying Py5 type ligands for tuning the reactivity of these complexes.
The complexes were fully characterized to verify the purity of the desired product by means of 1H-NMR, FT-IR, UV-VIS, HR-MS and elemental analysis as described in the ESI.† The oxidised metal complexes were obtained by electrolysis in acetonitrile solution (1 mM) as described in the next section.
Caution: Perchlorate salts are potentially explosive and should be handled with care.
Py5OH was synthesized following a procedure introduced by us recently.15 To a dry THF solution (40 ml) of 2,6-dibromopyridine (0.65 g, 2.72 mmol) in a 100 ml 3-neck round bottom flask, an excess of Mg (0.25 g, 102 mmol) was added. After sonicating the mixture for 20 minutes at 35 °C using an ultrasonic bath (45 kHz frequency, model USC300TH, VWR Collection) most of the starting solid Mg was dissolved and the transparent solution turned dark. A THF solution (20 ml) of di(2-pyridyl)ketone (1.00 g, 5.44 mmol) was added dropwise to the Grignard reagent with subsequent formation of a white precipitate. The mixture was stirred for 48 hours followed by the addition of 10% HCl (30 mL). The organic solvent was evaporated and the aqueous solution was washed with CH2Cl2 (2 × 50 mL). Neutralization of the aqueous solution with saturated Na2CO3-solution was followed by extraction with CH2Cl2 (3 × 100 mL). The CH2Cl2 solvent was evaporated and the penta-pyridylcarbinol product was recrystallized from hot acetone (250 mg, 0.558 mmol, yield: 10.2%). 1H-NMR (400 MHz, CDCl3): δ = 7.17 (4 H, t of d, J1 = 5.3 Hz, J2 = 2.3 Hz, 5-H of Py arms (py-a)), 7.55–7.60 (8 H, m, 3-Hpy-a, 4-Hpy-a), 7.71 (3 H, m, 2-H and 3-H of bridging Py), 8.50 (4 H, m, 6-Hpy-a) ppm. 13C-NMR (400 MHz, CDCl3): δ = 162.1, 161.2, 147.2, 137.8, 136.5, 123.5, 122.5, 120.8, 80.9 ppm. MS (+ESI-ToF): m/z: 448.1878 [Py5OH + H+]+, 470.1689 [Py5OH + Na+]+.
High Resolution ESI-MS shows two main molecular fragments at 541.08128 m/z, [CoII(Py5OH)Cl]+ and 505.10374 m/z, [CoII(Py5OH) − H+]+. The UV-Vis spectrum shows a strong absorption below 400 nm and a weak broad composite band between 425 nm and 550 nm (ε460 = 0.04 × 103 M−1 cm−1), see Fig. S15.† Solid FT-IR (KBr) of the complex shows the same vibration modes as the ligand with a blueshift of 5 cm−1 and the characteristic P–F stretching at 842 cm−1 from the PF6− ion.43 CoC27H21N5ClO2PF6 (686.84 g mol−1) calcd C 47.21, H 3.08, N 10.20; found C 48.64, H 4.16, N 10.43.
The UV-Vis spectrum shows a strong absorption below 300 nm with a shoulder at 320 nm (ε = 0.75 × 103 M−1 cm−1), see Fig. S15.† Solid FT-IR (KBr) of the complex shows the same vibration modes as the ligand with a blueshift of 4 cm−1 and the characteristic P–F stretching at 842 cm−1 from the PF6− ion.43 NiC27H21N5ClO2PF6·4H2O (758.66 g mol−1) calcd C 42.75, H 3.85, N 9.23, Cl 4.67; found C 42.55, H 3.90, N 9.23, Cl 4.91.
FeC28H25N5Cl2O11 (734.28 g mol−1) calcd C 45.80, H 3.43, N 9.54; found C 46.3, H 4.30, N 10.98.
The glassy carbon working electrode (3 mm diameter) was polished with alumina particles (0.05 μm) immediately prior use. The counter electrode was a platinum rod polished with sandpaper before use. Unless stated otherwise, the following parameters were used to record cyclic voltammetry on our samples: scan rate: 100 mV s−1, step potential 0.002 V. The sample concentration was 0.5 mM with tetrabutylammonium hexafluorophosphate supporting electrolyte (100 mM) in acetonitrile.
Calculated redox potentials are obtained using the reaction [MII–X] ⇌ [MIII–X] + e−. The energy of the solvated electron was calculated using 4.28 V for the absolute potential of the standard hydrogen electrode (SHE).55 The choice of reference value affects the absolute potentials, but not the comparison between complexes. Calculated values are given in V vs. Fc+/Fc for comparison with experimental results, with 0.40 V for the E1/2 of Fc+/Fc vs. the SHE.56 The analysis of the different contributions to the redox potential was made by separating the calculations of the oxidized species into three steps. First, the energy for removing a spin-up σ electron was calculated using the structure of the reduced complex (orbital contribution). Second, the structure was optimized using the same spin multiplicity (geometric). Finally, the energy of the most stable spin multiplicity was calculated (spin).
Footnote |
† Electronic supplementary information (ESI) available. CCDC 2013481-2013483. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/d0dt03695a |
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