Jarrod R.
Thomas
a,
Marcus J.
Giansiracusa
*b,
Jonathan T.
Mifsud
a,
Richard A.
Mole
c and
Scott A.
Sulway
*a
aSchool of Chemistry, The University of New South Wales (UNSW), Kensington, Sydney, 2052, Australia. E-mail: s.sulway@unsw.edu.au
bSchool of Chemistry, University of Melbourne, Parkville, Victoria, 3010, Australia. E-mail: marcus.giansiracusa@unimelb.edu.au
cThe Australian Nuclear Science and Technology Organisation, Lucas Heights, NSW 2323, Australia
First published on 17th January 2025
The synthesis and structural characterisation of [Ln(Tp2-Fu)2]I (1-Ln; Ln = La, Ce, Pr, Nd) (Tp2-Fu = hydrotris(3-(2′-furyl)-pyrazol-1-yl)borate) have been reported as an isomorphous series adopting pseudo-icosahedral ligand field geometries. Continuous shape measurement (CShM) analyses on the crystal field environments of 1-Ln show the smallest values yet reported for complexes employing two hexadentate ligands (e.g. bis-scorpionate environments), with the smallest belonging to 1-La. Single-ion magnetism for 1-Ce, 1-Pr and 1-Nd was probed with ac magnetic susceptibility studies revealing slow magnetic relaxation for 1-Nd in applied magnetic fields and in zero-applied field for 1-Ce, which is a rare observation for Ce(III)-based single-ion magnets. The energy barrier to magnetic relaxation for 1-Ce was experimentally determined to be Ueff = 30(5) cm−1, which is comparable to that of other cerium-based single-molecule magnets in the literature, where these systems stablise the mJ = ±5/2 state and possess large energy gaps between the ground and first excited state that do not agree with the experimentally determined barrier.
A recently charted ligand field for lanthanide-based SIMs is that of icosahedral geometry, which has been expanded by us through the use of hexadentate scorpionate ligands in complexes such as [Ln(Tp2-py)2](BPh4) (2-Ln; Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy; Tp2-py = hydrotris(3-(2′-pyridyl)-pyrazol-1-yl)borate) and [Ln(Tp2-Fu)2](BPh4) (3-Ln; Ln = Ce, Dy; Tp2-Fu = hydrotris(3-(2′-furyl)-pyrazol-1-yl)borate).13,14 The early lanthanide containing complex [Ce(Tp2-py)2](BPh4) 2-Ce exhibited field-induced slow magnetic relaxation; however, due to the complexity of the ligand field environment and pseudo-spherical nature of the charge distribution about the cerium(III) centre, the dominating magnetic relaxation occurs via a Raman mechanism. Thus by the fine tuning of the scorpionate ligand used, we present the synthesis and characterisation of [Ln(Tp2-Fu)2]I (1-Ln; Ln = La, Ce, Pr, Nd) by single crystal X-ray diffraction and magnetometry with supporting ab initio calculations. Herein, we explore the effects of heteronuclear hexadentate ligands on the slow magnetic relaxation in highly symmetric lanthanide-based SIMs.
The same synthetic procedure was attempted using hydrated EuCl3 and SmCl3 as lanthanide sources but recrystallisation resulted in discolouration and powdered samples. As per our previous publications, the size of the lanthanide ion plays a crucial role in the stability of twelve coordinate bis-scorpionate lanthanide complexes.13,14 The proximity of the scorpionate ligand, and the deviation from perfect ligand fields (measured by continuous shape measurements (CShM), vide infra), can be used to predict when these twelve-coordinate systems become unstable. We have attributed 1,2-borotropic shifting of the Tp2-Fu ligand as the likely cause for us not being able to isolate 1-Eu and 1-Sm given the relatively small lanthanide ions in these systems.14
The isomorphous 1-Ln·(CH2Cl2)2 series pack in the triclinic space group P (the solid-state structure for the ion-pair for 1-Ce is shown in Fig. 1 and the remaining compounds in Fig. S4–S6;† coordination geometries from the cations in 1-Ln and B⋯B axis views are shown in Fig. 2 and selected atomic distances and angles have been summarised in Table 1). When comparing the unit cell dimensions of 1-Ln·(CH2Cl2)2, there are no obvious trends, though the volume of each cell decreases, attributed to the lanthanide contraction (Fig. S8†). The cations in 1-Ln have inversion symmetry where one scorpionate ligand comprises the asymmetric unit, akin to that of 2-Ln,13 with a lanthanide ion and counter-ion of iodine having half occupancies (Fig. 1). The unit cell consists of one ion pair with two CH2Cl2 molecules (Fig. S7†). The iodide ions occupy the corners of the unit cell and lie on inversion points, and analogously the lanthanide ions also lie on inversion points yet are located at the centre of the cells. Due to the lanthanide lying on an inversion point the second Tp2-Fu is generated by symmetry which results in all X–Ln–X (X = coordinating atoms) angles being 180° alongside the B⋯Ln⋯B angle being linear and the molecule possessing a pseudo-S6 axis down the B⋯B axis (Fig. 2).
![]() | ||
Fig. 2 Coordination geometries of the metal centres in 1-Ln (top), shown with coordinated atoms drawn with 50% ellipsoids and view from the B⋯B axis (bottom). Metal centres are lanthanum, cerium, praseodymium and neodymium going from left to right. The colour scheme is defined in Fig. 1. |
1-La | 1-Ce | 1-Pr | 1-Nd | |
---|---|---|---|---|
a Conical angles are taken from N2–B1–Ln1, N4–B1–Ln1 and N6–B1–Ln1 (Ln = La, Ce, Pr, Nd). b Magnitude of the torsion angles is measured between N2–C3–C4–O4, N4–C10–C11–O2 and N6–C17–C18–O3. | ||||
Ln⋯B/Å | 3.891(7) | 3.872(5) | 3.861(5) | 3.846(5) |
Ln–Npz/Å | 2.670(2)–2.683(2) | 2.6502(15)–2.6641(15) | 2.6354(14)–2.6528(14) | 2.624(2)–2.643(2) |
Ln–OFu/Å | 2.8819(19)–2.8688(18) | 2.8478(13)–2.8753(13) | 2.8424(12)–2.8680(12) | 2.8390(17)–2.8674(17) |
Conical anglea/° | 43.06–43.23 | 42.85–43.16 | 42.70–43.07 | 42.70–43.12 |
Furyl torsionb/° | 1.2(4)–8.5(5) | 0.4(3)–9.1(3) | 0.4(2)–9.4(3) | 0.6(3)–8.9(3) |
Ln⋯Ln/Å | 11.1211(8) | 11.0781(6) | 11.0573(5) | 11.0672(6) |
CShM(Ic) | 0.340 | 0.352 | 0.362 | 0.391 |
The ligand field geometries present in 1-Ln are pseudo-icosahedral (Fig. 2) with the CShM values being below 0.4 for all compounds. The smallest CShM is observed in 1-La (CShM(Ic) = 0.340) and gradually increases across the lanthanide series. To our knowledge these are the smallest CShM values of Ic geometry for two hexadentate ligands; in particular, these are the smallest for bis-scorpionate complexes, or tripodal ligands in general. The smaller CShM values are attributed to the different ‘bite’ angle of the Tp2-Fu ligand (conical angle, Table 1). The five membered furyl rings produce differing coordination bond distances, conical angles (Ln1–B1–N2, Ln1–B1–N4 and Ln1–B1–N6) and furyl torsion angles (N2–C3–C4–O1, N4–C10–C11–O2 and N2–C17–C18–O3) when compared to the analogous Tp2-py ligand, where the smallest CShM(Ic) is 0.362, seen in 2-Ce.13 The coordinating distances of both the nitrogen atoms from the pyrazolyl group (Npz) and the oxygen atoms from the furyl groups (OFu) gradually decrease across the lanthanide series, which is seen in the 2-Ln series and is an excellent physical observation of lanthanide contraction.13 The coordination distances in 1-Ln are shorter than that of 2-Ln, which again is due to the different bite of the ligands allowing the scorpionate ligand to reside closer to the lanthanide ions, evident by the shorter B⋯Ln distances (3.891(7)–3.846(5) Å cf. 3.923(7)–3.904(6) Å when comparing 1-Ln to 2-Ln respectively, for Ln = La, Ce, Pr, Nd).13 The solid-state packing of 1-Ln·(CH2Cl2)2 allows for well-spaced lanthanide ions, which are defined by the a-axis with the smallest intermolecular Ln⋯Ln distance belonging to 1-Pr (11.0573(5) Å).
To examine the effects of the Tp2-Fu pseudo-icosahedral ligand field on SIM behaviour, alternating current (ac) magnetic susceptibility studies were performed on 1-Ce, 1-Pr and 1-Nd. Firstly, 1-Pr does not present any pronounced out-of-phase magnetic susceptibility (χ′′) signals regardless of applied fields (T = 2–20 K, Fig. S12 and S13†), implying 1-Pr is not a SIM. Based on the behaviour of 1-Ce and 1-Nd, vide infra, the use of the non-Kramers ion praseodymium(III) and weakly perturbing icosahedral crystal field (which is observed in 2-Ln)13 has been attributed to the poor behaviour of 1-Pr.
The zero-field behaviour of 1-Nd shows frequency dependence in χ′′ only below 5 K; however, no peaks are present (Fig. S15†). Applied field (Hdc = 2000 Oe) studies on 1-Nd reveal peaks in χ′′ between 2 and 4 K (Fig. 4 left and Fig. S18†), which were fitted to the generalised Debye equation (eqn (S1)†) to extract the magnetic relaxation times (τ) that were further modelled using a magnetic relaxation rate equation (eqn (S2)†). Plotting the natural logarithm of the magnetic relaxation times against inverse temperature (T−1) produces a non-linear regime, likely indicating Raman relaxation (Fig. S19†). Thus, these were fitted employing the Raman relaxation rate equation, τ−1 = CTn, yielding the values C = 0.028(7) s−1 K−n and n = 10.3(2).
The Raman exponent of 10.3(2) is unusually large for a Kramers ion, where reduced exponents are typically sought to improve SIM behaviour.18 When attempting to fit the magnetic relaxation rates for 1-Nd to an Orbach style equation, an energy barrier of Ueff = 19.9(5) cm−1 (τ0 = 3.0(9) × 10−8 s) is extracted. Despite it being similar to those of other reported neodymium(III) based SIMs,19 we note that the data points do not fit as well as for the purely Raman relaxation mechanism (Fig. S19†). We attribute the dominant Raman relaxation mechanism to the large ligand scaffold likely having a high density of low energy vibrational modes.
Surprisingly, the zero-field magnetic susceptibility for 1-Ce showed frequency and temperature dependence up to 15 K when using frequencies up to 10000 Hz and the sensitivity of cerium(III) based zero-field SIMs is highlighted by the high adiabatic susceptibility, indicating that a large percentage of the sample does not show slow relaxation under zero-field conditions. To date, only two other cerium(III) compounds have been reported as zero-field SIMs, [Ce(Cpttt)2Cl] (Cpttt = 1,2,4-tri-tert-butylcyclopentadineyl), though the authors only refer to the applied field data (Hdc = 1000 Oe), and [Ce{ZnI(L)}2(MeOH)](BPh4) (L = N,N,O,O-tetradentate Schiff base), with an effective anisotropic energy barrier of Ueff = 14.7(4) cm−1.20,21 The zero-field relaxation parameters for [Ce(Cpttt)2Cl] are included in their ESI and showed both Raman and quantum tunnelling of magnetisation (QTM) relaxation mechanisms, with applied field magnetic relaxation displaying solely Raman relaxation (Table 2).20 Upon reviewing the zero-field data for [Ce(Cpttt)2Cl], it seems the fitting to the generalised Debye equation at 2 K was not modelled appropriately, producing a non-existent QTM mechanism.
Complex | H dc/Oe | Orbach | Raman | QTM | ||
---|---|---|---|---|---|---|
τ 0/s | U eff/cm−1 | C/s−1 K−n | n | τ QTM/s | ||
a Zero-field behaviour may not be reported accurately (see in text). b The switch to a non-linear regime is identified as QTM though it is possible that this divergence is a consequence of Raman relaxation as at the time of publishing it was not widely adopted. c Value was fixed during fitting. | ||||||
1-Ce | 0 | 2.7(3) × 10−6 | 30(5) | 54(7) | 1.2(1) | — |
250 | 1.2(2) × 10−5 | 25.1(6) | 0.9(1) | 2.2(1) | — | |
2-Ce | 1500 | — | — | 6.9(6) | 4.34(5) | — |
[Ce(Cpttt)2Cl] | 0a | — | — | 1.28 × 10−3 | 8.28 | 1.74 × 10−2 |
1000 | — | — | 4.75 × 10−3 | 6.48 | — | |
[Ce{ZnI(L)}2(MeOH)](BPh4)b | 0 | 1.6(3) × 10−7 | 14.7(4) | — | — | 3.8(2) × 10−4 |
[Ce(NO3)3(1,10-diaza-18-crown-6)] | 1000 | 2.3(5) × 10−8 | 31(1) | 0.54(2) | 5c | — |
Zero-field ac magnetic susceptibilities for 1-Ce were collected between 2 and 8 K (Fig. 4 and Fig. S16†). Fitting this data to the generalised Debye equation resulted in distribution parameters (α) below 0.02, indicating a narrow distribution of magnetic relaxation times (Table S2†). The χ′′ at low temperature for 1-Ce bears a resemblance to the behaviour of 2-Tb;13 there is a limiting value for χ′′ at high frequency below 5.5 K before temperature dependence emerges above the said temperature. For 2-Tb, this behaviour was indicative of the switching between Raman and Orbach relaxation. After plotting the relaxation times for 1-Ce, the same is true where above 5.5 K there is a switch from Raman to Orbach relaxation. The relaxation rate fitting for 1-Ce produces an effective energy barrier to magnetic relaxation of Ueff = 30(5) cm−1 and Raman parameters of C = 53(2) s−1 K−n and n = 1.26(6) (Fig. 5). Notably, the zero-field ac susceptibility for 1-Ce does not present magnetic relaxation via a QTM mechanism, implying that the cerium centres are well isolated from each other (shortest intermolecular distance of Ce⋯Ce = 11.0781(6) Å), which differs from [Ce(Cpttt)2Cl] (Ce⋯Ce = 8.0712(5) Å) where an applied field was reportedly needed to supress QTM.20
![]() | ||
Fig. 5 Magnetic relaxation plots for 1-Ce under zero and applied magnetic fields. Both data sets have been modelled using Orbach and Raman fitting with parameters summarised in Table 2. |
Applied-field sweeps at 2 K (Fig. S11†) revealed the optimal applied field for magnetic relaxation in 1-Ce to be Hdc = 250 Oe, with the applied field data bearing a resemblance to the zero-field susceptibility, though magnetic relaxation is slower at a given temperature (Fig. 4). Applied-field ac data for 1-Ce were analysed analogously to the zero-field data, yielding a similar energy barrier (Fig. 5 and Table 2). The same limiting phenomenon was observed in the applied field data for 1-Ce; however, the switching temperature was lower at ca. 4 K. The energy barrier derived from the fitting for 1-Ce in zero-field is, to our knowledge, the highest for a cerium-based SIM but is approximately equal to the record of 31(1) cm−1 (within error), observed for [Ce(NO3)3(1,10-diaza-18-crown-6)] in an applied field (Table 2),22 and is a rare example where zero-field behaviour is observed, although we do acknowledge that a small residual field might be the cause of said zero-field behaviour.
The ground state of the non-Kramers praseodymium(III) ion in 1-Pr reflects that of a pseudo-doublet with states 2.70 cm−1 apart (Table 3). The relatively large energy gap within this ground pseudo-doublet is likely the reason for the fast magnetic relaxation in 1-Pr. The wavefunction decomposition reveals that the 3rd/4th and 6th/7th excited states are pseudo-doublets with slightly larger energy separation (Table 3). In a perfectly axial crystal field, there would be no wavefunction mixing for non-Kramers ions, and all energies would be doublet states with a singlet state of mJ = 0. This type of electronic structure is approximately established when stronger crystal fields are used and are not as susceptible to deviations from axial crystal fields.
Energy/cm−1 | g z | Wavefunction compositiona |
---|---|---|
a Contributions under 10% are not shown. | ||
0 | 5.9644 | 0.47|+4〉 + 0.47|−4〉 |
2.70 | 0.48|+4〉 + 0.48|−4〉 | |
48.9 | — | 0.44|+3〉 + 0.44|−3〉 |
142 | 2.3772 | 0.47|+2〉 + 0.47|−2〉 |
151 | 0.33|−2〉 + 0.33|−2〉 + 0.12|+1〉 +0.12|−1〉 | |
234 | — | 0.44|+3〉 + 0.44|−3〉 |
556 | 1.2040 | 0.41|+1〉 + 0.41|−1〉 + 0.12|0〉 |
563 | 0.35|+1〉 + 0.35|−1〉 + 0.12|+2〉 + 0.12|−2〉 | |
768 | — | 0.77|0〉 |
As stated, the Kramers ions (neodymium(III) and cerium(III)) prefer axial anisotropy for their ground states, although the mJ = ±9/2 state for neodymium(III) is more isotropic than cerium(III) (with respect to its electrostatic potentials).12,23 For 1-Nd, we find that the ground state wavefunction composition is 67% mJ = ±7/2 while the first excited state possesses a higher composition of the mJ = ±9/2 state at 51%. All states in the ground J-manifold for 1-Nd are heavily mixed and the first excited state sits 20.5 cm−1 above the ground state. This energy gap is comparable to the Orbach relaxation parameter derived from the magnetometry data, suggesting that an Orbach mechanism is probable for 1-Nd.
The electronic structure for 1-Ce is a simpler example as there are only 3 doublets that define the J-manifold. The ground state of 1-Ce is highly axial (gx = 0.13, gy = 0.23, gz = 4.05) and well defined by mJ = ±5/2, with the projection of this state deviating from the B⋯B axis by 0.9° (Fig. S20†). The ground state is highly stabilised with the first and second excited states in 1-Ce sitting 532 and 572 cm−1 above the ground state. The first and second excited states are predominately defined by mJ = ±1/2 and ±3/2, respectively (Table 4), and are not sequentially ordered; thus magnetic relaxation could occur via the first excited state. However, like most cerium-based SIMs, the experimental energy barrier to magnetic relaxation is less than 50 cm−1 even though the first excited state sits an order of magnitude higher than this.
Energy/cm−1 | g z | Angle/° | Wavefunction compositionsa | |
---|---|---|---|---|
a Contributions under 10% are not shown. | ||||
1-Ce | 0 | 4.05 | — | 0.99|±5/2〉 |
532 | 2.84 | 80.99 | 0.81|±1/2〉 + 0.15|±3/2〉 | |
572 | 2.68 | 43.32 | 0.84|±3/2〉 + 0.13|±1/2〉 | |
1-Nd | 0 | 4.88 | — | 0.67|±7/2〉 + 0.16|±9/2〉 + 0.13|±5/2〉 |
20.5 | 5.15 | 16.85 | 0.51|±9/2〉 + 0.22|±3/2〉 + 0.16|±7/2〉 | |
150 | 1.82 | 86.83 | 0.38|±3/2〉 + 0.28|±5/2〉 + 0.12|±1/2〉 | |
397 | 2.33 | 82.54 | 0.39|±5/2〉 + 0.27|±1/2〉 + 0.11|±3/2〉 | |
501 | 3.8146 | 11.43 | 0.42|±3/2〉 + 0.32|±9/2〉 + 0.12|±1/2〉 + 0.12|±5/2〉 |
Previous exploration by Rajaraman and co-workers looked into a similar cerium(III) problem and attempted RAS-probing calculations to explore if 4d orbitals contributed to the crystal field splitting states, to no avail.24 We explored an alternative avenue, performing calculations including the 5d orbitals in the RAS3 space. However, similar to the prior computational studies, we found minimal variations in the calculated results (Table S9†). Computational variations are ongoing, focussing on the double shell effect (5f orbitals) as well as the impact of simultaneous inclusion of 4d and 5d orbitals in RAS probing methods. However, to date, an explanation for the low experimentally observable cerium(III) energy barriers remains an unexplained phenomenon.
Footnote |
† Electronic supplementary information (ESI) available. CCDC 2395485–2395488. For ESI and crystallographic data in CIF or other electronic format see DOI: https://doi.org/10.1039/d4dt03231d |
This journal is © The Royal Society of Chemistry 2025 |