Single-Molecule Magnets

Michelle McKinney
The earliest recorded discussions of magnetism date from around 600 BC. Today, this naturally occurring phenomenon has found a range of applications both in industry and items we use everyday, such as ATM cards, televisions, speakers, among many others. Perhaps one of the most important applications of magnetism is in information storage devices such as computer hard drives. The increasing miniaturisation of these devices has seen the power of computers and other personal devices such as mobiles phones, games consoles etc advance at a dramatic rate over the last few decades, but some speculate this growth cannot continue. This may be true, if the manner in which we store this information remains the same. There is however, a new emerging technology which has the potential to miniaturise such data store to an unprecendented scale.

Magnetism
This review will assume a basic knowledge of the theory of magnetism in its different forms i.e. paramagnetism, ferromagnetism etc. Building on this knowledge, several new concepts relevant to understanding Single Molecule Magnets (SMMs) will now be introduced.

Microstates All chemists are familiar with the concept of an atoms electronic configuration, which describes the number of electrons in each orbital. This description, however, gives no information regarding the electrons spin and angular orbital momentum. To describe these parameters we introduce microstates, where ml and ms designate microstates for orbital and spin angular momentum respectively. For the moment, we will consider only the spin angular momentum microstates. In describing a single electron, which has a spin S = , it may have a spin microstate, ms, of either + (spin up) or (spin down). The number of spin microstates a system may possess is governed by the principal spin quantum number S, such that:

Number of spin microstates/Spin multiplicity = 2S +1 Therefore for a system with S = there are 2() + 1 = 2 spin microstates, namely ms = + and ms = - . For a S = 1 system, there will we 2(1)+1 = 3 microstates, ms = +1, 0, -1, depending on how the individual spins interact with each other.

Magnetism has historically been associated with bulk materials, and the notion of magnets capable of being isolated at the molecular scale is an extremely recent one. When one considers the different modes of magnetic behaviour observed in bulk materials, such as ferro and ferrimagnetism, it is observed that all modes of paramagnetism involve individual dipoles over the whole lattice, interacting to give rise to a net magnetic moment (or not, in the case of antiferromagnetism). While the essence of molecular magnetism is that it involves discrete molecules and not an extended lattice, the net dipole is still a result of interaction between individual dipoles. The first evidence found for magnetic interactions on this scale involved only two metal centres and indeed was first thought to contain only one metal centre! Though not a Single Molecule Magnet in itself, it merits discussion as an aid to describing how SMMs work. Copper(II) acetate hydrate was first assumed to be a monometallic complex, with formula [Cu(II)(OAc)2(H2O)x], where for x = 1 or 2. A mononuclear complex would be expected to obey the Curie Law, which states that for magnetically dilute complex (i.e. not subject to any interactions from neighbouring dipoles), the magnetization observed as a result of an applied magnetic field is inversely proportional to temperature. The copper acetate complex, however, did not return the anticipated results. It displayed lower magnetic susceptibility than the Curie Law predicted at all temperatures and was found to be practically diamagnetic at temperatures below 90K. It was not until a crystal structure was conducted several years later that it was revealed that the complex actually existed as a dimer [Fig 1], with the acetate ligands acting as bridges. If these centres could interact antiferromagnetically, susceptibility results [1]. this would explain the unexpectedly low magnetic

Figure 1: Cu2(O2CCH3)4(H2O)2]

Consider the possible interactions between two d9 Copper centres, each with one unpaired e- [Fig. 1].

Figure 2: Possible interactions between unpaired e- (a) Antiferromagnetic interaction (b) Ferromagnetic interaction

Both cases will always occur, but one will act as the ground spin state, implying there is an energy difference between the two possibilities[Fig 2].

Figure 3: Ground state possibilities for Cu dimer [Cu(II)(OAc)2(H2O)x]

This energy difference is called J, and describes the magnetic interaction between the metal centres. It is possible to measure J, and in doing so learn about how the metal centres are interacting. Without concerning ourselves about how J is determined experimentally, it can safely be said that if J is negative, centres are interacting antiferromagnetically and if J is positive, centres are interacting ferromagnetically Ferromagnetic interactions will clearly lead to a larger dipole moment, and the larger the S value the larger the magnitude of J, and the more stable the non-zero ground spin state.

Consequently, for a molecule to display interesting and more importantly useful magnetic properties, the molecule must have a non-zero spin ground state. This is one of the criteria which must be fulfilled for a compound to have any possibility of acting as a Single-Molecule magnet. The larger the spin ground state, the more pronounced the compounds magnetic behaviour large S values in the ground state are therefore desirable when designing single molecule magnets.

The other criterion for SMM behaviour to occur is for the complex to exhibit significant magnetoanisotropy, defined by a negative zerofield splitting parameter D. Above, we saw the formation of microstates due to interaction between nuclei. The spin of the system will typically only split into the microstates under the influence of a magnetic field, be that from a neighbouring nucleus or an external magnetic field. Zero Field Splitting refers to the removal of the degeneracy of the microstates in the absence of any external field. It arises due to anisotropy of the molecule, that is, a directional preference for its magnetic moment in zero fields. Most magnetic compounds will display some degree of anisotropy, unless they are in a highly pure and symmetric octahedral or tetrahedral symmetry. In d systems such as those around transition metal centres, Jahn-Teller distortions of the d orbitals means the majority of such systems will display some directional preference along which they will align their magnetic moment. This direction, whatever it may be, is designated as the complexs easy axis, and is arbitrarily set as the z-axis. Similarly to above, when zero field splitting occurs, there are a variety of configurations the system can take on when the microstates split, depending on what microstate is acting as the ground state. For example, an S =1 spin system will, as above, split into ms = 0, 1 microstates. The 1 states remain degenerate, and together are know as the triplet state, while ms = 0 is

called the singlet state. Whether the triplet or the singlet state becomes the ground state is described by the sign of D, which is defined as the energy separation between the lowest lying triplet and singlet states in the absence of an applied field [Fig 3]. The energy of each microstates is given by E(ms) = Ms2D, therefore the larger the value of Ms, the larger the barrier for a transition between given microstates. As the energy barrier is also dependant on the magnitude of D, the largest possible negative D value is desirable when discussing SMMs.

ms = 0

ms = +1, -1

ms = 0, +1, -1 D<0

ms = 0, +1, -1 D>0

ms = +1, -1 (a) (b)

ms = 0

Figure 4: Zero field splitting patterns for S = 1 system (a) negative D (b) positive D

Highly anisotropic materials will typically (but not always) display a negative D value, making anisotropic materials candidates as potential SMMs.

What systems fill these criteria? Transition metal ions (i.e. MnIII, NiIV, FeII) are likely candidates as building blocks in the construction of molecular magnets, due to their paramagnetic nature (unpaired valence electrons) and their inherent single-ion anisotropy. The first SMM discovered was manganese complex [Mn12O12(O2CMe)16(H2O)4]4H2O2CH3CO2H, herafter referred to as [Mn12]. This compound was first synthesised in 1980 [2] but its magnetic properties were not noted until 1993 by Christou et al [3].

Figure 5: Arrangement of Mn ions in Mn12 complex. Shaded circles represent MnIV, white circles MnIII, smaller white circles represent bridging O2- anions.

The complex consists of MnIV ions (S = 3/2) in the central [Mn4O4]8+ cube, surrounded by 8 MnIII ions (S = 2) in a non planar ring. 3 O2- ions and acetate bridging ligands hold the entire structure together, while the four H2O molecules act as terminal ligands.The MnIII and MnIV ions couple together antiferromagnetically, resulting in an S = 10 ground spin state (82 43/2 = 10). Using High Field Electron Paramagnetic Resonance (HF-EPR)[4], it was found that the zero field splitting parameter D must be < 0, indicating the states with the largest Ms ( 10) are lowest in energy. HF-EPR confirmed the presence of two low lying energy levels, corresponding to Ms = +10 and -10. While these energy levels are initially equal in magnitude, corresponding to a double well potential, an external magnetic field will tilt the potential energies, making one well higher than the other (i.e. higher in energy). The graph below [5] demonstrates this, along with quantum tunnelling, which will be discussed shortly [Fig 5].

Figure 6: Double wells representing potential energy of Ms = =-10 microstates in (a) zero external field (b)in presence of external field. Quantum tunnelling is present in both cases[5].

The ms = +10 and ms -10 states are equal in magnitude but opposite in direction one is said to spin up and the other spin down. The barrier which the system must overcome in order to go from spin up to spin down (or vice-versa) to the other is given by U = S2D for integer values of S and U = (S2 )D for half integer values of S. HF-EPR found this energy barrier to be 10cm-1[4]. Following application and removal of an external magnetic field, relaxation times became very long beneath 4K (known as the blocking temperature for this compound), reaching the order of 2 months at 2K extremely slow relaxation which the barrier to relaxation of 10cm-1 is at least partly responsible. The compound was also found to display a hysteresis loop below this temperature, signifying magnetic bistability.

Figure 7: Hysteresis loop of Mn complex with a SQUID micrometer at 2.2K (filled circles) and 2.8K (blank circles)

Such hysteresis is characteristic of materials used as information storage devices, with up and down conformations representing 1 and 0 (i.e. bits of information). The discovery of such behaviour on a molecular level represented a potential breakthrough for such magnetic storage devices. SMMs have also been heralded as a breakthrough as they are the first systems in which the phenomenom of quantum tunnelling, predicted by quantum mechanics, has been physically observed. Whereas above it was stated that in order to undergo relaxation the system must overcome the energy barrier of S2D, this is not strictly true. Quantum mechanically, some proportion of particles has a small probability of undergoing relaxation despite this barrier, due to resonance between microstates on opposite sides of the barrier. SMMs provided the first physical evidence of quantum tunnelling, observable as steps in a hysteresis loop, as illustrated below.

Figure 8: Magnetic hysteresis loops, measured at different temperature (4.2-1.8 K) displaying quantum tunnelling "steps"

Steps in a hysteresis loop mean the system is suddenly undergoing a drop in magnetisation despite the external field remaining the same. This unpredicted drop is due to a certain proportion of molecule relaxing via quantum tunnelling. The above loops also show a relationship between the size of the coercive field (the area within the loop) and temperature. Such a relationship is indicative of magnetic hysteresis which is molecular in origin.

Other SMMs
Despite being formed somewhat incidentally, and despite intense investigation into novel SMMs over the last 15 years, [Mn12] has remained the most effective SMM since its discovery, The majority of studies have focused on 3d transition metals, and an excellent review article by Aromi and Brechin [6] will provide detailed information for anyone who so wishes. In this article we will discuss but a few examples before going on to discuss a new breed of SMMs which has eventually surpassed the [Mn12] complex. The other most notable SMM, in terms of its value as a reference material and the amount of literature discussing it, has proved to be [Fe8O2(OH)12(tacn)6]8+[7], (where

tacn = 1, 4, 7-triazocyclononane) hereafter referred to as [Fe8]. As with[Mn12], this compound was synthesised a good ten years before its magnetic properties were realised. It was found to have a ground spin state of S = 10. However, whereas for [Mn12] the energy barrier to magnetisation relaxation has been reported as 67-70K, for [Fe8] it is only 25K. Nevertheless, this molecule remained an important reference point, as it was only the second system to display molecular hysteresis and quantum tunnelling, properties intrinsic to SMMs. As with [Mn12], this compound was the first in its family to be synthesised, and remains the main reference point when discussing FeIII based SMMs. NiII based molecules have drawn much interest as potential SMMs, as they are known to display large single-ion anisotropy. The first such NiII complex to be synthesised was [Ni12(chp)12(O2CMe)12(thf)6(H2O)6] [8], (where chp = deprotonated 6-chloro-2pyridinol). This compound was found to have an S = 12 ground spin state, larger than the Fe and Mn compounds we have discussed previously, but when coupled with a disappointedly small D = -0.05cm-1, gave a barrier to magnetic relaxation of only between 9 and 10 K. Quantum tunnelling was also observed for this complex. Utilising CoII ions in the synthesis of SMMs has also attracted much interest in the field [9]. However, the significant spin-orbit coupling present in CoII systems means that the subsequent fitting of their magnetic data is extremely difficult at best, and impossible at worst. Due to its air sensitivity, only one class of VIII (d2, S=1) SMMs have been prepared successfully [10, 11]. [V4O2(O2CEt)7(L-L)2]z, where z=-1 for L-L = deprotonated picolinic acid, and z = +1 for L-L = bipyridine. Slow relaxation was observed, however a ground state of only S = 3 was confirmed along with a D = -1.5cm-1 ZFS.

Mn6 the new record holders

Above mentions but a few SMMs made over the last decade and a half. As well as investigating the use of different metals, researchers have also investigated the effects of different structural architecture, different ligands and mixed valence metals. In the face of this extensive body of work, [Mn12] remained as the SMM with the highest barrier to magnetic relaxation and hence the highest working temperature, a high

working temperature being a crucial characteristic if SMMs are ever to have any real life applications. The truly amazing thing is that this complex was not designed the display these exceptional properties. Indeed, it was first synthesised by a somewhat serendipitous self assembly of Mn and acetic acid in solution. However, 2007 saw the end of [Mn12] as the champion of SMMs. Specific design saw the birth of a new family of molecules [12], one of which possessing a record anisotropy barrier for SMMs[13]. The founder of this family was [MnIII6O2(sao)6(O2CPh)2(EtOH)4] (where sao2- = dianion of 2-hydroxybenzaldehyde oxime) and was found to display a spin ground state of S = 12 and a zero field splitting factor of D = -1.39cm-1. Further members of the Mn6 family were synthesised, all of which shared a common core, which is shown below.

The

MnIII

Figure 9: Common core on Mn6 based clusters [12].

ions

within

each

of

the

triangles

couple

to

each

other

antiferromagnetically, while the triangles themselves undergo ferromagnetic interactions with each other, leading to the S = 4 ground state. Twisting of the manganese-sao linkage (Mn N O Mn) was induced by replacing sao2- ligands with bulkier Et-sao2- ligands. This structural distortion of the [Mn3] triangles leads to a switch in the mode of coupling between individual MnIII ions from antiferromagnetic to ferromagnetic, hence an S = 12 ground state. This ferromagnetic coupling is weak however, with low level excited states and a low barrier to magnetization reversal. The final step was to further increase the Mn N O Mn twisting with more bulky ligands, namely, replacement of benzoate with 3, 5-dimethyl benzoate, to afford final product [MnIII6O2(Et-sao)6(O2CPh(Me)2)2(EtOH)6], shown below.

Figure 10: [MnIII6O2(Et-sao)6(O2CPh(Me)2)2(EtOH)6]

Magnetic characterisation of [Mn6] and its family members make clear the profound effect of the bulky organic ligands and bond twisting. At low temperatures [Mn6] displays an S = 12 ground spin state with D = -0.43cm-1. Using this data, the barrier for magnetization relaxation has been calculated as 86.4K, thus exceeding the previous record held by [Mn12] by 12-13K. Relaxation studies on a micro-SQUID indicated a blocking temperature of 2K [13] Further studies on singlecrystal hysteresis loops revealed a blocking temperature not of 2K, but of 4.5K, a record operating temperature for an SMM.

The immediate significance of this work is apparent, in that we are now closer, if only by one or two degrees, to SMMs which can operate within real life temperatures. What is less immediately obvious but perhaps more significant is the fact that this was a targeted molecule, designed specifically to display a high spin ground state and barrier to relaxation, and was based on extensive investigations into correlations between structure and magnetic properties [14]. One of the major stumbling blocks in the field of SMMs is the difficulty encountered when one tries to make a transition

metal cluster in any predictable way, and there is a certain amount of happenstance involved in any successful synthesis. This work provides the first predicted, premeditated metal cluster acting as a SMM, and also happens to be the most effective SMM to date.

SMMs in the future

Following the discovery that significant structural distortion of polymetallic cluster cores can incur a higher spin ground state than the cluster in its natural state, it is extremely likely that research groups will revisit previously studied clusters in a effort to increase their spin ground state. As with the last decade of SMM research, the majority of research into novel SMMs will likely focus on manganese based clusters, though the onus is now on smaller clusters of 6 or less as opposed to 12. As well as synthesising and studying SMMs themselves, much work needs to be done to unearth the correlations between not only structure and magnetic properties, such as the work Mn6 was based on, but on any correlations which may help chemists understand and predict magnetic behaviour of metal complexes. All of this study will contribute towards the ultimate goal of achieving an SMM with a practical working temperature.

1. B. B. Bleaney, K. D. Proc. R. Soc. London A214 (1952). 2. L. T. Acta crystallogr. B36, 2042-2046 (1980). 3. R. Sessoli, H. L. Tsai, A. R. Schake, S. Wang, J. B. Vincent, K. Folting, D. Gatteschi, G. Christou, D. N. Hendrickson. J. Am. Chem. Soc. 115, 1804-1816 (1993). 4. R. G. Sessoli, D.; Caneschi, A.; Novak, M.A. ature 365, 141-143 (1993). 5. M. F. Bal, J. R.; Rumberger, E. M.; Shah, S; Hendrickson, D.N; Avraham, N.; Myasoedav, Y; Shtrikham, H; Zeldov, E. (2008). 6. A. B. Guillem, E. Struct Bond, 1-67 (2006). 7. e. a. W. W. Science 284, 133-135 (1999). 8. W. R. Hanspeter Andres. Chem. Eur. J. 8, 4867-4876 (2002). 9. Y. En-Che, N. H. David, W. Wolfgang, N. Motohiro, N. Z. Lev, D. S. Roger, L. R. Arnold, L.-G. Marisol, C. George. pp. 7382-7384. AIP (2002). 10. P. R. Chaudhuri, E; Birkelback, F; Krebs, C, Bill, E; Weyhermuller, T, Florke, U. Eur J Inorg Chem 541 (2003). 11. S. S. Castro, ZM; Bollinger, JC; Hendrickson, DNl Christou, G. 2517 (1995). 12. C. Milios, J; Piligkos, S; Brechin, E.K. Dalton Trans., 1809-1817 (2007). 13. C. J. V. Milios, A.; Wernsdorfer, W.; Moggach, S.; Parsons, S.; Perlepes, S.P.; Christou, G.; Brechin, E,K. J. Am. Chem. Soc. 129, 2754-2755 (2007).

14. C. J. I. Milios, R.; Vinslava, A.; Bagai, R.; Wernsdorfer, W.; Parsons, S.; Perlepes, S.P.; Christou, G.; Brechin, E,K. J. Am. Chem. Soc. 129, 12505-12511 (2007). My principal resources included an excellent review article of transition metal SMMs by Brechin and Aromi, as well as a much cited paper about [Mn12], the first SMM and a relatively recent paper about new [Mn6] SMMs, which has recently become a hot article on Dalton Transactions. After reviewing these papers, it was obvious to me that these 2 classes of SMMs basically constituted the SMM story, with lots of inferior SMMs lying in between their respective discoveries, and I designed my essay to reflect this. My conclusions came naturally when I realized the significance of the manner in which [Mn6] family of SMMs was developed.