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By S. T. BRAMWELL University College London, Department of Chemistry, Christopher Ingold Laboratories,20 Gordon Street, London WCIH OAJ, UK

1 Introduction
Magnetism forms a gigantic field of research of which magnetochemistry is a small part. It is an exceedingly rich subject, which does not fit easiIy into the traditional disciplines of science. This report strives to d o justice to the richness and diversity of the subject, whilst concentrating on developments of direct reIevance to chemistry. In no sense is an attempt made to give an exhaustive account of the literature; this is clearly unfeasible when the 1996 literature contains over twenty thousand references that allude to magnetic properties. The report is divided into four sections. The introductory section will try to identify the major highjigbts and trends in magnetochemistry, and will mention some of the more interesting developments across diverse fields that may give inspiration to the magnetochemist. Some books and general reviews will also be described. Section 2 is devoted to a more detailed summary of the year’s literature in several selected topics. The remaining sections, 3 and 4, group work according to the type of materia1 under investigation. Section 3 describes work on ionic, covalent and metallic materials, particularly oxides and halides which are the traditional interest of solid state chemists. Section 4 describes work on metal complexes and molecular solids, more traditionally the domain of coordination chemists. In this section the materials are cfassified by dimensionality of the complex, which from the magnetic point of view seems to provide a natural division. This report follows on from the excelIent series by Harrison and colleagues,’ their policy of not reporting on the simple characterisation of magnetic materials has been adopted, apart from in cases that this is relevant to a more general problem in magnetism. Perhaps the highlight of the year is the discovery by several groups of dramatic quantum tunnelling effects in molecular clusters. These results, which are described in detail in Section 2, raise hopes that one day such effects can be harnessed to make nanoscale magnetic memory devices. They provide a clear motive for the magnetochemist to synthesize and study such cIusters, and open up exciting prospects for future research. It is to be hoped that coordination chemists wilI rise to this challenge, as it is clear from this survey of the literature that the huge amount of work on small magnetic clusters, although worthy, has little scientific motive beyond basic characterization. A rather more focused, and equally popular subject of research is ‘molecu1ar


S. T.Bramwell

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ferromagnetism’, but unfortunately progress in this field is slow, with transition temperatures largely rooted to liquid helium levels. In solid state chemistry giant magnetoresistance is the most popular current topic of study, and is again motivated by a commercial goaI. Progress in this field is much faster than in the rather ailing ‘high-T,’ industry, although there are stiH many chemists involved in studying magnetic oxides related to the superconducting cuprates. From the point of view of pure science, frustrated magnets are the main focus of attention, and although only a relatively modest number of researchers are involved in this field, the collaboration of chemists and physicists ensures steady progress. The research areas described above form the main subject of the forthcoming sections of this report. Also selected are some topics which are really physics, but are of genera1 relevance to magnetochemistry. These include new magneto-optic effects, nucIear magnets and various theoretical studies. It is interesting to put all these subjects into a wider context by examining the magnetic research that has made it into the pages of the semi-popular scientific journals. Both Nature2 and Science3 have devoted editorial space to discussing the quantum mechanical tunnelling phenomena and the described in section 2, giant rnagnetoresi~tance,~~~ new magneto-optic effects described in section 3.6*7Science also carried an editorial article on the effect of ‘negative viscosity’ in magnetic fluids.8 This topic is so fascinating that it would seem worthy of a brief description. Negative viscosity refers to the reduction in viscosity of a magnetic fluid-a colloidal suspension of single-domain magnetic partictes-when subject to changing magnetic fields. Almost magical effects can be observed, for exampie, if a drop of magnetic fluid is suspended in another fluid in a rotating magnetic field: the drop develops starfish-like spiny arms, and, depending on the frequency, weird eel-like structures. Although magnetic fluids are widely used in hard disk drives, audio speakers, printing and magnetic resonance imaging, there is as yet no practical use for these effects. Other magnetic headlines in these journals have concentrated on magnetic fields in space. Nature has reported an interesting result from the Galileo space probe, that Jupiter’s moon Ganymede is the first moon to be discovered that has a magnetic field, possibly arising from convection in a layer of salty water below the ~ u r f a c eOn a more .~ popular leveI, New Scientist described how PobelI and colleagues at Bayreuth University have made the ‘coldest lump of metal ever’, a 32g piece of Pt cooled to 3 pK by adiabatic demagnetization of the nuclear spins.” A number of magnetic devices have been reported in engineering magazines. Professional Engineering describes a torque magnetometer that traveIs along the 17 000 krn of Britain’s steel gas pipelines, detecting flux Ieakage into corroded regions on the exterior of the pipe.” Insight magazine noted that Oxford Instruments have announced the successful operation of the world’s first cryogen-free superconducting magnet; the work required to cool the magnet to 5 K being provided entirely by the externaI power Electronics Today reported an ingenious new type of magbased on a xylophone resonator, it is sensitive to netometer designed by Givens el a[+:’ a wide range of fields and Iends itself to miniaturization. This introductory section is concluded by noting a number of books and reviews that have appeared this year. Aharoni has pubIished a book on the theory of feromagnetism that covers basic aspects of exchange, anisotropy and magne tostatics, as well as giving a more comprehensive coverage of the theory of rnicr~magnetics.’~ Although

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mainly intended for physicists and engineers, magnetochemists may find this book a useful guide to the more mysterious aspects of ferromagnetism. At a much more popular level, Livingstone’s book, Driving Force-The Natural Magic of Magnets,’ has been reviewed very favourably by G r a n t x 6 Volume 544 of the American Chemical Society Symposium Series, the published proceedings of the 1995 International Chemical Congress of the Pacific Basin Societies at Honolulu, is devoted to molecular-based magnetic materials. l 7 It contains 22 reviews and research papers on theory, technique and applications in molecular magnetism. Gatteschi el a!.” have reviewed the magnetism of large iron-oxo clusters. Giant magnetoresistance in layered and granular alloy systems has been reviewed by Levy.I9 The giant or coIossal magnetoresistance of the Ianthanide manganates has been reviewed by Rao et aL2” Several reviews on molecular ferromagnetism have appeared.’ l S 2 ’ Kirchmayr has reviewed permanent magnets, with an emphasis on hard magnetic materials based on rare-earth inter metallic^.^^ Mydosh has reviewed disordered magnetism and spin gIasses, and suggested that future avenues of research will concentrate on the changes of magnetic behaviour caused by nanostructuring such material^.^^ Govord e t have reviewed the magnetism of intermetallics with non-magnetic constituent elements, such as weakly ferromagnetic PdTiAl. There have been several rather less general reviews, concentrating on work from particulargroups. Khan et al. have reviewed their work on the magnetism ofmolecular based bimetdlic species,26 and Day has reviewed work at the Royai Institution of Great Britain on organic-inorganic layer corn pound^.^^ Broholm et at. have published a short review of the magnetism of transition metal oxides in which there are strong magnetic fluctuations at low temperature.28 They discuss frustration, the Haldane effect in one-dimensional chains, and the unusua1 case of (V, -xCr,),O, in which orbital fluctuations limit spin correlations to small ciusters. Some other reviews are mentioned in the forthcoming test.

2 Selected topics
Quantum mechanical tunnelling As mentioned above, one of the highlights of the magnetic year is the demonstration by several groups of quantum tunnelling effects in moIecular magnets. Physicists have for a number of years being trying to make an ensemble of identical nanometer scale magnets. This is of interest both for theoretical reasons, as a probe of the ‘grey area’ between quantum and classical mechanics, and for practicaI reasons, as a development in the nanomolecular engineering of magnetic memory elements. It is well known that small magnetic clusters behave quantum mechanically with the projection of the magnetic moment on the field direction adopting a series of discrete values labelled by the quantum number M,. Much larger assembhes of magnetic ions, however, behave as classical monodomain particles, that is, as tiny ‘compass needles’, with statistical averaging masking all evidence of discreteness in the magnetization. In the presence of uniaxial magnetic anistropy, a cIassical cIuster will not be able to ‘flip’ its magnetization if the temperature is much lower than the anisotropy barrier which prevents rotation of the particle’s magnetization; but a quantum mechanical cluster may

but antiferromagnetically to the central core. an assembly of identical nanopartides is required.C0. gives the complex an easy axis of magnetization and causes the M. each with spin 3/2. as all particles will have identical tunnelling rates.1039/IC9969300457 Fig. the rate of decay is suppressed. Brnmweli View Online n Downloaded by University of Calgary on 03 July 2012 Published on 01 January 1996 on http://pubs.. 2. an effect that should be Iargest when ‘spin up’ and ‘spin down’ states are degenerate in energy.C0.. rather than enhanced. 3). which behaves at low temperature as a single ‘super spin’. T. as would be intuitively supposed. arising from spin-orbit coupling. which are strongly exchange-coupled ferromagneticall y to one another. = -t 10 states to lie lowest in energy. Mn3’ (open) showing Mn4’ (shaded) and support resonant tunnelling of the magnetization through the potential barrier. the sample is found to have a stepped hysteresis loop. illustrated in Fig. Friedman et used the sample [Mn. The anisotropy axis corresponds to the crystaIline c-axis. with their spins (S = 2) coupled ferromagnetically t o each other. These remarkable observations provide clear evidence for quantum mechanical tunnelling between the different M . but more remarkably the rate of approach to equilibrium of the magnetization at a given external field depends sensitively on the magnitude of the field. Friedman et at.0.(CH.. In order to measure the tunnelling. consider the following: if the sarnpIe is initially magnetized in say the M . with maxima in the rate at fields corresponding to the steps in the hysteresis curve (Fig.6fH.). + . 1 Structure of Mn. However. then individual complexes will occasionally ff ip their spins and the bulk magnetization will decay slowIy.460 S. Experimentally.rsc. if a weak field is applied opposite to the magnetization direction.). 1.0).O l. have exploited this to magnetically align a polycrystalline sample which is then immobiiized in epoxy resin. These are surrounded by eight Mn3 ions. This gives the complex an overall spin S = 10. = + 10 state and the field is switched | doi:10. states on either side of the potential barrier. It has a tetrahedral core of four Mn4+ ions. = f 9 Iying next lowest and so on. To appreciate just how remarkable this result is.6(H20)4] the structure of which is illustrated in Fig.(CW. with M . obviating the need for large single crystals. Large molecular clusters can be crystallized easily into such an ensemble. Anisotropy.

05 . 2 Magnetization-v-field isotherms for Mn..0). Thus the magnetization is more prone to ‘flipping’ at every field at which such a degeneracy occurs.15 -3 1 I t I I -2 -1 0 H / Tesla 1 2 3 Fig. states with negative M .0. which become increasingly metastable.rsc. accidental degeneracies occur between states of positive and negative M.1039/IC9969300457 View Online 46 1 0.0s 3 \ 5 0.)4(H20).. Fig.Magnetism 0..0 z -0.O 12(CH3C0.0 10 . are stabilized with respect to states with positive M.10 Downloaded by University of Calgary on 03 July 2012 Published on 01 January 1996 on http://pubs.).(CH..(H. leading to the steps in the hysteresis Ioop and the oscillating . and resonant quantum mechanical tunnelling through the potential barrier is greatIy enhanced..: the difference between the magnetization ( M ) and its asymptopic value ( M .O.15 0. 3 Relaxation of the magnetization in | doi:10.CO. At regular intervals of the fietd.. ) as a function of time for two different fields As the applied field is increased.

= . however. which gives rise to a concise description of the phenomenon as ‘thermally assisted quantum tunnelling’.S 2. for exampIe Searle and Wang reported it in La. + + Giant and colossal magnetoresistance Among solid state chemists. There is evidence that the main tunnelling processes are in fact from excited states on the left hand side of the potential barrier.30*31 comprehensive A complex [Mn. = S to M. BramwelI View Online Downloaded by University of Calgary on 03 July 2012 Published on 01 January 1996 on http://pubs. HgCr. have also been known for many years. -. Doped ferromagnetic semiconductors such as the chromium chalcogenide spinels (e. some do not see what a11 the fuss is about.j3 The origin of the effect in these magnets has traditionally been ascribed to the Zener double exchange mechanism of ferromagnetic interaction between Mn3 and Mn4+.S relaxation times.462 S. It is therefore interesting to identify the factors that motivate the current research.U.9.32 which is relevant to zero temperature.rsc. Magnetoresistance is the change in resistivity with magnetic field. giant magnetoresistance in magnetic oxides continues to be a very popular subject of research. However.. 2(CH. at the field which brings the M.0. This can be thought of as arising from the scattering of conduction electrons by spin deviations in much the same way as normal metaIlic resistivity arises from the scattering by lattice vibrations or impurities. When + .S 2 and then decays to the ground state M . forcing the remaining IocaIized spins on Mn4+ to align parallel by Hund’s rules.: tunneHing from the metastable state M. theory of tunnelling effects has been published. T.6(H.C0. = . 4 Schematic representation of tunnelling in Mn. = S state degenerate with M. the theory does not immediately support the experimental findings.C02H-4H. as such effects have been known for years. The appIication of a field in this region suppresses the spin disorder and hence reduces the resistivity. Similar effects have been observed in the closely reIated 2CH. In reality the ‘excess’ electrons become delocalized over several Mn4’ sites. The magnetization tunnels from M .S + 2 followed by thermaIly assisted decay to the ground state M .S.) have Iong been known to show particularIy large magnetoresistance. negative rnagnetoresistance. = .0). leading to large. 4. Just Iike the scattering of light or neutrons.1039/IC9969300457 Fig. This process is illustrated schematically in Fig.Pb. and the authors discuss possible reasons for this. = S t o M .MnO. = . = . as long ago as 1969.S by losing quanta of energy to the lattice vibrations. .org | doi:10. In private.).6(H:20)40121.). this spin disorder scattering reaches a maximum at the magnetic critical point.(CH3C0.This mechanism arises because it is particularly easy for Mn3+ and Mn4+ to exchange an electron. Similar effects in doped LaMnO.

To that can be added several other factors. The series Ln. this is aIso equivalent to the effect of hydrostatic pressure. Harrison. (Ln = lanthanide.MnO. has lent support to this picture.96Mno.rsc.MnO.and hence can precipitate the transition to the metallic state. Zhou et at. in last year’s AnnuaI Report. but also encourages | doi:10. However the doping of LaMnU. -.Ca. and has emphasized that the ‘rediscovery’ of the lanthanum manganates is due in part to the improvements in experimental diffraction techniques allowing a more detailed analysis of the complex phases that exist in this system. O n the other hand only time wilI tell if the rewards justify the magnitude of the effort. -.Magnetism View Online 463 these ‘magnetic polarons’ form a percolating cluster.Mn0336 and La0. is correlated with the size of the Ln ion. which is generally competing with antiferromagnetism. Experimental work by Ramirez et al. . and the rediscovery of magnetoresistance in the manganates is timely.39 have presented a theory that incorporates the effects of both double exchange and the Jahn-Teller effect.40 It is undoubtedly the case that electron-phonon coupling is as important as double exchange in determining the electronic properties of these sysfems.Mn20.1039/IC9969300457 . and there is a direct relationship between the magnitude of the magnetoresistance and the final storage capacity of the disk drive. Other work has emphasised the importance of Jahn-Teller induced strains leading to charge ordering. on La. and there are a growing number of examples of giant magnetoresistance materials that adopt structures different to varying degrees from the cubic perovskite structure of LnMnO. Wollan and Koehler and Goodenough. Magnetoresistance thus clearly has a role to play in the computer age.MnO. and the modern emphasis of research funding bodies on research with an applied aspect. B = alkaline earth) have crysta1 structures of Downloaded by University of Calgary on 03 July 2012 Published on 01 January 1996 on http://pubs.. As described by Brug et heads have recently been introduced into the magnetic recording industry.B.35 -.Ca.38 M i l k et al. the renewed interest in magnetoresistance among the physics community arising largely from the discovery of giant magnetoresistance in metallic mu1tilayers. However perhaps the most important single factor motivating the research is the genuine increase in the importance of magnetoresistance as a commercially exmagnetoresistive recording ploitable magnetic property.42have shown that the coIossal magnetoresistance in Ln. At the time of the discovery of the giant magnetoresistance in the doped lanthanum manganates. The appIication of a magnetic field not only reduces spin disorder.Ca. -. B = alkaline earth metal). has given a detailed account of this early work.43 The occurrence of giant magnetoresistance in the mixed vaience manganates does not seem to depend too crucially on the crystal structure.960337 Pr. +. emphasizing the correlation between magnetic ordering and resistivity. A question of current interest is whether the simple double exchange mechanism described above does indeed account for the ‘coIossaI’ magnetoresistance in Ln.B2-. also reduces the concentration of the Jahn-Teller ion Mn3+ and so leads t o structural changes. (Ln = lanthanide. among others. have gone as far as suggesting that the strong coupling between conduction eIectrons and cooperative local lattice distortions leads to a new type of electronic Fontcuberta et at. Field-induced antiferromagnetic insulator to ferromagnetic metaI transitions have been observed in Nd. including the widespread availability of commercial magnetometers with magnetoresistance probes. a transition occurs to a ferromagnetic metal. the complex magnetic and structural properties of these materials had already been extensively characterized by the pioneering work of.xCaxMn03.

However f both Sr. Brarnwell View Online Downloaded by University of Calgary on 03 July 2012 Published on 01 January 1996 on http://pubs... 43)._.Ca.. (adapted from ref.rsc. Inplane resistivity (upper panel) and magnetization (lower panel) as a function of magnetic field the Ruddlesdon-Popper type which consist of layers formed of alternating perovskite have reported coIossal negative magand rock-sah-type blocks.1Mn207. The authors suggest that the large spin fluctuations associated with two dimensionality enhance the magnetoresistance in this range of temperature..Sr. with each phase adopting the Ruddlesdon-Popper structure. Both have low resistivity..NdMn.1039/IC9969300457 ..BMn. in the temperature range 4.O. and having very similar lattice ..O... Moritomo et netoresistance in La. Magnetic field I T Fig.0. ... and the magnetoresistance rises as the temperature falls in this region. and Sr.2Srl.Mn..464 S .. It appears that both compounds are biphasic.O.Mn...Nd..NdMn.__.2-100K.. Battle et al.... The closely related La. and neither are bulk ferromagnets.46-48 These compounds exhibit colossaI magnetoresistance of more than lo4%at 14T. which the authors interpret as casting doubt on the involvement o double exchange.. over a wide range of temperatures above the ferromagnetic Curie temperature of 124 K.. 5. and Sr._. which could be interpreted as evidence of the competing ferromagnetic and an tiferromagne tic interactions that are in heren t to the double exchange mechanism. show a difference between the field cooled and zero field cooled susceptibility.O..__...~9Ndl.O. These results are illustrated in Fig. 5 Colossal magnetoresistance in | doi:10. T. have made a detailed study of Sr...Mn.. is a ferromagnetic metal below 215K and shows large resistivity and magnetoresistance (60%) over a wide temperature range below the Curie point.45 There is a peak in the resistivity at 100K..

and on the three-dimensional pyrochlore lattice. + . KCr.(SO. which adopt the cubic pyrochlore s t r ~ c t u r e . has for several years been considered to approximate to a kagome lattice antiferromagnetic. and chromium jarosite.Ga. most interest currently centres on those systems. and showed a surface coverage of Fe3’ on the kagome lattice of97% in the best samples. or. In these materials.. it is probably fair to say that progress in understanding this interesting material is rather slow owing to the compiexity of its structure.with the magnetoplumbite structure. __O 19.. In zero magnetic field these systems d o not order even at temperatures well below the Curie-Weiss constant (which is a measure of the near-neighbour exchange). Despite a huge Curie-Weiss constant of .Magnetism View Online 465 parameters. is its apparent spin glass transition at T = 3.. -x019. It may sound surprising that entropy can favour ordered arrangements in this way. 6. have been carefully investigated by the muon spin rotation techn i q ~ eThe Curie-Weiss constants in these materials are 600 K and 67.). A particularly interesting representative of this series is hydronium jarosite. and long-range ordered ground states. In an effort to characterize more suitable model materials than SrCr.. with general formula AM3(OH)6(S0. The most important property of SrCr.).and SO.-.(SO.. and is thus comparable to | doi:10. a phenomenon referred to as ’order by disorder’.O. (x 1 SrCr. the M 3 ions occupy a kagome lattice in layers formed by the O H .(OH).Ga. The ordered ground states may be stabilized by weak terms in the spin Harniltonian.In. attention has turned to the jarosite series. but rather has an apparent spin glass freezing transition at 17.1039/IC9969300457 . and has been the subject of numerous studies.(SO. in which oniy near neighbours are strongly correlated.O.(OH). been synthesized by Harrison el solutions.Ga.. and the lack of chemically ordered single crystals. Competing with the spin liquid are spin glass.Iron jarosite. Lee et aL5I have characterized the spectrum of magnetic excitations in the low temperature phase and shown that this has more structure than that of a conventional spin glass. which as a consequence of frustration.Ga. ~ ~ Frustrated antiferrornagnets Frustrated antiferromagnets continue to provide the major themes in magnetic research.rsc. ~ ’ pressure behavthe iour of these materials is different to that of the p e r ~ v s k i t e s . -. an important mineral. However. . where A is a monopositive cation and M = Fe or Cr.ions. The relationship between these two lattices is illustrated in Fig. The full crystal structure of the synthetic material was determined by powder neutron diffraction.1200 K.. which has by direct hydrolysis in an autoclave of Fe..3 K. The prototypical examples are the Heisenberg model on the two-dimensional kagomC:lattice. more remarkably. have an infinite number of degenerate spin structures at zero temperature. the material does not adopt a long range ordered state down to at least l S K . -xO19 z 4 . but rather adopt a ‘spin liquid’ ground state. by thermal or quantum fluctuations. but in magnetism it is certainly a powerful ordering force.). in which the spins occupy the vertices of an infinite network of corner-linked triangles.. which bear more chemical similarity to hydroxides that to sulfates.Mn.. Another series of oxides showing giant magnetoresistance are TI. in which the spins occupy the vertices of an infinite network of cornerlinked tetrahedra. a temperature far below the Curie-Weiss temperature of 500K. The iron compound was observed to order magnetically at 55 K in agreement Downloaded by University of Calgary on 03 July 2012 Published on 01 January 1996 on http://pubs.). As described in last year’s report.2 K. KFe.5 K respect-~~ ively.

1039/IC9969300457 Fig.).rsc. but in the chromium compound spin fluctuations were found to persist even at T = 25 mK. Brurnwell View Online Downloaded by University of Calgary on 03 July 2012 Published on 01 January 1996 on http://pubs. showing a kagome plane (medium circles) decorated by lattice points above and below the plane (large and small circles respectively)..(SU. a temperature well below that at which history dependence of the bulk susceptibility sets in (T = 2 K). 2.(UH). Figure (b) represents a siice of cubic pyrochlore lattice perpendicular to (1. 6 Relationship between the two-dimensionaI kagome lattice (a) and the threedimensional pyrochiore lattice (b).466 S. with R = | doi:10. T. A susceptibility and nuclear magnetic resonance study of the jarosite RFe. Na and K5* reveafed successive phase transihas tions to long range order around 60 K. but is far more fluctuating. which have been ascribed to the effect of weak . to form a network of corner-linked tetrahedra with previous measurements. l). This result again lends support to the idea that the Iow-temperature phase of the kagornt: lattice antiferrornagnet bears a certain resemblance to that of a conventional spin glass.

in which the lanthanide ion is also magnetic.U. In Y. have investigated the pyrochIore oxides Ho.0. but the magnetism is compIicated by the possibility of the A site being Downloaded by University of Calgary on 03 July 2012 Published on 01 January 1996 on http://pubs. have reported susceptibility and neutron inelastic scattering measurements on the pyrochlore compound Tm2Ti207.Magnetism View Online 467 Ising-like anisotropy in the Heisen berg Hamiltonian. although a number of alternative systems are available. It is thus like a 're-entrant' spin glass. Zinkin et a!. by dc and ac susceptibility. only the Mn4+ sublattice with spin S = 3/2 is magnetic. This year Greedan et a! | doi:10. occurring. which is close to the Curie-Weiss constant of 8 K. However the crystal-field ground state of the Tm3+ ion has zero magnetization.B. there is no evidence that the Ni2+ ions lie on a kagome lattice. It exhibits a spin glass-like transition at Tg = 4. whilst the fluoride pyrochlores ABCF... preceeded by an apparent ferromagnetic transition at 17 K. These include the RCuO. The Ho and Yb homologues.O.1039/IC9969300457 .) and in interrnetallics with the C15 structure (e-g. heat capacity and neutron diffraction. the B sites occupy a pyrochIore lattice. Y. Jarosite-type materials currently offer the best prospects for future experimental study of the kagomk lattice antiferromagnet.56 Although an imaginative chemical approach to the problem of preparing kagome lattice magnets. leading to a non-magnetic ground state in the As mentioned above.Mn. has been studied by nun-linear susceptibility measurementss9 and the spin dynamics of Y.6Ti0L407and Tb. suggesting IittIe relationship with the kagomk lattice antiferrornagnets discussed above. The spin glass transition in the oxide pyrochlores YZMo. The compound is nevertheless interesting on its own right.58 In these materials both the Ianthanide and Mn4+ ions occupy interpenetrating pyrochlore lattices..Mn.O.Mo20.rsc. This is contrary to the received wisdom that a spin glass requires both frustration and disorder.0. and CsNiCrF. the B-sublattice of the spinels A3. The ferromagnetic transition is at about 40 K in both cases.). the kagome lattice. which have been the subject of a theoretical study this year. displays conventional spin glass behaviour below 7 K.B. and the predominant coupling is ferromagnetic. A striking generality is that the oxide pyrochlores A..U. have reviewed experimental and theoretical work on these systems.5K. delafossite-type oxides. various fluorides (e.O..Mn... are chemicaIly ordered but thought to form conventional spin glasses.O.55 and fluormica days intercalated with magnetic Ni2 ' ions. but with a large density of states for magnetic excitations near zero energy.. display similar behaviour.U.. and 23 K for Yb.Mo. and it was found that the crystal-field interaction dominates any superexchange between the Tm ions. but at a higher temperature.Mn.. The pyrochlore lattice is much more common in nature than the kagome Iattice.Mn. and Yb. FeF. while the fluoride pyrochlores have mainly been studied in Europe. Y 2Mn2U. Harris and Zinkin5. for example in the pyrochlore oxides A.g. Work on the oxide pyrochlores has been pioneered by Greedan and co-workers in Canada. in the which only the rare earth ion Tm3+ may be magnetic.O.Mn. The pyrochlore lattice antiferrornagnet has received if anything more attention than its two-dimensional counterpart. rather than a partially filled triangular lattice. have been investigated by muon spin In general the results show that the low temperature state of these magnets is like a conventional spin glass.O. are chemicalIy disordered yet d o not. and compared the results with those of the previously studied Y. but the divergence of the field cooled and zero field cooied susceptibility occurs at about 33 K for Ho.

but uncorrelated over long timescales.g. which are technologically important magnetic materials. was observed to coexist with the long range order below TNThis study may provide's link between pure research on the pyrochlores and appIied research on the spinel | doi:10. the short range magnetic order observed at temperatures as high as 10 T. have long been of interest in connection with unusual modes of ordering.66 Another important class of frustrated antiferromagnet is the triangular lattice antiferrornagnet (Fig. Most intriguingly. The stacked triangular lattice is well-represented by the ABX.~~ It was found that the spins on individual tetrahedra were strongly correlated as a spin singlet over short tirnescales. unconventional phase transitions and critical exponents.rsc.97S~0.468 S. BramwelI View Online magnetic. The previous five years' reports by Harrison and co-authors should be referred to for a detailed overview of recent work in these systems. The spinel was found to exhibit magnetic order at TN = 10SK. the stacked triangular tattice unusually Iow temperature scale for magnetic ordering in a spinel. 7). and a high resolution powder diffraction study pubIished this year shows that Na. In ZnFe. are LiNiO.).. CsMnBr.'~ The samples were prepared by ceramic techniques.O. which the Mn in ions occupy a pyrochlore lattice. but there are relativeiy few reaIizations of essentidly two-dimensionaI systems. involving slow cooling from 1500OK. In particular the onIy known examples of the interesting S = 1/2 triangular lattice antiferromagnet. and NaTiO. and the possibility of formation of a Pauling-Anderson resonating valence bond (RVB) solid. However the latter is a poor model compound. T. has been studied by inelastic neutr~n-scattering. with negligible inversion. has been the subject of a thorough investigation. using neutron diffraction. the Zn ions are nonmagnetic and the Fe3' ions with spin 5/2 occupy the pyrochlore lattice. and its three-dimensional relative. The intermetallic C15 Laves phase compound Y0. and 57Fe Mossbauer ~pectroscopy.~ couplings in C15 and spinel structures. Further reports of frustrated magnetism in spinel oxides are described in Section 3. This. making this compound closely analogous to the p yrochlores.TiO. hexagonal perovskite type halides (e.03Mn2.U. m u m spin rotation and relaxation.. as we11 as by the well-known inversion properties of spinels. ZnFe. which according to Anderson is a candidate for RVB behaviour. has been d e s ~ r i b e dand~Plumier has calculated magnetic structures as a function of exchange . A theoretical study of the effect of lattice distortion on the spin structure of YMn. 7 Regular triangular lattice with all magnetic bonds equal .1039/IC9969300457 Fig. (x E 1) has previously N Downloaded by University of Calgary on 03 July 2012 Published on 01 January 1996 on http://pubs.

it will be interesting t o compare the behaviour of KFe(SO.). and is a realization of the quantum row model. 8.). when subject to a transverse magnetic field. in which the spin value can be varied from S = 5/2 to S = 1/2. The structure type is such that magnetic ions (e. It is therefore always of interest when new effects are discovered. have extended work on the yavapaiite compounds to the anaIogous molybdates.67 A new series of essentially two-dimensional triangular lattice antiferrornagnets has been identified. The susceptibiIity us. and KTi(S0J2 which both have isosceles triangular lattices. as described below.2K. temperature for these two compounds are plotted in terms of reduced units in Fig. and can be thought of as a realization of the so-called ‘row model’. in which an electrical current. with horizontal bonds (double lines) of different strength to other bonds (single lines) unsuspected multiple-phase behaviour.. reflecting the relief of frustration which results from the orthorhombic distortion.1039/IC9969300457 Fig. as a model S = 1/2 material. described in Fig.). Inarni et a!. develops a component perpendicular to both the current direction nd the field.). Bramwell et reported a susceptibility study of RbFe(SO.~* Another frustrated triangular lattice system is 3He adsorbed on graphite. KTi SO.rsc.). which casts doubt on the validity of Na. They are an extensive series of compounds related to the mineral yavapaiite. as well as being of practical use in the optical industry. New magneto-optic effects Magneto-optical effects provide some of the most sensitive methods of investigating magnetic materials.). and KFe(SO. and CSF~(MOO. has S = €/2. KFe(SO.. 8 The ‘row’ model for frustrated triangular lattice antiferrornagnets. Zhitomirsky69 has published an analysis of the phase diagram of the classical stacked row modei as a function of the various magnetic couplings involved. and its relatives with these predictions.. 9.). with a weak cusp in the magnetic susceptibility at T = 4.TiO.. KFe(SO.Fe3*) occupy a regular or very slightly distorted triangular lattice in we11 separated layers. which was made for the first time. also with S = 5/2.g. appears to be a good example of an S = 5/2 two-dimensional Heisenberg lattice antiferrornagnet. and have published a high field magnetization study of CsFe(SO. Rikken and van Tiggelen” reported the observation of a new magneto-optic effect which they had previously predicted theoretically. It is to some extent analogous to the Hall effect. RbFe(SO.). which has an equilateral triangular | doi:10. In a non-scatter- .Magnetism View Online 469 Downloaded by University of Calgary on 03 July 2012 Published on 01 January 1996 on http://pubs.. has a more rounded susceptibility curve.).

probably as a result of the difficulty in making magnetic measurements on such systems. (lower curve).). The authors show that in-plane antiferromagnetic coupling.1 5 Fig. powder suspended in glycerol.5 times more than the previous record rotation of 14" and it is the absolute maximum observable rotation in a single reflection. The former approximates to the model in Fig. The latter order magnetically at about 15 K. but Pittini et a!. 7. Such 'beam walk off can be caused by absorption.). In recent years magnetochemists have shown renewed interest in such systems. Mn(0. Normally the effect is rather small. the so-called Kerr effect. 3 x 0. have shown that a crystal of CeSb at 1. and Rikken and vanTiggelen have now shown that scattering can have the same effect.5 K and in a field of 5 T has a giant Kerr effect of90".. but the resonance signal . the latter to Fig.8H. This is 6.470 S.1039/IC9969300457 03 .25 02 .U. This year sees an electron paramagnetic resonance study by Seip et on a monolayer Langmuir-Biodgett film of manganese octadecylphosphonate. reduced temperature for RbFe(SO. 9 Reduced susceptibility us. T. The experiments were performed using fine (2 pm) CeF. (upper curve) and KFe(SO. typically only a few degrees. non-absorbing medium there is no analogous effect on a flux of photons. The authors suggest that the effect is caused by the proximity of the band edge to an optical transition involving the paramagnetic f electron of | doi:10. 8 ing.)-H. which has a different refractive index.Brumwell View Online Downloaded by University of Calgary on 03 July 2012 Published on 01 January 1996 on http://pubs.8 K.2. is similar to that observed in bulk samples of manganese octadecylphosphonate. which arises from spin-dependent transitions. 0.rsc. The effect observed may be compared to the well-known Faraday effect in which a magnetic field applied longitudinally to a sample causes rotation of the plane of polarization. A perhaps more dramatic magneto-optic effect was discovered by Pittini et following on from earlier work by Reiem et When light is reflected from the surface of a ferromagnet its polarization rotates. J = . Langmuir-Biodgett films Following the pioneering work of P ~ r n e r a n t z ' ~ subject of magnetic Langthe muir-Blodgett films lay dormant for several years.

Nuclear magnetic ordering has been observed in AuIn. Gross et have described a SQUID ac susceptometer which has been tested by measuring the nuclear susceptibility of HoVO. This year Schulz et aLS3 report exact diagonalization of clusters of up to 36 spins of the Heisenberg antiferromagnet on the square lattice with competing antiferromagnetic ( J I )and ferromagnetic (JJ bonds. to probe this effect in the film. but quantum fluctuations lift this degeneracy leading to phase separated ground states. They find that for 0. at 35 pK. Salem and GoodingS6 have determined the ground state of such a system in both the classical and quantum cases. Downloaded by University of Calgary on 03 July 2012 Published on 01 January 1996 on http://pubs. Albrech t and MilaS4 have investigated the transition between valence bond order and magnetic order in a two-dimensionaI frustrated Heisenberg modeI.34 < J J J .78Other nuclear ordering phenomena reported this year include hexagonal dose packed solid 3He which is ordered ferromagnetically at 0.Magnet ism View Online 471 was too weak. while for the kagome lattice they d o not. Ando et ~ 2 1 ." In 3He absorbed on graphite three partjde exchange Ieads to ferromagnetic coupling and two particle exchange to antiferromagnetic coupling: the result is a two-dimensional frustrated Heisenberg magnet with a triangular lattice. Deaven and R o k h ~ a r have used variational methods to investigate the ground states of the *~ quantum spin S = 1/2 magnet on various two-dimensional lattices. the role of nuclear spins in bulk magnetism is usually ignored.rsc. Co and Ni. advances in instrumentation have in recent years allowed physicists to observe nuclear magnetism. The results have been reviewed by Godfrin and Rapp. In this materia1 the nuclear paramagnetism of Ho is enhanced by hyperfine coupling to the electronic spin | doi:10. In the classical case there are an infinite number of degenerate arrangements of the ferromagnetic bonds. A problem of direct relevance to cuprate superconductors is the annealed positions adopted by ferromagnetic bonds when doped into a two-dimensional antiferromagnet. ' ~ reported the formation of Langmuir-Blodgett films of stearates of Mn. NevertheIess. The ferromagnetic order-disorder transition in the classical Heisenberg model in a . This is acceptable because the magnitude of the nuclear contribution to the paramagnetic susceptibility is usually only about l o A 6that of the electronic susceptibility. The Ni film has ferromagnetic interactions. in the range 15 mK-130mK. honeycomb and triangular lattice they find evidence of order. For the square.1039/IC9969300457 Nuclear magnets Although nuclear magnetism piays a decisive role in chemistry uia nucIear magnetic resonance. and the temperature scale for ordering of the nuclear moments is of the order of mK or even pK. and has been shown to affect the superconductivity of the sample. Fe. below 17 K. such as stripes of ferromagnetic bonds.** Theoretical work A small selection of theoretical studies that are of relevance to magnetic materials are listed here.80 and may be compared to the behaviour of other truly two-dimensional systems such as Langmuir-Blodgett films74and ultrathin metallic films. The question of quantum disordered ground states in low dimensional frustrated magnets has been of interest to theorists for a number of years.6mK.78 The nuclear magnetism of 3He has been exploited as a method of making truly twodimensional magnets.68 fhere is a region of no magnetic order. < 0.

The question then arises as to why isostructural La. and all three critical exponents have been calculated in 8 arbitrary dimension for the first time. has the value 0. orbitals gives rise to ferromagnetism by enforcing orthogona1 overlap. by removing half the K ions and shifting the layers relative to one another.Both spin waves and central peak are found below the Koster~~ Iitz-Thouless transition temperature.89 has been investigated n u m e r i ~ a l i y .95 with the main result that increasing the external pressure to the order of G P a has a similar effect to decreasing the size of the A ion.1039/IC9969300457 and it is claimed that the critical exponents differ by a small fluid has been but significant amount from the ones for the lattice Heisenberg model. which order at 5. relevant to Co.CuF. to monochic NaMnF.NiF. Rb. which was interpreted in terms of a change from antiferrodistortive to ferrodistortive orbital order. a canted antiferrornagnet which orders at 13.g.rsc.02. K. has ferrodistortive orbital ordering and concomitant antiferromagnetism? Ishizuka et have shed light on this question by characterizing the magnetism of K.CuF.9 K.0K.CuF. This year Moron et al.Zn. at pressures of up to 13GPa. but have found that in this case the ferromagnetic exchange increases with increasing pressure.2 K and at 3.. -xF2..-type crystal structure are classic quasi two-dimensional magnetic model materials. ~ ' 3 Ionic. Thus there is a gradual crossover in magnetic behaviour between tetragonal CsMnF.. Brarnwell View Online Downloaded by University of Calgary on 03 July 2012 Published on 01 January 1996 on http://pubs.472 S. a collinear ferromagnet which orders at 18.have recently demonstrated that the series AMnF. = 6. They have observed a pressure induced change from ferromagnetism to antiferromagnetism at 8-9 GPa. T. layers which have a significant effect on the magnetism.. is a prototypical two-dimensional easy-plane ionic ferromagnet. The spin dynamics of the classical two-dimensional XY model. Cs) has a particularly rich magneto-structural hemi is try. the parent compound of the high temperature superconductors. Moron et a / .org | doi:10. in agreement with e ~ p e r i m e n t .25 K. The distortion associated with the orbital ordering can be thought of as a cooperative Jahn-Teller effect. The isolated A ions induce small structural distortions in the MnF. Ferromagnetic exchange arising from a cooperative Jahn-Teller distortion also occurs in related cornpounds with the Jahn Teller ions Cr2' and Mn3 *.. The magnetic ions (e.(p-cyan~anilinium)~]under hydrostatic pressure. (A = Na.'^ The structure type can be thought of as derived from K2NiF. covalent and metallic materials Halides Halides with the layered perovskite K." In three dimensions the exponent . which is of relevance to many ul trathin films'' and layered magnets. Sekine et aLg3have studied the magnetism of the related compound [CuCl. of which a well known exampIe is Rb. The random field Ising model.7 K respectively. has been investigated by reaI space renorrndization group techniques. Ni2+) occupy a square Iattice in well-separated Iayers formed by the haIide ions.. The K and Rb compounds are respectively a monoclinic canted antiferrornagnet and an orthorhombiccollinear antiferrornagnet.CuO. K. but is also of interest as an example of a compound in which a cooperative antiferrodistortive ordering of the partly filled Cu e. the Cu2 moments with S = 1/2 order ferromagnetically below T. report a pressure study of the crystal structures of the series. in that it + . In K.CrCI. presumably because of the shrinkage of Cu-C1-Cu exchange pathway.

This year Petrenko et af. The anisotropy of their magnetization at high magnetic fields has been ascribed to quantum effects. forms a different crystaI structure with CuZ+spin chains running parallel to the orthorhombic b-axis. = 0.62 K. Oxides As well as for their magnetoresistance described in Section 2..1039/IC9969300457 . Amow and Greedan lo' have investigated the structural and magnetic properties of the orthorhombic (almost tetragonal) perovskite-type phases Nd. CsCoX. are so-called 'singlet ground state' systems. oxides with the perovskite structure continue to be of interest for other reasons.6.TiO.99have reported neutron scattering measurements to reveal an unusual effect in a seemingly perfect crystal of KNiCl.CuCl.Fe. They might therefore be regarded as either one-dimensional or as triangular lattice magnets. are nearly Heisenberg systems with weak king anisotropy.0.CuF. with a temperature-independent ordering wavevector (0.3 K is cycloidal with the spins rotating in a plane that contains the b-axis." have shown that the anisotropy occurs at a cIassical level provided thermaI fluctuations are accounted for.x C ~ x 0 3 -which were prepared by pressure treatment and high temperature g. such that the inter chain interactions in the ab plane are frustrated. = 12. has the complication of small structural distortions. arising from structural phase transitions. Cs."' have investigated the magnetic properties of the cubic perovskite solid solutions SrFe.472. The hexagonal perovskite halides AMX.Cl.. and CsNiC1. is an antiferrornagnet with a Niel temperature of 134K. Kawasaki et a!.rsc. (A = Cs. With x = 0. 0.1.'O0 have solved the magnetic structure of this compound using elastic neutron scattering. KNiC1. CsMnI. the Cu2' spins ( S = 1/2) form an incommensurate structure. M = transition metal. (mentioned above). it would seem that the phase Sr. ~ and the results interpreted '~ in terms of a crossover from king-Iike to XY-like anisotropy with substitution of Fe2 ions.At x % 0. The magnetic phase diagram of the mixed crystals CsNi. The proposed magnetic structure at 0. .Magnetism View Online 473 induces a series of distortions from tetragonal to orthorhombic to monoclinic. with x = 0. Coldea el a1. while CsFeX. and arises as a result of the frustrated inter-chain interactions. 0). is responsible for the ferromagnetism. Rb) are | doi:10.FeCoO. Br) are Ising-like. These phases contain Fe and Co in the rather unusual oxidation state of +4. Visser et aLg6 have described pressureinduced changes in the magnetic ordering of AFeX. It segregates into two phases with different lattice distortions in the basal ab plane at temperatures below T z 270 K. The crystaI structure consists of linear chains of magnetic M ions stacked in a triangular array. which reaches a maximum of 240 K at x = 0.1 a change occurs to a ferromagneticstate with a high Curie temperature. . although of the same stoichiometry as R.6 K. depending on the phenomenon being investigated. -. These two phases have different magnetic structures with T. the Ti ions have spin S = 1/2 and the Nd3+ ions have + Downloaded by University of Calgary on 03 July 2012 Published on 01 January 1996 on http://pubs. X = halide) form another classic series of model magnets. It would be of evident interest to study the magnetism of the pressure-induced phases. but Santini et al. as the ground term of Fe2 ' in the absence of an applied field has M . Br). The compounds AMnBr. have been investigated by Takeuchi et ~ 2 1 . (X = C1. (A = alkah metal. oxidation of oxygen deficient samples prepared at ambient pressure.5 and 0. (X = CI.5 K and 8. SrFeO.. They find that below the ordering temperature TN= 0.

with the neodymium ions ordering magnetically below 3 K.-based phases.1 no antiferromagnetic transition was found above 4K. as previously discussed by Goodenough and N g ~ y e n .which establishes a remarkable coexistence of two-dimensional magnetic and charge order below 50 K. = 37. is a quasi two-dimensiona1 antiferrornagnet with a Neel temperature of 325 K..03. The primary effect of hole doping in La.'" The Pr and Gd compounds are found to be non-superconducting down to 1.Cu.~.25 antiferromagnetism is restored. I .O.05 samples respectively.CuO. with the K.Sr..rsc. ' although short range order of the ~~ Tb3 moments is observed at low temperature.8Cu04. -.Ba. The sensitivity of superconductivity to lanthanide substitution is also well known in the '123' type superconductors LnBa. For x > 0.CuO. La. Gd) in which the Y cornpound is a superconductor with a transition at 13 K. Substitution of La in La.Nd. order antiferromagnetically at the relatively high temperature of 17 K.CuU. However for the phase with x = 0. by isovalent ions does not have a strong effect on the magnetic or electronic properties.-. and low temperature neutron diffraction on these samples indicated that both the Nd and Ti sublattices were ordered. cuprate oxides with the layered perovskite f structure continue to command a great deal o interest.-..+. which lends support to this picture. also hole | doi:10.CuO..~.Cu. increasing substitution of Ti decreases the ordering temperature. until at x = 0. Thus the phase La.. Birgeneau et al.9 and x = 1.NiF..Cu. of -9OK."' Substitution of La for Nd in otherwise superconducting lanthanum cuprate compositions causes an anomalous suppression of the superconductivity.Cu04 behaves as a spin glass.. but while the Gd Downloaded by University of Calgary on 03 July 2012 Published on 01 January 1996 on http://pubs. . leads to hole doping with well known and extraordinary consequences.0 phases display negative magnetization. As in the case of Nd. and the phase La. The x = 0.474 S. In particular the compound YJ3a. -xTiO. have reviewed their extensive studies of the static and dynamic magnetic fluctuations in La. -xV. T. and LaVO.CuO. BramwetI View Online J = 9/2. pIanes of La. but it is interesting to compare the behaviour of the related series LnSr.Pr. This section will concentrate on purely magnetic problems. The dopant-induced holes collect in domain walls which separate antiferromagnetic antiphase domains.. report a susceptibility study of La. are antiferromagnetic insulators with Neel temperatures of 148K and 140K respectively.... while the homologous compounds of the other lanthanides only order at temperatures below 2. Thus La1.reported this year.~. Other evidence of the anomalous nature of Pr comes from the fact that the Pr moments in PrBa.Cu. as a superconductor with T. Tranquada et al.O.5 K. C U U .2Tb0. has a similar magnetic structure to L ~ . . ' ~ ~ Ten years after the discovery of 'High-T.O.CuO.~. is nonsuperconducting. but Y.Sr. has a T. The end members LaTiO.1039/IC9969300457 -. Pr. (Ln = lanthanide).3 K.'.'" Zakharov et a!. However onIy Pr among the lanthanides has this effect.1 a paramagnetic and poorly metallic phase is formed.NbO.Sro~. Antiferromagnetic ordering of the Ti3+sublattice was observed at TN= 90 K and 75 K for the x = 0 and x = 0.Cu30. + d (Ln = Y.8 K.. There is no fully accepted explanation of this anornaIy. Eylem et have investigated the isostructural series LaTi. Between 340 K and 820 K the correlation length behaves exactly according to the predictions of the two-dimensionaI quantum non-iinear sigma mode1 (a continuum approximation to the Heisenberg model) in the renormalized classicai regime.l o g have described a neutron scattering study of the charge and spin order in the CuO. structure. is believed to be the formation of ferromagnetic clusters or ferrons. The substitution of aliovalent ions on the other hand..12Cu04.

Nowadays.Ni.' 2 1 Mg. The x = 0 composition.Cu. suggests a spin Iiquid.2. +a.Ti...5 for the Mn ion.. Nd. are described in Section 2.Mn.CuO. It is a candidate for a non-magnetic 'spin liquid' ground state. The Ni3* moments have a moment of 0. has a formal oxidation state of + 3.-a'23 have also been investigated. by susceptibility measurements.. +.. Another chain-like cuprate Ca. x > 1)'17 and the compound CeSr. a value which is much less than the per spin only value of | doi:10.08C1. competing magnetic exchange and mixed valency all playing a role. AbdeIgadir et a!.O.5 pLe atom. Lu).]0.-.CI and Ca4Gd. superconductors contain magnetic ions with spin S = 1/2 means that any related magnetic oxides with S = 1/2 are immediately of interest. Matsumoto et have reported that although the susceptibility of LaCuO.Cr. have Iong been popuIar subjects of research.CuO.Fe.. apparently by introducing excess oxygen to form Ca.19 K. James and Attfield have described several new Ni3+ oxides with S = 1/2. LiMn.Cu.'16 the solid solutions Ln. a temperature far above the ordering temperature 0.. with Curie-Weiss temperatures of .1039/IC9969300457 .l2 o CoFe. spinel structure.367 K for the tetragonal form and .. Other cuprates of interest include the 'spin ladder' type compound LaCuU. However it is interesting to note that the doping of 5% holes by substituting La for Sr suppresses this transition. . The structure and frustrated magnetism of the mixed spinels Cu ..6 K. Staub and Ritter'" have investigated Ho13azCu. The compounds are normal spinels with Li on the A-sites and Mn on the €3-sites of the spine1 structure. Sm. has antiferromagnetic interchain couphng.O.273 K for the cubic form. a1though results on the site-ordered frustrated antiferromagnetic ZnFe.'18 The latter is a metallic compound adopting the K2NiF. although these are all paramagnetic down to 6 K.TiO. Oxides with the 'other' majority ternary oxide structure type. The spin ladder model was described in the 1994 Report. most attention is focused on spinei solid solutions. The dominant exchange coupling is antiferromagnetic.CuU.Li.Ba. Tm. the AB. Other phases which illustrate the sensitivity of electronic properties to lanthanide substitution include the series Ln. (M = Sc.'l' With Ln = G d or Eu the behaviour is ferromagnetic below about 25 K. while with Ln = Sm there is a spin glass transition at about 15 K. In. by neutron scattering and have observed two-dimensional short range ordering of the Ho3+ moments even at 1.. described above.2K. the P r moments remain magnetically disordered at this temperature.0. and exists in both cubic and tetragonal forms. SrxNi4kd(Ln = La. Gd.xAIxTiO.l 1 have reported that sintering in oxygen produces a remarkable transition to room temperature ferromagnetisrn.O. 63Cu NMR measurements indicate antiferromagnetic ordering at 110 K.Zn.. type structure with Ce and Sr disordered over the K sites.rsc...l LiCr .73. strongly antiferromagnetically coupled spin S = 1/2 chains. related oxides are also a popular field of research.Magnetism View Online 475 moments order at 2.01. The magnetic properties of the lanthanide ions themselves in high-T. The magnetostructural properties of the spineIs are very complex with cation ordering. The fact that the high-T..O. The latter series is particularly interesting.. and consists of parallel. Yb.04.NiO.04122and Li[Mn2_. one might tentativeIy suggest a similarity to oxygen excessive La. Quasi two-dimensional ordering of Gd moments below 4 K is observed in CaCdCu0. There is a spin freezing transition at 60 K for the tetragonal from and 55 K Downloaded by University of Calgary on 03 July 2012 Published on 01 January 1996 on http://pubs. These include the series MSr.

U. and the Sm compound has negiigibIe magnetic coupling.BaZnO. The intralayer interactions are ferromagnetic. but have been rather neglected in the past..0 K in the analogous Cu compound Gd. Metal hydroxide layers are a common structural motif in later transition metal hydroxides and hydroxy-salts. The compounds [Cu. which is identicai to the pyrochIore lattice described in Section 2. The Ti and V homologue of LiMn.. The Eu compound has a singlet ground state. . The Dy and Ho compounds have quite large antiferromagnetic coupIing for rare earth compounds. indicative of V4+. show a decrease in superconducting transition temperature with increasing x. perhaps because of difficulty in obtaining good quality crystalline samples.476 S. for example tCo.11 K respectiveIy. In the three-dimensional ordered magnetic phase. €30 and Gd mainly by susceptibility measurements.O.BaCuO. At x=O. Goya et have investigated the magnetic properties of the series of orthorhombic ternary rare earth oxides tn.(C. I Downloaded by University of Calgary on 03 July 2012 Published on 01 January 1996 on http://pubs. LiTi20. These localized moments are believed to be responsible for the destruction of superconductivity.~. and the spin freezing temperature is also 10 K. Sm.4K. have been the subject of an investigation by Kirchambare er These compounds are again both norma1 spinels.1039/IC9969300457 af-1259126 Hydroxides and other hydroxy-salts Hydroxides often have very interesting magnetic properties..Re.05. 8 and 9 appear to have an antiferromagnetic intralayer interaction.(U~). Among other rare earth oxides.U has a Curie temperature of 8 K. the Curie-Weiss temperature is + 10K. with Ln = Sm. Thus in Co(OH). with a Curie-Weiss temperature of .(C. the Iayers can be forced up to 25A apart by exchange of (OH) by organic or inorganic anions. while LiV.15 and . The V ions are found to have a moment of 1. reflecting the frustration of the 3-site spinel lattice. The compositions LiTi rV.. however. a new ternary samarium rhenium oxide.7ps. is a superconductor with a transition temperature of 13 K. which also has a large Curie-Weiss temperature of 15-9K. The absence of magnetic ordering in these materials down to 1. shows an antiferromagnetic transition at 2. undoubtedly arising from structural changes with the layer on intercalation.H. and form the full range of solid solutions. Gd. this is raised to 12.)C02] with n = 0 and 1 similarly have ferromagnetic intralayer magnetic exchange.rsc. Dy. apparently with localized magnetic moments. indicating ferromagnetic coupling. Eu. only very smaIl magnetic coupling between the Re ions.H. and altering the interlayer separation can be used as the basis for chemical ‘tuning’ of the magnetic properties. with Curie-Weiss temperatures .1. The substitution of Li on to the B-sites increases the formal oxidation state of manganese and causes a progressive decrease of both the magnitude of the Curie-Weiss temperature and the spin freezing | doi:10. which corresponds to an oxidation state of +4.and the superconductivity is destroyed at x = 0. There is.+ .(OH).O.127The Re ions appear to be in the + 5 oxidation state with S = I and the Sm ions show a very large temperature independent paramagnetism.BaZnO. is metallic.129 However their homologues with n = 7.2H. T.3 K. and show metamagnetic behaviour at 20 K... the ferromagnetic planes are stacked an tiferromagneticatly for ma11 interlayer spacing and ferromagneticaly for large interlayer spacing.O.8K was interpreted in terms of frustrated interactions. has been described. Bramweil View Online for the cubic form.)SU.33.

NO. 8.14) however show spin gIass behaviour below 10 K.O.7.).Magnet ism View Online 477 Downloaded by University of Calgary on 03 July 2012 Published on 01 January 1996 on http://pubs. I 3 * Salts of oxy-anions: phosphates. with a maximum in the susceptibility 11 K.9 K and + 6.).. with two Ferromagnetic intrachain interactions between neighbouring S = 1 spins of magnitude + 26.9 K .)]. separated by Sr2 ions. The magnetic critical exponents of FeCO.). perrhenates.CH. Such materials can be of interest magneticalIy as examples of quasi two-dimensional systems in which the magnetic coupling in the third dimension can be perturbed in a systematic way by intercalation.Mn.)]-H.H.Mn.Sb. Sb have been found to be quasi two-dimensional metals.O.5 K.. Fe. while ordering effects are not observed in the Pn layer until much tower temperature.I (x = 0. the Mn ions in the pnictide layer order antiferrornagnetically at 65K. Another Iayered material.. The magnetic behaviour is not strongly affected by intercahtion.). is also a layered compound with Ferromagnetic intralayer interaction. showing that the substitution of nitrate severely disrupts the magnetic long range order..NCH.l3O The series [Ni(OH). The Ni compound exhibits substantial coercivity (-0.O.(PO.135 The magnetic behaviour is similarty anisotropic.Pn.'-. despite a build up in two-dimensional | doi:10. In Sr.rsc.74. + 1NH2). Another nickel(I1) hydroxynitrate. with Pn = As. [Ni(OH)(NO. The Mn occupy a centred tetragonal lattice in the pnictide layer and a primitive one in the oxide layer.(P0.25T at l~~ 4.O is antiferromagnetic.64.As. The Nee1 temperatures are 4 K and 17 K respectively. they remain disordered until at least 4 K .0 with n = 3-7. The crystal structure of these compounds consists of alternating tetragonal iayers of MnOZ2.)] -H..O and its intercaIated derivatives [NiH(C. have Goni et d..and Mn.' 3 4 Pnictides and pnictide oxides The compounds CePdPn with Pn = As. The pyrosilicate BaCo.Mn. while in Sr.131 prepared the new layered compound [NiH(PO. tFe(OHXH. but semiconducting behaviour parallel to c.'32 homologues with different alkyl chain lengths have not been reported. contain chains of distorted tetrahedral COO.Si.5 K and 4. exhibiting metamagnetism below TN= 25. 340K As). but apparently antiferromagnetic behaviour paralIel to c. with CePdAs and CePdSb showing paramagnetic susceptibility perpendicular to c. The perrhenates [M(ReU.H.Pn. groups interlinked by Si.)].0. an antiferrornagnet ordering at 38 K. + .(P0.O. reflecting two-dimensionality: [NiH(C. has a weak ferromagnetic transition at about 30K.2 K).] (M = Ni.1039/IC9969300457 Ni(OH). with metallic conductivity perpendicular to the crystallographic c-axis. [NiH(PO.)]*H2U is aIso antiferromagnetic.)f*H. behaves as a double chain system. have been determined by time-of-flight neutron diffraction techniques and have been found to be in good agreement with those of the three-dimensional Ising model.8 K. +.NH.O.1.SNH. Co) again have a layered crystal structure. and order ferromagnetically at 12.136 have reported neutron diffraction results for the pnictide oxides Sr. Sb. Thus in both the Pn = As and P n = Sb cdmpounds the manganese ions in the oxide layer order antiferromagnetically at ambient temperature (300K Sb.H. silicates and carbonates Phosphates of the first row transition metals commonly adopt layered structure which can intercalate long chain alkylammonium cations.O. Brock et a!.7 K r e s p e c t i ~ e 1 y . -. with a maximum in the susceptibility at 12 K. The compound has a weak ferromagnetic transition at 21 K. however the symmetry of the structure is such that the layers are substantiaIly decoupled.

NbS2. At low temperatures it behaves like a semiconducting.4.52. and Th.B2C by resonant and non-reson'~~ ant X-ray ~ c a t t e r i n g . GdNi. and Th.Mo.).. The compounds show metallic behaviour. have determined the entropy change for this phase transition by specific heat measurements.'37 Wet1 known for their electronic and intercalation properties are the layered transition metal dichalcogenides of Groups IV.Se8 appears to have &~ a superconducting transition at 3 K.Se.C exhibits superconductivity below f 1 K and mag'~~ netic ordering below 1. Gadolinium has very large neutron absorption.and of GdNi. 0) planes of Tm moments. the expected magnetic entropy for S = 1/2 spins of V4+ ions. Ch = S.PS. Between these two temperatures the modulation wave vector increases with decreasing temperature. the magnetic transitions occur at slightly higher temperatures (15. . However the Curie-Weiss temperature changed from positive to negative at x = 0. Mn) similarly consist of van der Waals bonded layers which may intercalate a variety of species. which can be prepared by the metathesis reaction between FeCI. and there is a further magnetic transition at 13.S. is paramagnetic down to 2K. T. and there is no superconductivity down to 2 K.. which arise from the electron transfer from the A ion to the molybdenum chalcogenide host have reported the magnetic behaviour of UMo.C142led to increased activity in the fieid of intermetallic superconductors.19 < x < 0.478 S.C by neutron d i f f r a ~ t i o n . Zhang el ~ 1 .. Imai et al. The Chevrel phase type cornpounds M.5 K. I.139report a new intercalation compound Mn. of amorphous Fe. Se. type compounds (M = Ni. V and VI.. There is much interest in the magnetism of the members of the series LnNi. however at 70 K there is a transition to a metallic state. Miwa et reported the synthesis and magnetic properties of Mn. Te) are also well known for their remarkable physica1 properties. With Ln = Tm. orders magnetically at 19. Ho and Dy. U J .Mo.Mo.. has a hexagonal crystal structure consisting of chains of face-sharing VS. It is suggested that the modulated structure allows the coexistence of magnetism and | doi:10. ' ~ reported the magnetic properties '. 1. - Boron carbides The discovery in 1994 of superconductivity at 12 K in tetragonal YNi2B.4K respectively). but with Ln = Th and Gd. Er.. octahedra.B. on the other hand.Se. Qin et a!..B.. Thus while UMo. x 1.2'-bipy). superconductivity and magnetism coexist below typically 10K. with the magnitude of the moments sinusoidally modulated along the crystalline (1. one-dimensional antiferromagnet with spin S = 1/2. 0) direction. Among many other papers. Daoudi et U.rsc.5 K and 19. TmNi2B. the compound has a spin glass-like transition at about 6 K.(2.. which means that neutron investigations of G d salts require expensive isotopic substitution.C. MPS. clusters.(InTe.1039/IC9969300457 Chalcogenides and phosphidechalcogenides BaVS. this year sees magnetic structure determinations of TmNi.Ch. which is ferromagnetic below the Curie ternperature of 40 K.Mo. ~ ~ M Ois weakly ferromagnetic below 25 K.. with paramagnetic Mn2+. (M = metaI. .5 K.4 K with a n incommensurately modulated antiferromagnetic spin structure. The use of X-ray techniques in this magnetic structure determination is noteworthy. which illustrate the sensitivity of the electronic properties to the A ion. with 0.C (Ln = lanthanide) with magnetic Ln ions.. Bramwell View Online Downloaded by University of Calgary on 03 July 2012 Published on 01 January 1996 on http://pubs. and shown that is close to Rh2.S. and the Zintl phase K5(XnTe4)in water... the magnetic structure consists of aligned ferromagnetic(1.-.B.

_. (x = 0.Pdo...rsc. Plutonium is at the critical composition between the light actinides. with a Lorentzian line shape. and once again observed the two length scales. which have f itinerant 5f electrons.Ru. '"~ Frustration effects are as common in intermetallics as they are in ionic and covalent soIids.. quasicrystals. However the origin of the effect remains unclear. becomes a spin glass._. This agrees with the theoreticaI prediction of Srnirnov and Bratovsky.Magnetism View Online 479 Metallic elements and intermetallic compounds Although not of immediate interest to many chemists. The alloys CeFe. recent improvements in instrumenta1 resolution have reveaIed that the scattering is often described by two Lorentzian line shapes. -.1039/IC9969300457 <- .Pd. is a frustrated antiferromagnet and when alloyed with ferromagnetic Copt. Other metallic metamagnets include EuPdIn and E U A U I ~ which order at 13 K and 21 K respectively. aligned antiferromagnetically in zero field. Gehring et 0 1 . In are aligned ferromagnetically by the application of a field.08) show a rnetarnagnetic transition in which ferromagnetic sheets.Mn.23 predicted by Bramwell and Holdsworth8' (see last year's report). and the TbNiAl shows sinusoidal ~rdering.'^^ At a critical point one expects critical fluctuations on a11 length scales up to a 'cut-of. who considered AlMn liquids. Major improvements in nanotechnology in the last decade have meant that ultrathin metallic films of one to three monolayers thickness can be deposited on nonmagnetic metallic substrates. acquire a local moment of about 3pB in the liquid.2' The Mn atoms. intermetallic compounds display a huge wealth of magnetic phenomena. They conclude that 'the delocalization-localization transition of the 5f electrons along the actinide series starts within the plutonium phase diagram'. An exampIe of this is ferromagnetic Fe on the (1.0. of which a small selection are illustrated here. Dy. the correlation length In quasielastic neutron or X-ray scattering the criticai spin fluctuations give rise to a scattering function in reciprocal space.. a on the basis of band conclusion which was previously predicted by Antropov et structure calcuiations.. Ho) show successive ferromagnetic and antiferromagnetic transitions below 30 K. Micron thickness films of Ho have been used to probe the phenomenon of 'two length scales' observed in neutron and X-ray scattering experiment^.' 5 1 Hippert et have reported an interesting effect that occurs in the melting of Al..Ru. the width of which is equaI to l/& However.. ' ~ have measured the critical scattering at the 131 K magnetic phase transition in 1 pm Ho films. -. In order ~ to prove the possible involvement of surface effects.0. and the heavy actinides. the LnNiAl series (Ln = Tb. the second with a width about 1/10 that of the first.'45 There is a 24% votume expansion at the x-6 phase transition. which can possibly be explained in terms ofa different local environment. which the authors argue is indicative of electron localization.i47*'48 CeFe. Meotreymond and Foucnier have argued that that the high temperature 6-Pu phase has far more localisation than the low temperature x-Pu phase.' Shi et ~ 1 .org | doi:10.0) surface of W.207Mno. such as A1. which are diamagnetic in the solid state. have~ ' ~ made submicron ferromagnets in GaAs semiconductors by the ion implantation of Downloaded by University of Calgary on 03 July 2012 Published on 01 January 1996 on http://pubs.155 material appears to be an almost ideal realization of a twoThis dimensional XY magnet showing the finite size critical exponent fi = 37c2/128 = 0. the transition is accompanied by giant ( > 20%) magnetoresistance.. As a result of frustrated interactions.07.'~' FePt. which have localized 5 electrons.

'1 are room temperature ferromagnets with coercive fields of 100 Oe and 300 Oe respectively. The bulk behaves as a room-temperature ferromagnet.0. Another reported chemicai method to nanoparticulate magnets is the reduction of Fez' ions to Fe by KBH. the materials show ferromagnetic properties at room temperature.2propylenebis(oxamato)].162 A 1% substitution of Mn for Cu or Cd leads to a remnant magnetization when samples are field cooled through the three-dimensional Nee1 temperature of 4. with additional spin-glass-like transitions at about 10 K. Leslie-Pelecky et al.'57 have used this technique to make ultrafine Co particles stabiIized in a polymer matrix. is of interest as a three-dimensional ferromagnet. There is continued interest in developing pureIy organic ferromagnets. although only slightly.(TCNQ-') [R Cs' and N(CH.F.).I. Methods of a more chemical nature to nanoparticulate magnets include the reduction of a metal halide using organic solvents in the presence of | doi:10.. The main problem is not to find a ferromagnet.480 S.22 at x = 0.).As.1039/IC9969300457 MnZ+. Bramweli View Online Downloaded by University of Calgary on 03 July 2012 Published on 01 January 1996 on http://pubs.(solvent). -.NH. and has rather a large coercive field of about 6 kOe at 2 K.(pba)] [pbaOH = 2-hydroxy-I.12 K. three-dimensional systems The bimetallic complex.J order magnetically below about 2K. followed by annealing. crystal structure 1 . the positive r means that critical exponents will depend upon dilution. room-temperature molecular ferrornagnet is the amorphous [V(tetracyanoethene). T. [CoCu(OH)(H.107 K and a weak ferromagnetic transition at 34 K.164 A novel new molecular magnet is the suIfurnitrogen radical p-NC-C. and the saturation moments are onIy about 1/1000 that expected for full spin ordering.19 at x = 0&014 y = 1. A metal-containing. They are expected to show critical exponents of the universality class predicted by K a ~ a r n u r a ' ~which has a large positive specific heat exponent x. which precipitates GaMn ferromagnetic clusters.(CH.O).. Thus a report of interest is that by Ueda et the purely organic tetracyanoquinodimethane (TCNQ) charge-transfer salts R '(TCNQ). 16' show that the susceptibility exponent 7 does indeed depend OR x.~~~ 4 Coordination complexes and molecuIar compounds Framework structures. However the materials are not fully structurally characterized. Careful susceptibility measurements by DeFotis et al. ' According to the Harris criterion. It to increases from 7 = 1.rsc. the improved synthesis of which has been reviewed.165 The sensitivity of molecular magnetism to chemical substitution.159 dilute The ferromagnetic complexes [Fe.CN(C. An unusual effect has been observed in the linear chain antiferrornagnet [MnC1. in aqueous soIuti~n. but to find one with a reasonably high Curie who have found that temperature.H.040. which orders at 38 K.C~~S. which has a Curie-Weiss constant of .)-H.-CNSSN 1.

the Ni(maleonitriIe).O. an antiferromagnetic Curie-Weiss temperature was found which was much higher than this: .~~ structure of this charge transfer salt consists of The stacked planar metal Iigands separated by ammonium cations.1039/IC9969300457 2 I 3 and pressure effects has been demonstrated by several groups.).2. At 6.4. for the compound 2. which depends upon the metals M" and M1"and the nature of the A ion. but this is lowered to 0. and ascribed this large change to a switch from dominant metal-sulfur to dominant metal-metaI interactions with increasing pressure.}2.35 K under . and neighbouring layers are separated by the organic cations. Thus Togashi et al.]-H. Interestingly. The M" = Fe series behave as ferrimagnets with Curie temperatures between 30 K and 50 K. metamagnetic and ferromagnetic at low temperature.75 K. [MI' = Mn. ' ~ have character' ized an extensive series of cornpounds AM"Fe(C.] [Ni(male~nitrile). phosphonium.166 studied 165 organic radicals of the type 4-arylmethyleneamino-2.167*168 Different behaviour is observed for the compound [NH.O. The prototypical purely organic ferromagnet j3-nitrophenyl nitronylnitroxide has a Curie temperature of 0 6K under ambient pressure. anion is 4. In simple terms the ferrimagnetic behaviour can be thought of as arising from the imbalance in atomic magnetic moment between antiferromagnetically coupled Fe2 and Fe3'.). Mathonikre et ~ 2 . The metals are coordinated by oxaiate. Thus the charge-transfer salt Fe(C5(CH. and found that 52 compounds exhibited ferromagnetic coupling. A = alkyl. In these compounds the metal ions occupy alternate sites in a two-dimensionai honeycomb lattice.and aryl-ammonium. and arsonium ionsJ.rsc. probably as a result of a structural phase change.8 kbar the ferromagnetic order abruptly disappeared. but several exhibit an unusual crossover to negative magnetization at low temperature when cooled in a fieId of 10mT.24 K for the compound 3.TCNQ exists as three different structural phases which are respectively paramagnetic.5 K at ambient pressure to 7 K at 6 kbar. but the highest Curie-Weiss temperature among these was only 0."' 4 Layered structures. Coomber el found that the ferromagnetic Curie temperature increased from 4. and this can affect the magnetic | doi:10. Fe.I-yloxyls (and related compounds). two-dimensional systems The layered bimetallic oxalate complexes AM1iM11'(C204)3 = monovalent organic (A cation) show a wealth of interesting magnetic behaviour.Magnetism View Online 48 1 Downloaded by University of Calgary on 03 July 2012 Published on 01 January 1996 on http://pubs. Polymorphism is always a possibility with molecular compounds.'. a pressure of 7 kbar.6-tetramethylpiperidin. but the origin of the negative + .

The magnetic susceptibility of the semiconducting G a compound is well described by a model containing two antiferromagnetic spin dimers with couplings of 108 K and 212 K.Hg).0. only the even-spin chains have an energy gap to the first magnetic excited state. 7 Bhattacharjee et d. For example. Kurrnoo et MCl.H9)3Fe”Cr’”(C.5-dimethyi-~-thioxoverdazyi. but mainly with spin S = 1.). Lang e al.). Layered charge-transfer salts based on bis(ethy1enedithio)tetrathiofuIvalene (BEDT) are well known as ‘molecular metals’ and also show magnetic coupling with a quite high temperature scale.Fe”Fe”’(C.21 K. That of the Fe compound is modelled by a single antiferromagnetic dimer with coupling 45 K in addition to an ahnost paramagnetic term arising from the Fe3+ moments.‘~~ also a The is quasi two-dimensional metamagnet. and order is easily restored by minor perturbations&From a practical point of view this means that the only systems that actually show a marked reluctance to order magnetically are one-dimensional magnets that approximate the Heisenberg or XY model. The one-dimensional Heisenberg antiferromagnet also has the unusual property of the magnetic ground state depending strongly on spin value. and behave as low dimensional antiferromagnets. For x > 0. I n the M” = Mn series.482 S . which makes them particularly resistant to magnetization. Another series of honeycomb layered magnets are the azides M. with a broad susceptibility maximum at about 50K. although so far only antiferromagnetic coupling has been have investigated the compounds observed. and at that temperature no magnetization in fields of up to 1 T. The exchange coupling between the magnetic moments on the Fe and those on the organic layer is apparently negligible. one-dimensional systems From a theoretical point of view.68 K induced by inter-chain exchange of magnitude 0. An example is the organic radica1 3-(4-chIorophenyI) | doi:10. and also exhibits negative magnetization below the Nee1 temperature of 16 K. ’ ~compound has exchange coupIing of about 30K.Fe”Fe’~’.(bipyridinium) (M = Co” and Fe”).0~~~ a ferromagnetic transition at c ) ) . For 0 x < 1. while N(C4H. M r ~ C I ~ ( b i p y H ) . (M = Ga. has 14 K.Cr”l.rsc. T.(BEDT-TTF).(N. the transition temperature varies smoothly between these extremes. Several quasi one-dimensional Heisenberg ferromagnets have been reported. BrarnweIl View Online Downloaded by University of Calgary on 03 July 2012 Published on 01 January 1996 on http://pubs. Thus while in general the grounds state is a singlet. -= Chain structures. and a transition to an ordered state at 0. .and two-dimensional magnets are not expected to order magnetically. This so-called Haldane gap has been observed in several compounds. but no The ~ magnetic order at 30 mK.).but an increase in the magnetization characteristic of spin canting at lower temperatures.1039/IC9969300457 magnetization is not yet understood. Fe).177 The Iow ordering temperatures of ferromagnetic chains have not deterred workers from seeking chain-like molecuIar magnets. 7 8 have reported a magnetic r . both ions have spin S = 5/2. has a ferrimagnetic transition at 35 K.0-~alen)Mn(CN). These compounds exhibit rnetarnagnetic behaviour below 60 K and 40 K respecti~ely. which has ferromagnetic exchange coupling of about 6 K .’2 have investigated the series N(C. report evidence of the Hddane gap in a spin S = 2 chain.4 a spin glass-like transition is observed at a temperature just below the ferrimagnetic transition. However.”~ compound KMn(3-CH. one. the one-dimensional Ising model and the twodimensional Heisenberg and X Y models are all at their lower critical dimension.x( & 4 3 The compound N(C. This year Granroth el a!.

E. I O I . there have been a huge number of reports of dimers. f MS.4-triazolenitronylnitroxide. Yakhrni and I. Stamp.274. I996.938. Harrison and S. Cheetham and R. B. W.8. K.substituted for MOO. 1630. 21 S . which exhibits magnetic frustration. although the Curie-Weiss temperature is only about 9 K.87. E. Aharoni. Annu. 644. ]*4CH. 20 C. Rao. Annu. 1996. 125. Caneschi.N. M.383.92. Ser. 2 3 4 5 6 7 8 9 .382. ferromagnetic coupling can result. T.25.. 1996.OH.208. A.Magnetism View Online 483 Downloaded by University of Calgary on 03 July 2012 Published on 01 January 1996 on http://pubs. Prog. Grant.. R. Proy. Sfotr Phys. A . C.. J. Science. Cambridge. ACS Symp. Bohm et a/. 175. R. S.5 K. Goldman.381. ‘zero’ dimensional systems As well as being centre stage this year in terms of quantum mechanical tunnelling.A. It has formula [V.47. 1996.383. Harrison.3. 69. 1996. Rep Prog.D.]4H2O.477.Levy.91. Clarke. A 1993.rsc. 15 P. Muter.. K.273. Mahesh. M. Harvard University Press. Boca et a!. 880. 1996.149 (2016).431.21 I. and Applications.1996.1996.5 -di-tert-bu t yl-4-hydroxypheny1)porphinatoj manganese@r) t et racyanoethenide.39I. 10 R. Bland. The crossover between a low-temperature low spin state to a high-temperature high spin state occurs in the temperature range 9tr160K.Xacpa).38 (31. Nature (London). ‘introduction to the Theory ofFerromaynetisrn’. 1986. SOC. Chem. Adc. Gopalakrishnan.2. 1996. ~ ~ being antiferromagnetically coupled.. 12 Insight. A. Lerr.425.4H2O and the exchange coupling is about 10 K [Hacpa = N-( l-acetyl-2-propyridene)(2-pyridylmethyI)amineJ With CrO.CEt).614. A. G. A handful of examples will suffice. However in most cases the magnetic measurements stop at the characterization stage. Livingston. J. C . Castro et dl”have described a complex of V’I’ with a butterfly structure.’ report spin crossover behaviour in an Fe” complex. Chem.. Washington. Eng. Marer. K. Sol. 1994.90. Oxford.(bipy)2(C104)] and contains both ferromagnetic and antiferromagnetic interactions. vol. Srcr.bridge. Techniques.. 13 R. Cu2’ dimers are well known for . 1995.’ ..89. Appl. for which the authors claim ‘exceptionally strong’ magnetic interactions.’ . M. 1996. Murphy.A.. 1996. V. 1994. Cornia. R. I4 A. C. P. 1996. 160. Wills. Rex Appl. The Cu complex is [Cu(pCrO. 1996. 7 9 report a ferromagnetic Curie-Weiss constant of about 90 K and a Curie temperature of 15 K for the complex [meso-tetrakis( 3. C. 367. 1996. 2754.405.1996. Science.J. Edwards.1039/IC9969300457 characterization of the organic radical methy1-1. trimers.271.Rm.. Chem.Secr. Thooft and M .274. J. Annu Rep. I7 Symposium On Molecute-Based Magnetic Materials-Theory. I 5 1.there is antiferromagnetic exchange coupling of magnitude about . A. 1995. 19 P. Sci. B. 1996. Rosensweig. J. Wickenden. Chem. Science. 18 D. Osiander. ‘DriGiny Force: The Naturol Magic o Magners’.(0. 1990. Hellmans.Sect. Vandermark. Kistenmacher and D. A . 1 1 Prufiss. give the complex [Cu(p-MoO4)(acpa). 1992. Nature (London).0. Isolated | doi:10. 407. Rep. Gatteschi.2421. Nature (London). E.27. Nature (London).32. Phys.’. SessoIi and A. Chem. 1996. Eny. Chavan.4. Oxford University Press. New Sci. Givens.679. A. References 1 A.88. Norure (London). A . M . and so there is little purpose in listing them all here.9 ( I 81. Science.380. tris(pyridy1benzimidazole)iron(rI). Chudnovsky. 1991. R. but Oshio et ~ ~ 1havel shown that with a GO. Harrison and A. A. tetramers and so on.

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