Molecule-Based Magnetic Materials. Theory, Techniques, and Applications PDF
Preview Molecule-Based Magnetic Materials. Theory, Techniques, and Applications
A CS S Y M P O S I UM SERIES 644 Molecule-Based Magnetic Materials Theory, Techniques, and Applications g 01 acs.or4.fw0 bs.64 u0 p://p996- Mark M. Turnbull, EDITOR October 8, 2012 | htt6 | doi: 10.1021/bk-1 ToUynoivnerasCritliya rSokuf gOUisnmaikvoear tsPoitr,ye fEeDctIuTreO R 32 on 4, 199 6.152.ober 2 Laurence K. Thompson, EDITOR 7.6Oct Memorial University of Newfoundland ed by 21n Date: do oaati ownlublic Developed from a symposium sponsored DP by the International Chemical Congress of Pacific Basin Societies and the ACS Division of Inorganic Chemistry, Inc., at the 1995 International Chemical Congress of Pacific Basin Societies American Chemical Society, Washington, DC In Molecule-Based Magnetic Materials; Turnbull, M., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 1996. QD 940 .M66 1996 Copy 1 Molecule-based magnetic materials Library of Congress Cataloging-in-Publication Data Molecule-based magnetic materials: theory, techniques, and applications / Mark M. Turnbull, Toyonari Sugimoto, Laurence K. Thompson, editors. p. cm.—(ACS symposium series, ISSN 0097-6156; 644) "Developed from a symposium sponsored by the International Chemical Congress of Pacific Basin Societies and the ACS Division of Inorganic Chemistry, Inc., at the 1995 International Chemical Congress g 01 of Pacific Basin Societies, Honolulu, Hawaii, December 17-22, 1995." acs.or4.fw0 Includes bibliographical references and indexes. bs.64 ISBN 0-8412-3452-3 u0 p://p996- 1. Molecular crystals—Magnetic properties—Congresses. 8, 2012 | htt0.1021/bk-1 2DII.Ii vI.M .i sTToiholuneorc mnoubfplue sIslonl—,no Mr,M gLaaaanrgukincr eMe Cnti.c,hc e e1p mK9ro5i.,sp 6t1re-y r9t.4i e3.Vs -—. I IIC..n oStIenuVrggn.ria emAtsisoomentsoea.r, l iT cCaonhy eoCmnhaiecrima,l i1cC9ao4l nS5go-rceisest yo.f October 6 | doi: 1 QPaDci9f4ic0 .BMa6si6n S1o9c9ie6t ies (1995: Honolulu, Hawaii) VI. Series. 32 on 4, 199 548'.85—dc20 96-292C35IP 6.152.ober 2 7.6Oct This book is printed on acid-free, recycled paper. ed by 21n Date: Copyright © 1996 do oaati American Chemical Society wnlblic ou All Rights Reserved. The appearance of the code at the bottom of the first page of each DP chapter in this volume indicates the copyright owner's consent that reprographic copies of the chapter may be made for personal or internal use or for the personal or internal use of specific clients. This consent is given on the condition, however, that the copier pay the stated per-copy fee through the Copyright Clearance Center, Inc., 222 Rosewood Drive, Danvers, MA 01923, for copying beyond that permitted by Sections 107 or 108 of the U.S. Copyright Law. This consent does not extend to copying or transmission by any means—graphic or electronic—for any other purpose, such as for general distribution, for advertising or promotional purposes, for creating a new collective work, for resale, or for information storage and retrieval systems. The copying fee for each chapter is indicated in the code at the bottom of the first page of the chapter. The citation of trade names and/or names of manufacturers in this publication is not to be construed as an endorsement or as approval by ACS of the commercial products or services referenced herein; nor should the mere reference herein to any drawing, specification, chemical process, or other data be regarded as a license or as a conveyance of any right or permission to the holder, reader, or any other person or corporation, to manufacture, reproduce, use, or sell any patented invention or copyrighted work that may in any way be related thereto. Registered names, trademarks, etc, used in this publication, even without specific indication thereof, are not to be considered unprotected by law. PRINTED IN THE UNITED STATES OF AMERICA In Molecule-Based Magnetic Materials; Turnbull, M., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 1996. Advisory Board ACS Symposium Series Robert J. Alaimo Cynthia A. Maryanoff Procter & Gamble Pharmaceuticals R. W. Johnson Pharmaceutical Research Institute Mark Arnold University of Iowa Roger A. Minear g 01 University of Illinois acs.or4.fw0 DUnaivveidrs iBtya kofe Tr ennessee at Urbana-Champaign bs.64 Omkaram Nalamasu u0 8, 2012 | http://p0.1021/bk-1996- APRNfaroizvibenareld rRCatmee snFe t.arB raBcol rhsRa eLed sayeba,o rJrcrah.t o ry AUVTnini&vceTer snBittey lP lo Lef caMobroicarharitgooar nie s October 6 | doi: 1 MChaermyE Edi.t CCaosmteplalnioyn NGoerothr gCea rWoli.n Ra oSbtaetret Us niversity 32 on 4, 199 Margaret A. Cavanaugh JUonhivner sRit.y S ohf aIpllilneoyis 6.152.ober 2 National Science Foundation at Urbana-Champaign ed by 217.6n Date: Oct AUnritvheursrit yB .o fE Wlliissc onsin at Madison DCoonucugrlaresn At T. eScmhniotlhog ies Corporation oadatio Gunda I. Georg L. Somasundaram wnlblic University of Kansas DuPont ou DP Madeleine M. Joullie Michael D. Taylor University of Pennsylvania Parke-Davis Pharmaceutical Research Lawrence P. Klemann William C. Walker Nabisco Foods Group DuPont Douglas R. Lloyd Peter Willett The University of Texas at Austin University of Sheffield (England) In Molecule-Based Magnetic Materials; Turnbull, M., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 1996. Foreword THE ACS SYMPOSIUM SERIES was first published in 1974 to provide a mechanism for publishing symposia quickly in book form. The purpose of this series is to publish comprehensive books developed from symposia, which are usually "snapshots in time" of the current research being done on a topic, plus g 01 acs.or4.fw0 ssaormy et hraetv itehwe mpaapteerrsia bl eo np uthbeli sthoepdic a. s Fquoric tkhliys arse apsoosnsi,b ilte .i s neces ubs.064 Before a symposium-based book is put under contract, the p://p996- proposed table of contents is reviewed for appropriateness to 8, 2012 | htt0.1021/bk-1 rtphoaeup netrdos p oiuactr eat hneedx csfclouordp ecedo om fap ttr hetehh evisno sliupvmoeinene.t s,s I anon afd d tdhoitethi oecnros,l laea cdrtreiao fnat. d odfSe edoam ctheo October 6 | doi: 1 Tperah^pis)e rao nfi sot nhpyeem esryo-murespv oiresewivuieemdw , pwprhriooorc betseosc ofimsin eas lu tphaeecr cveeidpsiettadonr c(bsey) otohrf etr heoejre gbcatoinooiknz.. 6.152.32 on ober 24, 199 Tmcahemen edaraaut-tirohenoasrd sy o tfhc oepbnyo ,rt heav nitsdhe e s tuhbreemivrii etp wtaheprees r fsian anacld c potarhpdeei nresgd ttiotoo rtthsh,e e perrdeeciptooamrrse , 7.6Oct who check that all necessary revisions have been made. ed by 21n Date: view Apsa pae rrsu aler,e oinnlcyl uodreidg iinna lt hree sevaorluchm epsa. peVres rbanatdim o rriegpinroadl urec oadatio tions of previously published papers are not accepted. wnlblic DoPu ACS BOOKS DEPARTMENT In Molecule-Based Magnetic Materials; Turnbull, M., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 1996. Preface THE HELD OF MOLECULAR MAGNETISM began in 1983 at a NATO Advanced Study Institute two-week summer school in Castigleone della Pescaia, Italy (Magneto-Structural Correlations in Exchange Coupled Sys tems). Organized by Olivier Kahn, Dante Gatteschi, and Roger Willett, it was devoted to the study of magnetic interactions in insulators. The school was designed to bring together chemists and physicists with com org 001 mon interests, but differing backgrounds, and was therefore of a tutorial acs.4.pr nature. A second NATO conference (Organic and Inorganic Low- http://pubs.k-1996-064 Dtchhiiemsm eiinnststseio"rnd waislic tihCp ltrihnyesa traoylr lgifniaeenl diMc bcayot nebrdriuainclstg,o irnMsg i cntooomgrecmtah,u enrSi ptytah.i ne, S ein1m9ce8er7 tg)h inasgtt rt"iemnmgeat, hgtnehneeterode- October 8, 2012 | 6 | doi: 10.1021/b whnmaaoostrli keAobcinsnue agelalen -a rbinenaasd s u eigtlndhtr t oeoem wrf naittnhgahgentei oeosirtenniyc at,me lmr cedeoeasetnttsi enfigregiirnnsae, ,l n stc haahe enssa dosfdl iiegedslrdtd ouic cwdoaaryntse e dojoouv ffted orcg t htehthedheem es b eissp uyta bsns tjetheaw centt w.d n ceupllavmhseys bseyeisecr ai srotossff. 6.152.32 on ober 24, 199 Tbpeehrtew tieefose cnuo ssf trtouhfce t tuhbreueilr ka wt sotuhrbkes tamcnooncletei,cn uuwleaistrh lteotvh ebel e o abunjnded ctethirvese ta renosdfu inldtgien stgigh nemi nargge nlanetteiiowcn spahrniopd 7.6Oct better magnetic materials. Molecular magnetism has become so well esta oaded by 21ation Date: bndloaiwushn ettaeddk t ihnbagyt a th" seoe urbtiosriuedase dritsnh"t e owrfe osertx kpiinne rgtth iisene f ifrerelidnqg.u ei raerde taos , mwahkoe ma icgohnt tortihbeurtwioinse, abree wnlblic Molecular magnetism also lends itself to, or perhaps even requires, DoPu collaborative work largely because of the dearth of magnetometers, partic ularly in chemistry departments. For the field to continue its develop ment, "membership" needs to be expanded further. Thus, a symposium titled "Molecule-Based Magnetic Materials" was sponsored by the 1995 International Chemical Congress of Pacific Basin Societies (Pacifichem '95) and the ACS Division of Inorganic Chemistry, Inc., on December 17-22, 1995, in Honolulu, Hawaii. The symposium presented a mixture of tutorial talks on the various theoretical and practical aspects of work in molecular magnetism along with lectures describing the most recent developments in the field. The goal of the symposium was to present an introduction to the field that showed both its fundamentals and its excite ment. This book has the same purpose. The first section deals primarily ix In Molecule-Based Magnetic Materials; Turnbull, M., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 1996. with tutorial papers on the theory of magnetic exchange and the various techniques by which the magnetic properties of these materials may be investigated. Subsequent sections are devoted to finite systems (organic and metal-based dimer, oligomer, and cluster molecules), extended organic systems, and extended metal-based systems. Here, the distinction between organic and metal-based systems is made by the source of the magnetic moment in the sample. Each of these sections begins with tutorial chapters encompassing the fundamentals specific to that area fol lowed by chapters relating recent results. We hope that this book will be of interest to a broad audience. Scientists working with organic radical systems or paramagnetic transition or lanthanide metals will find a general overview of molecular magnetism that may suggest new directions for their studies or applications for their org 001 materials. Scientists joining established molecular magnetism groups will s.pr find that the chapters relating to exchange theory and measurement tech ac4. 8, 2012 | http://pubs.0.1021/bk-1996-064 Awinanlicisoqlk lru fngpeooasrrw n owpilvcerio ddosrguevkm pieadere ersnr cetaiosfn e nu rdresuenelfccautetol e rdoisnn , at lrrtoheowaed-s ud pcoiomtfti oeemnnnt asititaooel nr itaaahpll espsi yrlsi scctsaietetumniodcsnie,e s sa s.no ufdc F hmim naaaagslgn lnyoe,etr itgctoha -mneo piacbtt ioeacrosni.kd October 6 | doi: 1 We are grateful to all those who have supported the production of this 32 on 4, 199 bmoaodke aton dt hteh eD osynmorpso soiuf mT hue pPoent rwolheiucmh iRt eisse abracshe dF. unAdc, kandomwilnedisgtemreendt biys 7.66.152.October 2 tFhine aAncmiaelr iscuapnp oCrht efmroicma l LSaokceie tSyh, ofroer Cprayrotitarlo nsuicpsp, oQrut aonft uthme Dsyemsigpno,s iaunmd. by 21Date: tnhoew lAedCgeSd D. ivWisieo na losof Ianpoprrgeacniiact eC thheem iastsrsyis,t aInncc.e, iosf aKlsuon igor aAtewfuallgya aacnkd ded on Hisashi Okawa in the organization of the symposium. Finally, we thank oaati all those who have contributed their time and efforts to the work wnlblic described in this book. ou DP TOYONARI SUGIMOTO MARK M. TURNBULL University of Osaka Prefecture Clark University Sakai, Osaka 593, Japan Worcester, MA 01610 LAURENCE K. THOMPSON Memorial University of Newfoundland St. John's, Newfoundland A1B 3X7, Canada June 3, 1996 x In Molecule-Based Magnetic Materials; Turnbull, M., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 1996. Chapter 1 Molecule-Based Magnets: An Introduction Joel S. Miller1 and Arthur J. Epstein2 1Department of Chemistry, University of Utah, Salt Lake City, UT 84112 2Departments of Physics and Chemistry, Ohio State University, Columbus, OH 43210-1106 acs.org 4.ch001 HistorTyh e of shmepahgenrde ts Maangdn es miang ntehteis ma ncient Greek province of October 8, 2012 | http://pubs.6 | doi: 10.1021/bk-1996-064 rMMmoLteoraciac anthkggewdnrsnne a oeedylssso it i naugh scyiLtk siocna an ptft.rei Tlosa)o hnc1teksa2hafs 0eets r0 ano,,ltfa n yh ta etusihi ilrnhsseat e ilemlaowyfptfle t.ho r amahiwbttiai suTneg trghwnese edeha st soceil tcaoe o tms esp evrpbeae araenmrhks disaniet ,nphto ytgsewh l F yenoif t gifhrtu amiseprst ma e gatfolooiigf1rc d ns,a eenthl ts oiwitsttroe eaeonx s sca ettka(m hsfFianf (p tlevecl 3eeaOaas nsdlo4l t)imeeo.nh ddfgee 32 on 4, 199 itnh oCseh inoaf. thTeh e nceowm pwasosr ldw.a s cIrnu caiadl dittoi onfu tutore beexipnlgo ractirouncsi ali nctlou ditnhge 6.152.ober 2 edvevoelulotpiomne nto f of soscciieentyc,e ams awgneellt ica s mteacthernioallos gyw.1 ere crucial to the 7.6Oct ed by 21n Date: do oaati wnlblic ou DP Figure 1. Example of an early floating compass. Reproduced with permission of Dover Publications, Inc. Copyright 1986. 0097-6156/96/0644-0001$15.00/0 © 1996 American Chemical Society In Molecule-Based Magnetic Materials; Turnbull, M., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 1996. 2 MOLECULE-BASED MAGNETIC MATERIALS Although Galileo Gallelei is often attributed to be the father of experimental science, in 1269 Petrus Peregrinus de Maricourt preceded him with his important empirical observations aimed to prove/disprove theory. He (1) identified and named the north /south magnetic poles, (2) noted that opposite magnetic poles attracted while acs.org 4.ch001 8, 2012 | http://pubs.0.1021/bk-1996-064 October 6 | doi: 1 Reproduced with permissionF firgoumr ere f2er.e nWcei l2l.i aCmo pyGriiglbhte r1t9 58. Dover Publications, Inc. 32 on 4, 199 similar magnetic poles repelled, (3) noted that breaking a magnet 6.152.ober 2 wona sa npoint . destructive, and (4) improved the compass by mounting it 7.6Oct Man's fascination with magnets continued and William ed by 21n Date: G(1i)l becrrte, atFedig uare n2e,w atntroitb unteadtu rbayl lyG oacliclueor riansg thmea gfnirestt -e xipreorni mtehnatta li(s2t,) do oaati upon heating lost its magnetic force which returned upon cooling wnlblic and (3) identified the Earth as a magnet. Furthermore, in 1600 he ou DP wrote' De Magnete Magneticisque Corporibus et de Magno Magnete Tellure Physiologia Nova - the first systematic Treatise based on an experimental scientific study.2 In the nineteen century additional key development occurred, namely (1) Hans Christian 0ersted observed that electricity affected magnets (1819); (2) Michael Faraday invented the electromagnet (1823); and (3) the use of magnets enabled the production of low-cost electricity at an ac generating station built by Westinghouse in Buffalo, NY (1886). In a major triumph for the then-fledging theory of quantum mechanics, Niels Bohr in 1913 identified the underlying physics from which magnetism results, i. e., the minute spin associated with an unpaired electron.1 Throughout this time magnets were limited to metallurgically processed inorganic materials with little, if any, thought given to organic materials. In Molecule-Based Magnetic Materials; Turnbull, M., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 1996. 1. MILLER & EPSTEIN Molecule-Based Magnets: An Introduction 3 History of molecule-based magnets Use of molecules (or molecular ions) instead of atom (or ions)presents an exciting prospect as it is expected to enable (i) the modulation of the magnetic properties by energy efficient low- temperature organic-synthesis methodologies, (ii) the improve ment of commercially useful magnetic properties, and (iii) the combination of magnetic properties with other physical properties (e. g., mechanical, electrical, and/or optical). Nonetheless, despite these potential attributes the concept of molecule-based magnets, let alone its realization, was slow to evolve. The early history of molecule-based magnets was dominated by theory. In 1963 Harden H. McConnell then at the California acs.org 4.ch001 cInosutpitluinteg obfe twTeeecnh nomloogleyc usleusg gethstaetd inav omlveecdh atnhiesm s pfaotria l fearrrroamnaggenmeetnict 8, 2012 | http://pubs.0.1021/bk-1996-064 omeawfxp ioctphliretn eoceduami cglahahsrg bt naoaeitroetiiimn ncs gie n dott ohrr daaatedtt hr iiecinn asgtvlg asor.b-l3o viuleiondzIndni nl ytg hs1 te9fa e6ftre7earr .dor4 mmoMmiaxcNgaCinnegoiengtnth eintceoi recf l lc ooafcupn opu tuhlbcpielnhli agsinhmn gegob dede tebwlatesrnet awoendnteshe efaeenarlrt 32 on October 4, 1996 | doi: 1 pmthaoeir d elloasAft tlesdmroi. dol eicnnuo lte 1s 9a6p-7p eaanrHd . u rneHtsielo alrl1ics9h 8 7Wf5o iccufkosrme da tnh teo weftao. rrdma eltr.h ea tnhteden st 1in9agt8 2t6B heefolslre 6.152.ober 2 Lchalboororbatiso(rdiieest hlyrdeipthoirotceadr bamthaatte )irionnt(eIrImI),e dia1t, e-sCpliFne in-(S(52 CN= Et3)/22, ) ed by 217.6n Date: Oct rw1e9ap7so0 r atRe d.f erLrt.oh maMta agrntaeinnt oatwhniedtrh coai- nwctoerrirtkmiceaersld iataettme -ptshpeeri nat Uurne(i5,v eTrs=c,i tyo 3f /o22f). 4M6 ceoKlbmo.7p ulrIennxe , do oaati manganese phthalocyanine (MnPc), 2, was a ferromagnet.8 Its 8.3 wnlblic K T as well as its detailed characterization as being a canted- ou c D P ferromagnet were reported by William E. Hatfield's University of North Carolina group in 1983.9 In 1973 Claudine Veyret and co workers in Grenoble, France reported that bis(2,2,4,4-tetramethyl- 4-piperidinol-l-oxyl), 3, tanol suberate, was a ferromagnet with a T of 0.38 K.10 In 1981, additional data from the same group led c to the recharacterization of tanol suberate as being a metamagnet, i. e., it had an antiferromagnetic ground state; however, above a critical applied magnetic field of 100 Oe and below a T of 0.38 K it c had a high moment, ferromagnetic-like state.11 In 1979 the 7,7,8,8-tetracyano-/7-quinodimethane (TCNQ), 4, electron-transfer salt of decamethylferrocene, FeCp*2, 5, was reported to be a metamagnet below the T of 2.55 K with a critical applied magnetic c field of 1600 Oe.12 In Molecule-Based Magnetic Materials; Turnbull, M., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 1996.
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