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MMM.indd 1 11/22/12 5:39:15 AM Multifunctional Molecular Materials ~~~~""~"""'c..=......J TThhiiss ppaaggee iinntteennttiioonnaallllyy lleefftt bbllaannkk Multifunctional Molecular Materials edited by Lahcene Ouahab 'rrr PAN STANFORD PUBLISHING CRC Press Taylor & Francis Group 6000 Broken Sound Parkway NW, Suite 300 Boca Raton, FL 33487-2742 © 2012 by Taylor & Francis Group, LLC CRC Press is an imprint of Taylor & Francis Group, an Informa business No claim to original U.S. Government works Version Date: 20130321 International Standard Book Number-13: 978-981-4364-30-0 (eBook - PDF) This book contains information obtained from authentic and highly regarded sources. Reason- able efforts have been made to publish reliable data and information, but the author and publisher cannot assume responsibility for the validity of all materials or the consequences of their use. The authors and publishers have attempted to trace the copyright holders of all material reproduced in this publication and apologize to copyright holders if permission to publish in this form has not been obtained. If any copyright material has not been acknowledged please write and let us know so we may rectify in any future reprint. Except as permitted under U.S. Copyright Law, no part of this book may be reprinted, reproduced, transmitted, or utilized in any form by any electronic, mechanical, or other means, now known or hereafter invented, including photocopying, microfilming, and recording, or in any information storage or retrieval system, without written permission from the publishers. For permission to photocopy or use material electronically from this work, please access www. copyright.com (http://www.copyright.com/) or contact the Copyright Clearance Center, Inc. (CCC), 222 Rosewood Drive, Danvers, MA 01923, 978-750-8400. CCC is a not-for-profit organiza- tion that provides licenses and registration for a variety of users. For organizations that have been granted a photocopy license by the CCC, a separate system of payment has been arranged. Trademark Notice: Product or corporate names may be trademarks or registered trademarks, and are used only for identification and explanation without intent to infringe. Visit the Taylor & Francis Web site at http://www.taylorandfrancis.com and the CRC Press Web site at http://www.crcpress.com Contents Preface xi 1. MagnetismandConductivity TadashiSugawaraandAkiraMiyazaki 1.1 Introduction 1 1.2 Interaction Between Conduction Electrons and Localized Spins 3 1.2.1 RKKY (Ruderman, Kittel, Kasuya,Yosida) Interaction 4 1.2.2 Double-Exchange Mechanism in Metal Oxides 6 1.3 Interaction Between Localized Spins and Itinerant Electrons in Metallic and Magnetic Nanoparticles 7 1.4 Magnetic Structures of Edge-State Spins in Nanographene 11 1.5 Coexistence and Cooperation of Conductivity and Magnetism in Transition Metal Complexes 14 1.5.1 Radical Ion Salts Containing Monomeric Magnetic Counter Ions 15 1.5.2 Radical Ion Salts Containing Polymeric Magnetic Counter Ions 19 1.5.3 Introduction of Halogen–Halogen Contacts 21 1.5.4 (cid:83)–dCoordinated System 22 1.6 Spin-Polarized Donor Radical as a Building Block of Organic Magnetic Conductor 24 1.7 Conductivity and Magnetism of TTF- and TSF-Based Donor Radicals 27 1.7.1 Molecular Design of a Building Block of Conducting Magnet 27 1.7.2 Electronic Structure of ETBN and Physical Properties of Its Radical Ion Salt 29 vi Contents 1.8 Magnetic and Conducting Properties of Ion Radical Salts of ESBN and TSBN 32 1.8.1 Nonlinear Conducting Behavior of ESBN ClO 32 2 4 1.8.2 Variable Range Hopping Mechanism of TSBN ClO 34 2 4 1.9 Magnetotransport Properties of Ion Radical Salts of TTF(cid:487)and(cid:23)(cid:22)(cid:9)(cid:487)Based Donor Radicals 35 1.9.1 Magnetoresistance of ESBN ClO Observed 2 4 in Nonlinear Conductance Region 35 1.9.2 Magnetoresistance Observed in (TSBN) ClO 37 2 4 1.9.3 Pressure Effect on Magnetotransport of (TSBN) ClO 38 2 4 1.10 Manipulation of Unicomponent Crystal of TTF-Based Donor Radical by Electric and Magnetic Fields 40 1.10.1 Design of BTBN and Its Self-Assembling Ability 40 1.10.2 Conducting Behavior of BTBN Through SCLC Mechanism 43 1.10.3 Magnetoresistance of BTBN 44 1.11 Summary and Future Scope 46 2. MultifunctionalitiesofSingle-MoleculeMagnetswith ElectricalConductivities 61 KazuyaKubo,HirokiHiraga,HitoshiMiyasaka,and MasahiroYamashita 2.1 General Introduction of Conducting Single-Molecule Magnet 62 2.1.1 General Feature of Single-Molecule Magnets 62 2.1.2 General Feature of Molecular Conductors Based on Metal Ditholene Complex System 64 2.1.3 General Feature of Hybrid Materials Based on Molecular Nano-sized Magnets 65 2.2 Tetra-Nuclear Manganese Cluster SMMs with Metal–Dithiolene Complex System 67 Contents vii 2.2.1 Introduction 67 2.2.2 Structures of{MnIIMnIII(hmp) (MeCN) } 2 2 6 2 {Pt(mnt) } ][Pt(mnt) ] ·2MeCN and 2 2 2 2 [{MnIIMnIII(hmp) (MeCN) } 2 2 6 2 {Pt(mnt) } ][Pt(mnt) ] 68 2 4 2 2 2.2.3 Physical Properties of [{MnIIMnIII(hmp) (MeCN) } 2 2 6 2 {Pt(mnt) } ][Pt(mnt) ] ·2MeCN and 2 2 2 2 {MnIIMnIII(hmp) (MeCN) }{Pt(mnt) } ] 2 2 6 2 2 4 [Pt(mnt) ] 71 2 2 2.2.3.1 Electricalconductivity 71 2.2.3.2 Magneticproperties 72 2.2.4 Conclusion 77 2.3 Manganese(cid:487)Salen Type Out-of-Plane Dimer SMMs with Metal–Dithiolene Complex:Integer Oxidation State of the Metal–Dithiolene Moiety 77 2.3.1 Introduction 77 2.3.2 Structure of [Mn(5-Rsaltmen) {MIII(dmit) }] (R = Me, MeO; M = Ni, Au) 79 2 2 2.3.3 Physical Properties of [Mn(5-Rsaltmen) {MIII(dmit) }] (R = Me, MeO; M = Ni, Au) 81 2 2 2.3.3.1 Electricalconductivity 81 2.3.3.2 DCmagnetic property 82 2.3.3.3 Magnetostructural correlation 84 2.3.3.4 AC magnetic property 86 2.3.4 Conclusion 88 2.4 Manganese–Salen Type Out-of-Plane Dimer with Metal–Dithiolene Complex:Noninteger Oxidation State of the Metal–Dithiolene Moiety 89 2.4.1 Introduction 89 2.4.2 Structures of [Mn(5-MeOsaltmen)(solvent)] 2 [Ni(dmit) ] .4(solvent) 2 7 (solvent = acetone, MeCN) 90 2.4.2 Physical Properties of [Mn(5-MeOsaltmen) (solvent)] [Ni(dmit) ] .4(solvent) 2 2 7 (solvent = acetone, MeCN) 92 viii Contents 2.4.2.1 Electricalconductivity 92 2.4.2.2 Magneticproperty 93 2.4.3 Conclusion 95 2.5 GeneralConclusion 95 3. MultifunctionalSingle-MoleculeMagnetsand Single-ChainMagnets 105 Ling-ChenKangandJing-LinZuo 3.1 Introduction 105 3.2 Conductive Single-Molecule Magnets 106 3.3 Photoluminescent Single-Molecule Magnets 112 3.4 Photochromic Single-Molecule Magnets 114 3.5 Chiral Single-Molecule Magnets and Ferroelectric Single-Chain Magnets 118 3.6 Functionalized Single-Molecule Magnets 122 3.7 Other Emerging Areas of Single-Molecule Magnets and Single-Chain Magnets 124 3.8 Conclusion 125 4. MagnetismandChirality 133 KatsuyaInoueandJun-ichiroKishine 4.1 Introduction 133 4.2 Space Groups of Crystal 135 4.3 Symmetry and Complex Magnetic Structures 136 4.4 Magnetic Structure for Asymmetric Materials 138 4.5 Nonlinear Magneto-Optical Effects of Chiral Magnets 138 4.6 Magnetic Structure of Molecule Based Chiral Magnet 139 4.7 Magnetic Chirality and Crystal Chirality 143 4.8 Epilogue 143 5. TowardBifunctionalMaterialswithConducting, Photochromic,andSpinCrossoverProperties 149 LydieValade,IsabelleMalfant,andChristopheFaulmann 5.1 Introduction 149 5.2 Conductive and Photochromic Salts 152 Contents ix 5.2.1 Association Donor/Photochromic Anions 155 5.2.2 Association Acceptor/Photochromic Cations 162 5.3 Conductor and Spin Crossover 163 5.4 Conclusion 174 6. Electroactive4fLanthanidesComplexesInvolving TetrathiafulvaleneDerivativesasLigands:Magnetism andLuminescence 185 (cid:38)(cid:258)(cid:271)(cid:396)(cid:349)(cid:272)(cid:286)(cid:3)(cid:87)(cid:381)(cid:349)(cid:374)(cid:415)(cid:367)(cid:367)(cid:258)(cid:396)(cid:410)(cid:853)(cid:3)(cid:94)(cid:410)(cid:288)(cid:393)(cid:346)(cid:258)(cid:374)(cid:286)(cid:3)(cid:39)(cid:381)(cid:367)(cid:346)(cid:286)(cid:374)(cid:853)(cid:3)(cid:75)(cid:367)(cid:349)(cid:448)(cid:349)(cid:286)(cid:396)(cid:3)(cid:18)(cid:258)(cid:282)(cid:381)(cid:396)(cid:853)(cid:3) (cid:258)(cid:374)(cid:282)(cid:3)(cid:62)(cid:258)(cid:346)(cid:272)(cid:287)(cid:374)(cid:286)(cid:3)(cid:75)(cid:437)(cid:258)(cid:346)(cid:258)(cid:271) 6.1 Introduction 186 6.2 Neutral Coordination Complexes: Molecular Building Blocks for (cid:83)(cid:515)(cid:3)fMagnetic Conducting Materials 188 6.2.1 Mononuclear Complex [Gd(hfac) 3 (TTF-CONH-2-Pym-1-oxide) ](CH Cl ) 3 2 2 0.5 (C H ) 188 6 14 6.2.2 Binuclear Complexes [Ln (hfac) (O CPhCl) 2 5 2 (TTF-CONH-2-Py-N-oxide) ]·2H O with 3 2 Ln = Pr and Gd 189 6.2.3 Binuclear Complex [Tb (hfac) (O CPhCl) 2 4 2 2 (TTF-CONH-2-Py-N-oxide) ] 193 2 6.3 Oxidized Coordination Complex(cid:3)(cid:533)(cid:529)(cid:10)d(cid:525)hfac(cid:526) 3 (cid:525)(cid:487)(cid:23)(cid:23)(cid:9)+COO(cid:515)(cid:526)(cid:530) (cid:534)(cid:483)(cid:3)(cid:4)(cid:3)(cid:6)oordinating(cid:83)(cid:515)fSystem 196 2 6.4 Conclusion 211 7. MultifunctionalMaterialsofInterestin MolecularElectronics 219 M.LauraMercuri,PaolaDeplano,AngelaSerpe,and (cid:38)(cid:367)(cid:258)(cid:448)(cid:349)(cid:258)(cid:3)(cid:4)(cid:396)(cid:415)(cid:460)(cid:460)(cid:437) 7.1 Introduction 219 7.2 Magnetic Molecular Conductors 222 7.2.1 Paramagnetic Conductors 224 7.2.2 Paramagnetic Chiral Conductors 230 7.2.2.1 Ferromagnetic conductors 236 7.2.3 Single-Component Paramagnetic Conductors 238

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MMM.indd 1 11/22/12 5:39:15 AM Multifunctional Molecular Materials ~~~~""~"""'c..=......J TThhiiss ppaaggee iinntteennttiioonnaallllyy lleefftt bbllaannkk Multifunctional Molecular Materials edited by Lahcene Ouahab 'rrr PAN STANFORD PUBLISHING CRC Press Taylor & Francis Group 6000 Broken Sound Parkway NW, Suite 300 Boca Raton, FL 33487-2742 © 2012 by Taylor & Francis Group, LLC CRC Press is an imprint of Taylor & Francis Group, an Informa business No claim to original U.S. Government works Version Date: 20130321 International Standard Book Number-13: 978-981-4364-30-0 (eBook - PDF) This book contains information obtained from authentic and highly regarded sources. Reason- able efforts have been made to publish reliable data and information, but the author and publisher cannot assume responsibility for the validity of all materials or the consequences of their use. The authors and publishers have attempted to trace the copyright holders of all material reproduced in this publication and apologize to copyright holders if permission to publish in this form has not been obtained. If any copyright material has not been acknowledged please write and let us know so we may rectify in any future reprint. Except as permitted under U.S. Copyright Law, no part of this book may be reprinted, reproduced, transmitted, or utilized in any form by any electronic, mechanical, or other means, now known or hereafter invented, including photocopying, microfilming, and recording, or in any information storage or retrieval system, without written permission from the publishers. For permission to photocopy or use material electronically from this work, please access www. copyright.com (http://www.copyright.com/) or contact the Copyright Clearance Center, Inc. (CCC), 222 Rosewood Drive, Danvers, MA 01923, 978-750-8400. CCC is a not-for-profit organiza- tion that provides licenses and registration for a variety of users. For organizations that have been granted a photocopy license by the CCC, a separate system of payment has been arranged. Trademark Notice: Product or corporate names may be trademarks or registered trademarks, and are used only for identification and explanation without intent to infringe. Visit the Taylor & Francis Web site at http://www.taylorandfrancis.com and the CRC Press Web site at http://www.crcpress.com Contents Preface xi 1. MagnetismandConductivity TadashiSugawaraandAkiraMiyazaki 1.1 Introduction 1 1.2 Interaction Between Conduction Electrons and Localized Spins 3 1.2.1 RKKY (Ruderman, Kittel, Kasuya,Yosida) Interaction 4 1.2.2 Double-Exchange Mechanism in Metal Oxides 6 1.3 Interaction Between Localized Spins and Itinerant Electrons in Metallic and Magnetic Nanoparticles 7 1.4 Magnetic Structures of Edge-State Spins in Nanographene 11 1.5 Coexistence and Cooperation of Conductivity and Magnetism in Transition Metal Complexes 14 1.5.1 Radical Ion Salts Containing Monomeric Magnetic Counter Ions 15 1.5.2 Radical Ion Salts Containing Polymeric Magnetic Counter Ions 19 1.5.3 Introduction of Halogen–Halogen Contacts 21 1.5.4 (cid:83)–dCoordinated System 22 1.6 Spin-Polarized Donor Radical as a Building Block of Organic Magnetic Conductor 24 1.7 Conductivity and Magnetism of TTF- and TSF-Based Donor Radicals 27 1.7.1 Molecular Design of a Building Block of Conducting Magnet 27 1.7.2 Electronic Structure of ETBN and Physical Properties of Its Radical Ion Salt 29 vi Contents 1.8 Magnetic and Conducting Properties of Ion Radical Salts of ESBN and TSBN 32 1.8.1 Nonlinear Conducting Behavior of ESBN ClO 32 2 4 1.8.2 Variable Range Hopping Mechanism of TSBN ClO 34 2 4 1.9 Magnetotransport Properties of Ion Radical Salts of TTF(cid:487)and(cid:23)(cid:22)(cid:9)(cid:487)Based Donor Radicals 35 1.9.1 Magnetoresistance of ESBN ClO Observed 2 4 in Nonlinear Conductance Region 35 1.9.2 Magnetoresistance Observed in (TSBN) ClO 37 2 4 1.9.3 Pressure Effect on Magnetotransport of (TSBN) ClO 38 2 4 1.10 Manipulation of Unicomponent Crystal of TTF-Based Donor Radical by Electric and Magnetic Fields 40 1.10.1 Design of BTBN and Its Self-Assembling Ability 40 1.10.2 Conducting Behavior of BTBN Through SCLC Mechanism 43 1.10.3 Magnetoresistance of BTBN 44 1.11 Summary and Future Scope 46 2. MultifunctionalitiesofSingle-MoleculeMagnetswith ElectricalConductivities 61 KazuyaKubo,HirokiHiraga,HitoshiMiyasaka,and MasahiroYamashita 2.1 General Introduction of Conducting Single-Molecule Magnet 62 2.1.1 General Feature of Single-Molecule Magnets 62 2.1.2 General Feature of Molecular Conductors Based on Metal Ditholene Complex System 64 2.1.3 General Feature of Hybrid Materials Based on Molecular Nano-sized Magnets 65 2.2 Tetra-Nuclear Manganese Cluster SMMs with Metal–Dithiolene Complex System 67 Contents vii 2.2.1 Introduction 67 2.2.2 Structures of{MnIIMnIII(hmp) (MeCN) } 2 2 6 2 {Pt(mnt) } ][Pt(mnt) ] ·2MeCN and 2 2 2 2 [{MnIIMnIII(hmp) (MeCN) } 2 2 6 2 {Pt(mnt) } ][Pt(mnt) ] 68 2 4 2 2 2.2.3 Physical Properties of [{MnIIMnIII(hmp) (MeCN) } 2 2 6 2 {Pt(mnt) } ][Pt(mnt) ] ·2MeCN and 2 2 2 2 {MnIIMnIII(hmp) (MeCN) }{Pt(mnt) } ] 2 2 6 2 2 4 [Pt(mnt) ] 71 2 2 2.2.3.1 Electricalconductivity 71 2.2.3.2 Magneticproperties 72 2.2.4 Conclusion 77 2.3 Manganese(cid:487)Salen Type Out-of-Plane Dimer SMMs with Metal–Dithiolene Complex:Integer Oxidation State of the Metal–Dithiolene Moiety 77 2.3.1 Introduction 77 2.3.2 Structure of [Mn(5-Rsaltmen) {MIII(dmit) }] (R = Me, MeO; M = Ni, Au) 79 2 2 2.3.3 Physical Properties of [Mn(5-Rsaltmen) {MIII(dmit) }] (R = Me, MeO; M = Ni, Au) 81 2 2 2.3.3.1 Electricalconductivity 81 2.3.3.2 DCmagnetic property 82 2.3.3.3 Magnetostructural correlation 84 2.3.3.4 AC magnetic property 86 2.3.4 Conclusion 88 2.4 Manganese–Salen Type Out-of-Plane Dimer with Metal–Dithiolene Complex:Noninteger Oxidation State of the Metal–Dithiolene Moiety 89 2.4.1 Introduction 89 2.4.2 Structures of [Mn(5-MeOsaltmen)(solvent)] 2 [Ni(dmit) ] .4(solvent) 2 7 (solvent = acetone, MeCN) 90 2.4.2 Physical Properties of [Mn(5-MeOsaltmen) (solvent)] [Ni(dmit) ] .4(solvent) 2 2 7 (solvent = acetone, MeCN) 92 viii Contents 2.4.2.1 Electricalconductivity 92 2.4.2.2 Magneticproperty 93 2.4.3 Conclusion 95 2.5 GeneralConclusion 95 3. MultifunctionalSingle-MoleculeMagnetsand Single-ChainMagnets 105 Ling-ChenKangandJing-LinZuo 3.1 Introduction 105 3.2 Conductive Single-Molecule Magnets 106 3.3 Photoluminescent Single-Molecule Magnets 112 3.4 Photochromic Single-Molecule Magnets 114 3.5 Chiral Single-Molecule Magnets and Ferroelectric Single-Chain Magnets 118 3.6 Functionalized Single-Molecule Magnets 122 3.7 Other Emerging Areas of Single-Molecule Magnets and Single-Chain Magnets 124 3.8 Conclusion 125 4. MagnetismandChirality 133 KatsuyaInoueandJun-ichiroKishine 4.1 Introduction 133 4.2 Space Groups of Crystal 135 4.3 Symmetry and Complex Magnetic Structures 136 4.4 Magnetic Structure for Asymmetric Materials 138 4.5 Nonlinear Magneto-Optical Effects of Chiral Magnets 138 4.6 Magnetic Structure of Molecule Based Chiral Magnet 139 4.7 Magnetic Chirality and Crystal Chirality 143 4.8 Epilogue 143 5. TowardBifunctionalMaterialswithConducting, Photochromic,andSpinCrossoverProperties 149 LydieValade,IsabelleMalfant,andChristopheFaulmann 5.1 Introduction 149 5.2 Conductive and Photochromic Salts 152 Contents ix 5.2.1 Association Donor/Photochromic Anions 155 5.2.2 Association Acceptor/Photochromic Cations 162 5.3 Conductor and Spin Crossover 163 5.4 Conclusion 174 6. Electroactive4fLanthanidesComplexesInvolving TetrathiafulvaleneDerivativesasLigands:Magnetism andLuminescence 185 (cid:38)(cid:258)(cid:271)(cid:396)(cid:349)(cid:272)(cid:286)(cid:3)(cid:87)(cid:381)(cid:349)(cid:374)(cid:415)(cid:367)(cid:367)(cid:258)(cid:396)(cid:410)(cid:853)(cid:3)(cid:94)(cid:410)(cid:288)(cid:393)(cid:346)(cid:258)(cid:374)(cid:286)(cid:3)(cid:39)(cid:381)(cid:367)(cid:346)(cid:286)(cid:374)(cid:853)(cid:3)(cid:75)(cid:367)(cid:349)(cid:448)(cid:349)(cid:286)(cid:396)(cid:3)(cid:18)(cid:258)(cid:282)(cid:381)(cid:396)(cid:853)(cid:3) (cid:258)(cid:374)(cid:282)(cid:3)(cid:62)(cid:258)(cid:346)(cid:272)(cid:287)(cid:374)(cid:286)(cid:3)(cid:75)(cid:437)(cid:258)(cid:346)(cid:258)(cid:271) 6.1 Introduction 186 6.2 Neutral Coordination Complexes: Molecular Building Blocks for (cid:83)(cid:515)(cid:3)fMagnetic Conducting Materials 188 6.2.1 Mononuclear Complex [Gd(hfac) 3 (TTF-CONH-2-Pym-1-oxide) ](CH Cl ) 3 2 2 0.5 (C H ) 188 6 14 6.2.2 Binuclear Complexes [Ln (hfac) (O CPhCl) 2 5 2 (TTF-CONH-2-Py-N-oxide) ]·2H O with 3 2 Ln = Pr and Gd 189 6.2.3 Binuclear Complex [Tb (hfac) (O CPhCl) 2 4 2 2 (TTF-CONH-2-Py-N-oxide) ] 193 2 6.3 Oxidized Coordination Complex(cid:3)(cid:533)(cid:529)(cid:10)d(cid:525)hfac(cid:526) 3 (cid:525)(cid:487)(cid:23)(cid:23)(cid:9)+COO(cid:515)(cid:526)(cid:530) (cid:534)(cid:483)(cid:3)(cid:4)(cid:3)(cid:6)oordinating(cid:83)(cid:515)fSystem 196 2 6.4 Conclusion 211 7. MultifunctionalMaterialsofInterestin MolecularElectronics 219 M.LauraMercuri,PaolaDeplano,AngelaSerpe,and (cid:38)(cid:367)(cid:258)(cid:448)(cid:349)(cid:258)(cid:3)(cid:4)(cid:396)(cid:415)(cid:460)(cid:460)(cid:437) 7.1 Introduction 219 7.2 Magnetic Molecular Conductors 222 7.2.1 Paramagnetic Conductors 224 7.2.2 Paramagnetic Chiral Conductors 230 7.2.2.1 Ferromagnetic conductors 236 7.2.3 Single-Component Paramagnetic Conductors 238

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