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    Lanthanide-Based Multifunctional Materials: From OLEDs to SIMs
    Lanthanide-Based Multifunctional Materials: From OLEDs to SIMs
    Lanthanide-Based Multifunctional Materials: From OLEDs to SIMs
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    Lanthanide-Based Multifunctional Materials: From OLEDs to SIMs

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    About this ebook

    Lanthanide-Based Multifunctional Materials: From OLEDs to SIMs serves as a comprehensive and state-of the art review on these promising compounds, delivering a panorama of their extensive and rapidly growing applications.

    After an introductory chapter on the theoretical description of the optical and magnetic behaviour of lanthanides and on the prediction of their properties by ab-initio methods, four chapters are devoted to lanthanide-based OLEDs, including the latest trends in visible emitters, the emerging field of near infrared emitters and the first achievements attained in the field of chiral OLEDs. The use of lanthanide complexes as molecular magnets spreads over another two chapters, which explain the evolution of 4f-elements-based SIMs and the most recent advances in heterometallic 3d–4f SMMs. Other very active research areas are covered in the remaining five chapters, dedicated to lanthanide-doped germanate and tellurite glasses, luminescent materials for up-conversion, luminescent thermosensors, multimodal imaging and therapeutic agents, and chemosensors.

    The book is aimed at academic and industrial researchers, undergraduates and postgraduates alike, and is of particular interest for the Materials Science, Applied Physics and Applied Chemistry communities.

    • Includes the latest progress on lanthanide-based materials and their applications (in OLEDs, SIMs, doped matrices, up-conversion, thermosensors, theragnostics and chemosensors)
    • Presents basic and applied aspects of the Physics and Chemistry of lanthanide compounds, as well as future lines of action
    • Covers successful examples of devices and proofs-of-concept and provides guidelines for the rational design of new materials
    LanguageEnglish
    PublisherElsevier Science
    Release dateJun 26, 2018
    ISBN9780128138410
    Lanthanide-Based Multifunctional Materials: From OLEDs to SIMs

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      Book preview

      Lanthanide-Based Multifunctional Materials - Elsevier Science

      Lanthanide-Based Multifunctional Materials

      From OLEDs to SIMs

      First Edition

      Pablo Martín-Ramos

      Manuela Ramos Silva

      Table of Contents

      Cover image

      Title page

      Copyright

      Contributors

      About the editors

      Pablo Martín-Ramos—Editor

      Manuela Ramos Silva—Editor

      Author biographies

      Chapter 1

      Chapter 2

      Chapter 3

      Chapter 4

      Chapter 5

      Chapters 6 and 7

      Chapter 8

      Chapter 9

      Chapter 10

      Chapter 11

      Chapter 12

      Foreword

      Preface

      1: Introduction to the electronic structure, luminescence, and magnetism of lanthanides

      Abstract

      1.1 Introduction

      1.2 Theoretical description of optical behavior of lanthanides

      1.3 Magnetism of lanthanide ions

      1.4 Conclusions and outlook

      2: Potential of europium and samarium β-diketonates as red light emitters in organic light-emitting diodes

      Abstract

      2.1 Introduction

      2.2 Artificial lighting sources

      2.3 Requisites for OLEDs for sustainable development

      2.4 Role of rare-earth complexes in OLEDs

      2.5 Eu³+ and Sm³+β-diketonate complexes state of art

      2.6 The appeal of Eu³+/Sm³+-based LEDs

      2.7 Key challenges in red OLEDs

      2.8 Future scope on the use of OLEDs in lamps

      2.9 Conclusions

      3: Lanthanide ion emission in multicolor OLEDs (Ce³+, Pr³+, Tb³+, Dy³+, Tm³+, and white light Eu³+/Tb³+ hybrid systems) and device characterization

      Abstract

      3.1 Introduction

      3.2 Luminescence

      3.3 Electroluminescence

      3.4 Ln³+-based emitting layers in OLEDs

      3.5 Conclusions and challenges

      4: OLEDs based on Ln(III) complexes for near-infrared emission

      Abstract

      4.1 Introduction

      4.2 Principle of operation and basic requirements of an organic light-emitting diode (OLED)

      4.3 Mechanisms to obtain near infrared emission

      4.4 Electroluminescent devices in the near-infrared wavelength range based on lanthanides

      4.5 Conclusions

      5: Emerging field of chiral Ln(III) complexes for OLEDs

      Abstract

      5.1 Introduction

      5.2 Ln-based circularly polarized luminescence

      5.3 CP electroluminescent devices

      5.4 Conclusion

      6: Ln(III)-based SIMs

      Abstract

      6.1 Introduction

      6.2 A brief historical review

      6.3 Molecular magnets and the lengthy walk to spintronic applications

      6.4 Conclusions and final remarks

      7: Heterometallic 3d-4f SMMs

      Abstract

      7.1 Introduction

      7.2 Purpose: Why combine 3d-4f to obtain SMMs?

      7.3 Survey of 3d-4f SMMs

      7.4 Concluding remarks and perspectives

      8: Rare-earth-doped germanate and tellurite glasses: Laser, waveguide, and ultrafast device applications

      Abstract

      Acknowledgments

      8.1 Introduction

      8.2 Our contribution to the field: Most relevant results

      8.3 Recent promising results from other research groups

      8.4 Summary

      9: Up-conversion processes in Ln(III)-doped luminescent materials for photovoltaics and photocatalysis

      Abstract

      9.1 Introduction

      9.2 Lanthanide ions' energy up-conversion processes

      9.3 Applications of lanthanide ions' up-converted luminescence

      9.4 Concluding remarks

      10: Lanthanide-based luminescent thermosensors: From bulk to nanoscale

      Abstract

      Acknowledgments

      10.1 Introduction

      10.2 Luminescence thermometric methods

      10.3 Thermometric properties of individual trivalent lanthanides

      10.4 Multiple non-thermally coupled lanthanide LIR

      10.5 Remarks on lanthanide-based inorganic nanothermometers

      10.6 Lanthanide-based molecular thermal sensors

      10.7 Applications

      10.8 Conclusions and outlook

      11: Lanthanide-doped materials as dual imaging and therapeutic agents

      Abstract

      Acknowledgments

      Conflict of interest

      11.1 Introduction

      11.2 Properties of lanthanide materials

      11.3 Lanthanide nanoparticles for bioimaging applications

      11.4 Lanthanide nanoparticles for therapeutic applications

      11.5 Conclusions

      12: Lanthanide materials as chemosensors

      Abstract

      Acknowledgments

      12.1 Introduction

      12.2 Lanthanide materials for electrochemical sensing

      12.3 Lanthanide materials for optical sensing

      12.4 Advanced chemical sensors

      12.5 Conclusions

      Index

      Copyright

      Elsevier

      Radarweg 29, PO Box 211, 1000 AE Amsterdam, Netherlands

      The Boulevard, Langford Lane, Kidlington, Oxford OX5 1GB, United Kingdom

      50 Hampshire Street, 5th Floor, Cambridge, MA 02139, United States

      Copyright © 2018 Elsevier Inc. All rights reserved.

      No part of this publication may be reproduced or transmitted in any form or by any means, electronic or mechanical, including photocopying, recording, or any information storage and retrieval system, without permission in writing from the publisher. Details on how to seek permission, further information about the Publisher's permissions policies and our arrangements with organizations such as the Copyright Clearance Center and the Copyright Licensing Agency, can be found at our website: www.elsevier.com/permissions.

      This book and the individual contributions contained in it are protected under copyright by the Publisher (other than as may be noted herein).

      Notices

      Knowledge and best practice in this field are constantly changing. As new research and experience broaden our understanding, changes in research methods, professional practices, or medical treatment may become necessary.

      Practitioners and researchers must always rely on their own experience and knowledge in evaluating and using any information, methods, compounds, or experiments described herein. In using such information or methods they should be mindful of their own safety and the safety of others, including parties for whom they have a professional responsibility.

      To the fullest extent of the law, neither the Publisher nor the authors, contributors, or editors, assume any liability for any injury and/or damage to persons or property as a matter of products liability, negligence or otherwise, or from any use or operation of any methods, products, instructions, or ideas contained in the material herein.

      Library of Congress Cataloging-in-Publication Data

      A catalog record for this book is available from the Library of Congress

      British Library Cataloguing-in-Publication Data

      A catalogue record for this book is available from the British Library

      ISBN: 978-0-12-813840-3

      For information on all Elsevier publications visit our website at https://www.elsevier.com/books-and-journals

      Publisher: Deans Matthew

      Acquisition Editor: Kayla Dos Santos

      Editorial Project Manager: Charlotte Rowley

      Production Project Manager: Joy Christel Neumarin Honest Thangiah

      Cover Designer: Greg Harris

      Typeset by SPi Global, India

      Contributors

      Ángel L. Álvarez     Rey Juan Carlos University, Madrid, Spain

      Maria J.V. Bell     Federal University of Juiz de Fora, Juiz de Fora, Brazil

      Ana de Bettencourt-Dias     University of Nevada, Reno, NV, United States

      Joana T. Coutinho     Centro de Ciências e Tecnologias Nucleares (C²TN), Instituto Superior Técnico (IST), Universidade de Lisboa, Lisbon, Portugal

      Carmen Coya     Rey Juan Carlos University, Madrid, Spain

      Sanjay J. Dhoble     RTM Nagpur University, Nagpur, India

      Lorenzo Di Bari     Department of Chemistry and Industrial Chemistry, Pisa University, Pisa, Italy

      Farnoush Faridbod     University of Tehran, Tehran, Iran

      Mohammad R. Ganjali     University of Tehran, Tehran, Iran

      Zhanjun Gu     Institute of High Energy Physics, Chinese Academy of Science, Beijing, China

      Morteza Hosseini     University of Tehran, Tehran, Iran

      Luciana R.P. Kassab     Faculty of Technology of São Paulo, São Paulo, Brazil

      Fernando Lahoz     Departamento de Física, and IUdEA, Universidad de La Laguna, San Cristóbal de La Laguna, Santa Cruz de Tenerife, Spain

      Víctor Lavín     Departamento de Física, MALTA Consolider Team, and IUdEA, Universidad de La Laguna, San Cristóbal de La Laguna, Santa Cruz de Tenerife, Spain

      Inocencio R. Martín     Departamento de Física, MALTA Consolider Team, and IMN, Universidad de La Laguna, San Cristóbal de La Laguna, Santa Cruz de Tenerife, Spain

      Bernardo Monteiro     Centro de Ciências e Tecnologias Nucleares (C²TN), Instituto Superior Técnico (IST), Universidade de Lisboa, Lisbon, Portugal

      Jorge H.S.K. Monteiro     University of Nevada, Reno, NV, United States

      Laura C.J. Pereira     Centro de Ciências e Tecnologias Nucleares (C²TN), Instituto Superior Técnico (IST), Universidade de Lisboa, Lisbon, Portugal

      Ulises R. Rodríguez-Mendoza     Departamento de Física, MALTA Consolider Team, and IMN, Universidad de La Laguna, San Cristóbal de La Laguna, Santa Cruz de Tenerife, Spain

      Thejo N. Kalyani     Laxminarayan Institute of Technology, Nagpur, India

      Akhilesh Ugale     G.H. Raisoni Academy of Engineering and Technology, Nagpur, India

      Liviu Ungur

      KU Leuven, Leuven, Belgium

      National University of Singapore, Singapore

      Carlos Zaldo     Instituto de Ciencia de Materiales de Madrid, Consejo Superior de Investigaciones Científicas, c/ Sor Juana Inés de la Cruz 3, Madrid, Spain

      Shuang Zhu     Institute of High Energy Physics, Chinese Academy of Science, Beijing, China

      Francesco Zinna     Department of Chemistry and Industrial Chemistry, Pisa University, Pisa, Italy

      About the editors

      Pablo Martín-Ramos—Editor

      Pablo Martín-Ramos (ORCID ID: 0000-0003-2713-2786) obtained his Ph.D. from the University of Valladolid, Spain, in 2013 with Professor J. Martín-Gil. He conducted research as a Fulbright scholar at Columbia University (New York, USA) and as a DAAD scholar at Max Planck Institut für Festkörperforschung (Stuttgart, Germany). He joined the faculty of University of Zaragoza in 2015 as an Associate Professor. His primary research interests include lanthanide-based LCMDs and their applications in OLED technology and fiber optic communications, and g-C3N4-based composites for photocatalysis.

      Affiliations and Expertise

      Associate Professor, Higher Polytechnic School, University of Zaragoza, Carretera de Cuarte s/n, 22071, Spain. Email: pmr@unizar.es.

      Manuela Ramos Silva—Editor

      Manuela Ramos Silva (ORCID ID: 0000-0001-9555-8856) earned her Ph.D. from the University of Coimbra, Portugal, in 2002 under the guidance of Professor L. Alte da Veiga. She has carried out research at ILL and ESRF (Grenoble, France) and at Risø National Laboratory (Roskilde, Denmark). She has served as an Associate Professor in Condensed Matter Physics at the Physics Department of the University of Coimbra for 15 years, obtaining her Agregação in Experimental Physics in 2010. She has published over 250 scientific papers in peer-reviewed journals. Her current research interests are focused on the physical properties of molecular materials, with emphasis on molecular magnetism and nonlinear optics.

      Affiliations and Expertise

      Associate Professor, Department of Physics, University of Coimbra, P-3004-516 Coimbra, Portugal. Email: manuela@uc.pt.

      Author biographies

      Chapter 1

      Liviu Ungur graduated in Chemistry at the State University of Moldova (Chisinau) in 2005 and received his PhD from the University of Leuven, Belgium, in 2010, under the supervision of Prof. Liviu F. Chibotaru. In 2011–17, he was a fellow of the Flemish Science Foundation. In 2015–16, he worked at University of Lund with Per-Ake Malmqvist and Valera Veryazov. He received the Best PhD Thesis in Molecular Magnetism from the European Institute of Molecular Magnetism in June 2014. He is presently working in the Theory of Nanomaterials group at KU Leuven with Prof. Liviu F. Chibotaru. His research is oriented toward the development and application of novel approaches for the theoretical description of magnetism and magnetic interactions in mono- and polynuclear compounds containing strongly anisotropic metal sites, as well as the investigation of electronic structures, optic and magnetic properties of magnetic molecules deposited on various surfaces. Since June 2018, he is appointed at the Department of Chemistry at the National University of Singapore.

      Chapter 2

      Akhilesh Ugale, born in 1983, received his BSc in 2003 and his MSc (Physics) in 2005 from Amravati University, Maharashtra, India. He is presently an Assistant Professor and coordinator at the Engineering Department at G.H. Raisoni Academy of Eng. and Tech. in Nagpur. He is pursuing his PhD at RTM Nagpur University under the supervision of Prof. N.T. Kalyani and Prof. S.J. Dhoble, and his research work is focused on the synthesis of red light-emitting complexes for OLEDs.

      Thejo N. Kalyani obtained her MSc in Physics from Sri Venkateswara University, Tirupati, in 1998 and was awarded her PhD from RTM Nagpur University, Nagpur, in 2010. Her research interests are focused on the synthesis and characterization of novel RGB light-emitting materials and on the fabrication of OLEDs for solid-state lighting and display applications. She has published over 25 research articles in reputed national and international journals and has authored 13 book chapters, 10 textbooks, and a book on Principles and Applications of Organic Light Emitting Diodes (OLEDs) in Elsevier. She has been the recipient of Ruthrabatla Krishna Mohan Award-1996 and Mrs. Seetha Gopalakrishnan Award-1998. She was also honored with Young Scientist Award-2008 and several best research paper awards in various national and international conferences. She is associated with various professional bodies, such as the Material Research Society of India and the Luminescence Society of India.

      Sanjay J. Dhoble obtained his MSc degree in Physics from Rani Durgavati University, Jabalpur, in 1988 and his PhD degree on Solid-State Physics from Nagpur University, Nagpur, in 1992. He is especially working in the field of luminescence. During his research career, he has been involved in the synthesis and characterization of energy-saving LED materials, the development of radiation dosimetry phosphors using thermoluminescence technique for gamma ray and carbon ion beam, and the utilization of fly ash. He serves as an editor for Luminescence: The Journal of Biological and Chemical Luminescence. He has published more than 646 research papers in international and national peer-reviewed journals on solid-state lighting, LEDs, radiation dosimetry, phototherapy, and laser materials. Two patents were published in 2014 and 2017. He recently received Fellow of Luminescence Society of India, Best Research Award-2016 by RTM Nagpur University, Prof. B.T. Deshmukh Research Award-2016, Prof. B.P. Chandra Research Award-2016, and Outstanding Scientist 2015 Award by Venus.

      Chapter 3

      Ana de Bettencourt-Dias has an MSc in Technological Chemistry from the University of Lisbon and a PhD in Inorganic Chemistry from the University of Cologne. She was a Gulbenkian Postdoctoral Fellow at the University of California, Davis. In 2001, she joined the faculty at Syracuse University and became interested in the coordination chemistry and photophysics of lanthanide ions. In 2007, she was promoted to Associate Professor and in 2013 to Professor at the University of Nevada, Reno. She publishes extensively on luminescent lanthanide-containing materials and is the editor of the book Luminescence of Lanthanide Ions in Coordination Chemistry and Nanomaterials. Her editorial advisory board activities include the journals Inorganic Chemistry, Journal of Rare Earths, and Comments on Inorganic Chemistry. She is the 2018 Chair-Elect of the Division of Inorganic Chemistry of the American Chemical Society and Associate Vice-President for Research at the University of Nevada, Reno.

      Jorge H.S.K. Monteiro received his Licenciatura and MSc in Chemistry from São Paulo State University (Brazil) with Professor Marian Davolos and his PhD in Chemistry from University of Campinas (Brazil) in 2014 with Professor Fernando Sigoli. He is currently a Postdoctoral Scholar in Ana de Bettencourt-Dias' research group at the University of Nevada, Reno. He has 1 patent, more than 20 publications in peer-reviewed scientific journals, and 8 h-index. His current research interests are the development of new theranostics and lanthanide luminescent complexes for bioimaging using excitation in the biological window.

      Chapter 4

      Carmen Coya was born in Madrid in 1968. She completed her Doctorate at the Institute of Materials Science of Madrid (CSIC) and works at Rey Juan Carlos University of Madrid, where she is Full Professor in Electronics. She is a founding member of the Research Group in Organic Optoelectronics (OOG) and directs the Laboratory of Characterization of Organic Devices (LABCADIO), belonging to the network of laboratories of excellence in Madrid (cod-351). Her lines of research are currently focused on the development of materials, manufacturing of devices, and optimization of profitable processes for organic electronics: hybrid materials based on graphene and organic-inorganic hybrids for optoelectronic applications.

      Ángel L. Álvarez received his MSc degree in Physics from Universidad Complutense de Madrid in 1990 and his PhD from ETSI Telecomunicación, Universidad Politécnica de Madrid, in 1996. Since 2007 to date, he has been an Associate Professor in Electronics at Universidad Rey Juan Carlos. With more than 25 years of experience in solid-state electronics, he has been involved in OLED manufacturing in the last 15 years, and his current interests cover infrared light-emitting devices and graphene/graphene oxide optoelectronic properties.

      Chapter 5

      Lorenzo Di Bari received his BSc and PhD in Chemistry from the University of Pisa and the Scuola Normale Superiore (Pisa). He worked a few years in Switzerland and in Sweden on NMR tools for conformational analysis of organic compounds. He returned to Pisa in 1992, where he started to work on chiroptical spectroscopies. Currently, he is a Professor of Organic Chemistry in Pisa, and his main research interests focus on the relationships between molecular and supramolecular structure and chiroptical properties of organic compounds and lanthanide complexes. Since 2000, he has been the member of the Editorial Board of the journal Chirality, and since 2009, he is in the International Advisory Board of the International Conference on Chiroptical Spectroscopies.

      Francesco Zinna received his PhD from the University of Pisa in 2016 under the supervision of Prof. Lorenzo Di Bari, working mainly on circularly polarized luminescence. He is currently a Postdoctoral Assistant at the University of Geneva in the group of Prof. Jérôme Lacour. His scientific commitment is mainly focused on (chiro)optical spectroscopies of both purely organic and lanthanide-based compounds, with a strong interest in basic and applied aspects of circularly polarized luminescence.

      Chapters 6 and 7

      Joana T. Coutinho received her PhD in Chemistry from Universidade de Lisboa in 2017, under the supervision of Doctor Laura C.J. Pereira and Prof. Eugenio Coronado. Her research is mainly focused on the magnetic properties of f-elements with potential as single-molecule magnets. She recently started a postdoctoral position at Instituto de Ciencia Molecular (ICMol), where she continues to pursuit the explanation behind the interesting behavior of these molecular magnets.

      Bernardo Monteiro graduated from the Department of Chemistry, Faculdade de Ciências da Universidade de Lisboa in 2000. After working in f-element coordination chemistry at the Nuclear and Technological Institute (now C²TN), he received his PhD degree from Aveiro University in 2009, under the supervision of Prof. Isabel S. Gonçalves and Martyn Pillinger, working on the functionalization of layered double hydroxides with d-metal complexes to be applied as heterogeneous catalysts. Since then, he has been working as a Postdoctoral Fellow at C²TN, and his research interests involve layered lanthanide hydroxide materials, host-guest systems, f-element coordination chemistry, MOFs, single-molecule magnets, and optical sensors.

      Laura C.J. Pereira received her BSc degree in Chemistry (1989), MSc in Physical Chemistry of Materials (1993), and PhD in Inorganic Chemistry (1998) (with Prof. Manuel Almeida), from the Faculty of Sciences, University of Lisbon. During her doctoral studies, she worked as Research Fellow with Doctor Jean-Claude Spirlet at the Actinide Research Group of the Institute for Transuranium Elements (ITU), EC-JRC, Karlsruhe, Germany, (September 1993–August 1996). Currently, she is a Senior Researcher at DECN, IST, Universidade de Lisboa. Her main research interests are focused on new advanced materials, with special emphasis in the establishment of detailed correlations between molecular and crystalline structure with the magnetic properties, namely, in multifunctional and nanostructured materials, single-molecule magnets, and intermetallic compounds with d- and f-elements.

      Chapter 8

      Luciana R.P. Kassab serves as a Full Professor of Physics at Faculdade de Tecnologia de São Paulo since 1992. She graduated in Physics from Pontifícia Universidade Católica de São Paulo (1983) and obtained her MSc (1987) and PhD (1996) in Physics from Instituto de Física da Universidade de São Paulo (Brazil). She has been the Director of Faculdade de Tecnologia de São Paulo in the period since 2006. She has published over 100 peer-reviewed papers and several invited chapters, and holds IP related to heavy metal oxide glasses for laser applications. Her current research interests are metal dielectric nanocomposites based on germanate and tellurite hosts with enhanced luminescent properties, fabrication processes of pedestal waveguides for integrated photonics, plasmonic effects on the optical gain of rare-earth-doped waveguides, and non-linear optical effects for ultrafast optical devices.

      Maria J.V. Bell is a Full Professor of Physics at Universidade Federal de Juiz de Fora since 2000. She graduated in Physics from Universidade Federal do Paraná (1988) and obtained her MSc degree (1992) from the Instituto de Física de São Carlos, Universidade de São Paulo, and her PhD degree (1997) in Physics from the Universidade Estadual de Campinas (Brazil). She has coordinated the graduate program in Physics of the Universidade Federal de Juiz de Fora (2004–07) and the Optics and Photonics Commission of the Brazilian Physical Society (SBF), and is also part of the Advisory Board of the Minas Gerais State Agency for Research and Development—FAPEMIG. She has published over 80 peer-reviewed papers and has invention patents related to phosphosilicate glasses doped with rare-earth ions for laser and dosimetry applications. Her research focuses on the optical and spectroscopic properties of condensed matter, with emphasis on rare-earth ions, luminescence, energy transfer, and thermooptical properties of materials.

      Chapter 9

      Víctor Lavín received his PhD degree from University of La Laguna (Spain) in 2000 and worked as a postdoc at the Faculty of Physics at Paderborn University (Germany). Since 2003, he is a Professor at the Department of Physics at University of La Laguna, where he is a member of the Laser Spectroscopy and High Pressure Group. He is the author of over 110 scientific papers in peer-reviewed journals. His research interests cover the optical characterization of lanthanide-doped optically active materials (glasses, glass-ceramics, crystals, and nanocrystals) at ambient and at extreme conditions of pressure and/or temperature.

      Inocencio R. Martín received his PhD from the University of La Laguna in 1996. He is an Associate Professor at the Department of Physics at this University and a member of the Laser Spectroscopy and High Pressure Group. His research interests encompass the optical characterization of glasses, crystals, and nanocrystalline glass-ceramics doped with optically active ions. He has over 180 publications in peer-reviewed journals. He is presently focused on the optical characterization of microspheres doped with rare-earth ions and their applications as sensors.

      Fernando Lahoz earned his PhD degree in Condensed Matter Physics from the University of Zaragoza, Zaragoza, Spain, in 1996. After 2 years at the Laboratoire d'Analyse et d'Architecture des Systèmes (CNRS), Toulouse, France, working on the fabrication and characterization of dielectric waveguide lasers, he joined the University of La Laguna, S.C. Tenerife, Spain, where he is a Lecturer in Electromagnetism. His interests include optical spectroscopy of rare-earth ions, dye lasers, bulk glass and crystal lasers, waveguides, and optical amplifiers. He collaborates with the Spanish Research Council in the development of optical sensors based on microresonators. He is currently involved in research projects on luminescent materials for energy and biomedical applications.

      Ulises R. Rodríguez-Mendoza received his PhD in 2000 from University of La Laguna and at present holds a tenure-track position in the same university. He is a member of the Laser Spectroscopy and High Pressure group, and his research interests cover the optical characterization of glasses, crystals, and nanocrystals doped with optically active ions at ambient and extreme conditions of pressure and temperature, which includes optical spectroscopy, X-ray diffraction, and Raman spectroscopy. He has over 80 publications in refereed journals and conference proceedings. Presently, he is working on optical sensors of temperature and/or pressure based on rare-earth-doped materials.

      Chapter 10

      Carlos Zaldo was born in 1956 in Madrid, Spain. He received his PhD degree from the Autonomous University of Madrid (UAM) in 1984. After working as a Postdoctoral Fellow (1984–85) at ETH, Zürich, he joined ICMM-CSIC in 1986, where presently holds a Research Professor Chair. He has taught at UAM, Carlos III and Politécnica Universities in Madrid. He worked as a visiting fellow at ORC, Southampton (1993), and at St. Andrews University (2009). His current research interests include the use of lanthanide ions in photonics, femtosecond pulsed lasers, crystal growth of disordered oxides, photonic nanoparticles, upconversion applications, and spectroscopic techniques.

      Chapter 11

      Shuang Zhu received her BSc in Pharmacy (2013) and MSc in Nutrition (2016) at Shandong University and Seoul National University, respectively. She currently works as a Research Assistant under the supervision of Prof. Zhanjun Gu at CAS Key Laboratory for Biomedical Effects of Nanomaterials and Nanosafety of the Institute of High Energy Physics, Chinese Academy of Science. Her research focuses on the synthesis of nanomaterials and on the exploration of their biosafety and biomedical applications.

      Zhanjun Gu received his BEng degree (2002) from Huazhong University of Science and Technology and his PhD degree (2007) from the Institute of Chemistry, Chinese Academy of Science, under the direction of Prof. Jiannian Yao. He then became a Postdoctoral Fellow at the University of Georgia. In 2009, he joined the faculty at CAS Key Lab for Biomedical Effects of Nanomaterials and Nanosafety of the Institute of High Energy Physics, Chinese Academy of Science. His current research interests include nanomaterial synthesis, optical spectroscopy, and bioapplications of luminescent nanomaterials.

      Chapter 12

      Farnoush Faridbod has a PhD in Analytical Chemistry obtained at University of Tehran in 2009. She currently works as an Assistant Professor at University of Tehran. Her research work has mainly been focused on the design of new chemical sensors and biosensors.

      Mohammad R. Ganjali has a PhD in Analytical Chemistry obtained at University of Tehran in 1997. He currently works as a Full Professor at University of Tehran. His research work has been mainly focused on the design of new chemical sensors based on nanomaterials and has coauthored 900 papers, with over 22,800 citations (h-index 83).

      Morteza Hosseini has a PhD in Analytical Chemistry obtained at Tarbiat Modares University in 2005. He is currently an Associate Professor in the Nanobiotechnology group at the Faculty of New Sciences and Technologies of University of Tehran. His research work has mainly been focused on the design of new optical nanosensors and nanobiosensors.

      Foreword

      It is a pleasure to be asked by the Editors to write a foreword for Lanthanide-Based Multifunctional Materials: From OLEDs To SIMs. This is a book that can serve as an introduction to the field for newcomers and students, as well as a reference for experienced researchers, in the rapidly growing field of lanthanide-based materials. Multifunctional materials are also a rising topic that brings together materials science, chemistry, biomedical, physics, and engineering communities.

      What better than lanthanides to be at the core of materials capable of multiple functions? They offer unique electronic, optical, magnetic, and catalytic properties, exemplified by their large intrinsic magnetic moment and narrow-band transitions between states with different electric/magnetic dipole moments. Lanthanides have long found their place in industry as catalysts, phosphors and magnets, and remain on the cusp of new scientific discoveries as multi-modality imaging agents or as qubit holders in quantum computing.

      The book reviews many aspects of the recent developments in research on lanthanide materials, from the description of their physical properties to current and expected applications. It will be of great use for all scientists working in this field.

      The contents are clear and appealing. I wish the reader the same pleasure and interest I have found in them myself.

      William Gillin, School of Physics and Astronomy, Queen Mary University of London, London, United Kingdom

      Preface

      Lanthanides have become part of our daily life and are at the forefront of many contemporary technologies. Their chemical and physical properties provide solutions for many challenges of modern society, having found applications in communication and consumer electronics, as catalysts, in lighting products, in displays, in the ceramics industry, in advanced optics and other glasses, in batteries, in permanent magnets, or in life science, to name a few. Beyond these main market sectors and products, lanthanides are also increasingly being used in other niche markets, which encompass nuclear technologies, laser or microwave crystals and garnets, carbon arc lights, textiles additives, paint siccatives, alloys for magnetic refrigeration, etc.

      This book does not aim to cover those already well-established applications, but instead it focuses on the importance of lanthanides for novel key-enabling technologies, of strategic relevance for development and innovation, which have rapidly blossomed in the past few years. In particular, it aims to deliver a panorama of the latest progress on lanthanide-based multifunctional materials, placing emphasis on their applications, associated to red-hot research fields at this moment.

      The accelerating number of literature reports on these materials makes it difficult to have a broad perspective of the field. Though some excellent review articles have covered one or another aspect of lanthanide applications, books with a wide and up-to-date coverage of the field—focused on applications rather than on fundamental science—are rather scarce. This book is primarily intended for academic and industrial researchers from the Materials Science, Applied Physics, and Applied Chemistry areas. It should not only allow experienced readers to stay informed of the most recent developments, but it should also serve as an in-depth introduction for those who are new to this area of knowledge. The contributors are university Professors and leading scientists in this field, who—in addition to having made significant contributions during the last few years in terms of publications—have also promoted transfer of technology (through patents and collaborations with companies and ventures). An effort has been made to combine scientific rigor with a pedagogical approach, so that undergraduate and postgraduate students alike can also highly benefit from the reading of this book.

      The introductory chapter sets the tone by describing the fundamentals of the optical and magnetic behavior of lanthanides and how these properties can be predicted by ab-initio methods. In line with the book's subtitle, Chapters 2–5 are devoted to lanthanide-based organic-light-emitting diodes (OLEDs), including not only the latest trends in visible emitters, but also the emerging field of near-infrared emitters and the first achievements attained in the promising field of chiral OLEDs.

      The use of lanthanide complexes as molecular magnets spreads over another two sections (Chapters 6 and 7), which explain the evolution of 4f-elements-based single-ion magnets and the most recent advances in heterometallic 3d–4f single-molecule magnets, together with useful strategies for a rational design of new materials for information storage.

      Other very active research areas are covered in Chapters 8–12, which are dedicated to lanthanide-doped germanate and tellurite glasses for lasers, waveguides, and ultrafast devices; luminescent materials for upconversion, aimed at enhancing the efficiency of current photovoltaics and photocatalysis processes; luminescent thermosensors that are immune to electromagnetic fields, and which feature fast response, non-contact character, and high spatial resolution; multimodal imaging and therapeutic agents that can pave the way to the detect-to-treat strategy in biomedicine; and chemosensors for electrochemical and optical sensor/biosensor systems.

      We would like to express our sincere thanks to all the contributors for providing their unique view to a hopefully broad audience, while warmly welcoming our suggestions and remarks throughout the iterations of the review process. With their dedication, they have been instrumental for the success of this book project. We wish to extend our warmest thanks to the team at Elsevier (Charlotte Rowley and Kayla Dos Santos) for their continued support.

      Finally, we gratefully acknowledge the following funding agencies that provided support during the period of emergence of the book: the European Union through CA COST Action CA15128 - Molecular Spintronics (MOLSPIN), Fundação para a Ciência e a Tecnologia (FCT) through project UID/FIS/04564/2016 and Santander Universidades through the Becas Iberoamérica Jóvenes Profesores e Investigadores, España scholarship program.

      Pablo Martín-Ramos; Manuela Ramos Silva

      Coimbra, January 2018

      1

      Introduction to the electronic structure, luminescence, and magnetism of lanthanides

      Liviu Ungur⁎,†    ⁎ KU Leuven, Leuven, Belgium

      † National University of Singapore, Singapore

      Abstract

      This introductory chapter describes theoretical tools and methods employed for the description of the optical and magnetic properties of lanthanide compounds. First, we introduce the electronic structure of the free lanthanide ions in gas phase, a multiplet structure with an overview of the effect of the ligand (crystal) environment on the low-lying multiplets. Second, crystal and ligand field theories applied in this field are briefly introduced together with their grounds and drawbacks. The foundations of the Judd-Ofelt theory describing the intensities of the optical transitions in lanthanide compounds are discussed. Recent advances in the ab initio theoretical methods used for the description of lanthanide complexes are introduced. Further, theoretical requirements for top-performant molecular magnets are reviewed alongside a brief review of the recent top-performant molecular magnets obtained experimentally. Finally, a personal opinion regarding the future (theoretical) work that needs to be done in this area is given.

      Keywords

      Ab initio; Judd-Ofelt; Lanthanide complexes; Molecular magnets

      1.1 Introduction

      Lanthanide ions are at the core of many important applications given their unique electronic, optical [1–9], magnetic [10–16], and catalytic [17–20] properties. The large intrinsic magnetic moment of lanthanide ions defines the blocking of magnetization behavior in molecular nanomagnets [21–23] and also plays an important role in strong macroscopic permanent magnet materials, such as Nd2Fe14B [24–26]. The sharp and intense luminescence displayed by lanthanide ions in various crystal environments is due to the narrow-band transitions between states with different electric/magnetic dipole moments. Lanthanides are also employed as contrast agents in magnetic resonance imaging medical investigations [2,27,28] and serve as important ingredients in commercial lasers [29]. The list of industrial and scientific applications of lanthanide ions is far from being complete. Some of the applications of lanthanides are shown in the following chapters of the present book. The purpose of this chapter is to describe the basic features of the electronic structure of lanthanide ions and to review theories used to explain their electronic structure, optical and magnetic properties.

      1.1.1 Free lanthanide ions: Electronic spectra and nature of wave functions

      In the absence of ligand environment, the electronic structure of free atoms is defined by the electrostatic interactions between each of the electrons and the central nucleus. In the simplest Hartree-Fock approximation, each electron feels the potential of the nucleus combined with an averaged potential of all the other electrons in the system. In this approximation, the wave function of each electron depends on four quantum numbers (n, l, m, and ms) and may be expressed as follows:

        

      (1.1)

      where Rnl(r) is the one-electron radial wave function, which depends only on the distance to the nucleus (r); Ylm(θ, φ) is spherical harmonics; and χms(σ) is spin eigenstates of the electron (ms = ±1/2). r(r, θ, φ) is the position vector of the electron. These one-electron eigenstates (Eq. 1.1) are used as basis states in the representation of the multielectronic atoms.

      Electrons in free lanthanide ions are coupled and form configurations (nlN), in the first approximation. An electronic configuration is a definite arrangement of all electrons in atomic-like orbitals. Ground electronic configuration of neutral free lanthanide atoms is [Xe]5d⁰6s²4fN+1, with small exceptions for La, Ce, Gd, and Lu, for which the ground configuration is [Xe]5d¹6s²4fN. In common complexes, the outer shell electrons spanning the atomic 5d and 6s orbitals possess relatively large radii and are highly susceptible to ligand field, and generally, the three outer electrons can be easily removed from the free lanthanide ion system. The relatively low ionization potential is due to the screening effects, which notably weaken the Coulomb interaction between 5d and 6s electrons and the nucleus [30,31]. The remaining triply ionized configuration for Ln³+ ([Xe]4fN5d⁰6s⁰) is very stable for the entire lanthanide series and dominates the wave function in the ground state. Relatively stable chemical compounds with Ce⁴+, Sm²+, Eu²+, Tb⁴+, Tb²+, Dy²+, and Yb²+ are also known [32–34]. In the present introductory chapter, we will restrict the discussion to the most common oxidation state (3+) of lanthanide ions.

      Since the electronic configuration of the [Xe] core is similar for the entire series of lanthanides, one may conclude that it is the partial filling of the 4fN shell (1 ≤ n < 14) that defines the properties of lanthanide ions. For the triply ionized lanthanide ions, excited electronic configurations like [Xe]4fN−15d¹, [Xe]4fN−16s¹, or [Xe]4fN−16p¹ are usually much higher in energy compared with the ground configuration (> 5×10⁴ cm−1) [35] and are used in various spectroscopic techniques.

      The N-electronic wave function of any configuration must respect the Pauli antisymmetry principle, which states that the wave function must change its sign when any two electrons exchange their coordinates. The most straightforward way to account for this principle is to represent the multielectronic wave function in the form of a Slater determinant:

        

      (1.2)

      where αi represents all quantum numbers (n, l, m, and ms) of electron i, while ψαi(ri, σi) is monoelectronic wave functions, in the form given by Eq. (1.1).

      In general, the energy state corresponding to a given configuration (e.g., 4fN or 4fN−15d¹) is highly degenerate. This means that there are many different Slater determinants corresponding to the same energy. Indeed, even though the main quantum numbers for the 4fN configuration are well defined (n = 4 and l = 3), the projection of the orbital momenta m of each electron can take any value from −3 to +3, while spin projection ms may have either one of the two values α (ms = +1/2) or β (ms = −1/2). As a simple example, we may take Ce³+, which has the ground configuration [Xe]4f¹. The unpaired electron of the last shell may occupy any of the seven f orbitals, while the spin projection may be either α or β. For this electronic configuration, there are 7×2 = 14 Slater determinants that are equally probable (in the absence of other interactions).

      1.1.2 Coulomb repulsion effects

      The degeneracy of the 4fN configurations where N > 1 is partly removed by electron correlation and intraionic spin-orbit coupling effects. The most important correlation effects include the Coulomb interaction (repulsion) between the N unpaired electrons from the last shell and exchange interaction between them. Within the one-electron picture approach, the effect of the core electrons ([Xe]) on the 4fN shell is constant, does not lead to splitting and therefore will not be considered in the discussion. The orbital states that arise after full-electron correlation within a given configuration is considered are called terms. In the case of free ions, terms are also highly degenerate. From another perspective, terms of a given N-electron system in spherical symmetry are characterized by a given total spin (S) and total orbital momenta (L), following the principle of conservation of angular momenta for an N-particle system. This results also from the general considerations of commutativity of the electronic Hamiltonian and the operators of total orbital and spin momenta, L² and S². Since terms correspond to different irreducible representations of the spherical symmetry group, they are not bound to have the same energy. It is convenient to recall Hund's rules for the term's energy:

      •Among all possible terms of a given configuration, the terms with the largest total spin multiplicity (2S+1) have the lowest energy.

      •Among all possible terms with the largest total spin multiplicity (2S+1), the term with the largest total orbital momentum has the lowest energy.

      There are many possibilities to combine individual electron's spin and angular momenta in a many-particle system to build eigenstates of a given term, for instance, by following addition rules for angular momenta [36]. Total degeneracy (number of states with the same energy) of a term with definite values of L and S is (2L+1)(2S+1).

      Energy spread of different terms arising from the same configuration is of the order of ~10⁵ cm−1, while the energy difference between the ground and first excited terms is in the order of ~10⁴ cm−1. Terms are denoted by ²S+1L, where S is the total spin and L is the letter defining the total orbital momentum (L = 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, … → S, P, D, F, G, H, I, K, L, M, …). As an example, the ground term of Ce³+ ion (4f¹, L = 3, S = 1/2) discussed above is ²F. In certain cases, terms with the same quantum numbers L and S may arise from different electron configurations. Such terms interact with each other via the electronic Hamiltonian.

      Sometimes, it is convenient to represent the eigenstates of a given term as |L, S, ML, MS⟩, where ML and MS are projections of the total orbital and total spin momenta, rather than in a linear expansion of Slater determinants.

      1.1.3 Spin-orbit coupling

      Spin-orbit coupling is an intrinsic effect of relativistic origin that leads to partial removal of degeneracy of electronic terms. It may be regarded as the interaction of the spin (s) of the electron with the magnetic field created by the same electron while moving in the closed orbit (l):

         (1.3)

      where V(r) is the potential of the central nucleus, c is the speed of light, m is the mass of the electron, r is the distance to the nucleus, and e is the electron charge. Within the first-order perturbation theory, the effect of spin-orbit interaction is dominated by the constant:

         (1.4)

      For a nucleus with potential V = Ze/r, the spin-orbit coupling depends on the given electron configuration nl:

         (1.5)

      From Eq. (1.5), it is clear that the spin-orbit coupling constant is strongly dependent on the atomic number Z, so it is element specific. For lanthanide ions, the effect of spin-orbit coupling is still reasonably described in the Russell-Saunders coupling scheme, that is, the effect of spin-orbit coupling on the radial functions is minor, and Eq. (1.1) is valid. For heavy atoms, the representation of the wave function as a product between orbital and spin functions (as in Eq. 1.1) is not accurate. In those cases, electron correlation effects and spin-orbit coupling must be simultaneously accounted, in the relativistic framework, by solving the two- or the four-component Dirac equation [37,38].

      Spin-orbit interaction in a given term with definite total orbital L and spin S momenta is approximately given by

         (1.6)

      where ζnl is the one-electron spin-orbit coupling constant for the ground configuration nl of the metal ion [39]. The negative sign in Eq. (1.6) is for elements with more-than-half-filled shell, i.e., from Tb³+ to Yb³+. Approximate values of the ζ4f parameter for the entire lanthanide series as extracted from NIST data are given in Table 1.1. Since the spin-orbit operator in Eq. (1.6) does not commute with the L² and S² operators, these quantum numbers are not conserved. Instead, the spin-orbit Hamiltonian in Eq. (1.6) commutes with the square of the total angular momentum J², implying that only the total angular momenta quantum number J = L+S is conserved. Following the rules for addition of two angular momenta, the quantum number J takes positive values running from |L−S| to L+S, with a step of 1. As an example, spin-orbit interaction within the ground ³F term of Pr³+ ion (L = 3, S = 1) splits it in three multiplets with J1 = (3−1) = 2, J2 = (3−1+1) = 3, and J3 = (3−1+2) = (3+1) = 4. In order to uniquely identify the multiplets originating from various terms, they are written in the format: ²S+1LJ. For example, the three multiplets arising from the ³F term are ³F2, ³F3, and ³F4. Hund's rule coupling allows to determine which of the multiplets will be in the ground state:

      •Among all possible multiplets arising from the ground term, the lowest will be J = |L−S| for a less-than-half-filled nl shell and J = L+S for a more-than-half-filled nl shell.

      Table 1.1

      Energy differences correspond to NIST data [35]. The spin-orbit coupling parameter is extracted from the NIST data and Eq. (1.6).

      a ζ4f was extracted by using the NIST data for the J multiplets originating from the ground LS term to best fit (Eq. 1.6).

      b Spin-orbit coupling is absent for the ground state of Gd³+: L = 0 and J = S.

      In order to compute the energies corresponding to the J eigenstates, we need to rewrite the spin-orbit Hamiltonian as follows:

        

      (1.7)

      for a given multiplet is diagonal when written in the basis of |L, S, J, MJ⟩ coupled eigenstates (Eq. 1.5)

        

      (1.8)

      are Clebsch-Gordan coefficients describing the coupling between two angular momenta L and S in a total angular momenta |J, MJ⟩ [36]. Clebsch-Gordan coefficients become zero whenever any of the following relations ML + MS ≠ MJ, ML ≥ L, MS ≥ S, or MJ ≥ J are true.

      Energies corresponding to individual J states are as follows:

        

      (1.9)

      The energy gap between J and J−1 eigenstates is given by the Landé interval rule [40]:

        

      (1.10)

      Deviations from the Landé interval rule are noticed for systems containing several unpaired electrons (see Table 1.1 and Fig. 1.1). This is explained by the coupling between identical J multiplets that arise from different LS terms via spin-orbit coupling.

      Fig. 1.1 NIST experimental energies [35] of the low-lying multiplets of free Ln³+ ions. Labels of some overlapping multiplets are not shown for clarity reasons. Energy states are plotted at the true scale.

      1.1.4 Crystal field splitting

      When a lanthanide ion is placed in a low-symmetry crystal matrix, each multiplet of the lanthanide becomes further split in individual components, either in Kramers doublets for odd-electron systems (Ce³+, Nd³+, Sm³+, Gd³+, Dy³+, Er³+, and Yb³+) or in individual nondegenerate levels for even-electron systems (Pr³+, Pm³+, Eu³+, Tb³+, Ho³+, and Tm³+). This splitting depends on the properties of the ligand environment and is usually in the order of 300–1500 cm−1. Crystal field theory, which is one of the first to explain the effect of the ligand environment, is based on the following approximations [41,42]:

      •Only the 4f electrons of the lanthanide are considered. The effect of the metal's core orbitals or virtual (empty) orbitals is neglected.

      •The effect of the ligand atoms is limited to providing an external (electrostatic) potential that influences the 4f shell. This effect is considered a small perturbation over the free-ion spin-orbit multiplet structure.

      •No overlap between metal and ligand's orbitals is considered.

      Fig. 1.2 shows a rank of various interactions leading to the splitting of the initial 4fN configuration in lanthanides.

      Fig. 1.2 Effect of various interactions on the splitting of the degenerate 4 f ⁹ configuration of the free Dy ³ + ion. Interactions are ranked from strong ( left ) to weak ( right ). Only the splitting of the ground state is shown for clarity, while it should be understood that excited states are subject to similar splitting effects. As a result of all interactions, on the right-hand side of the picture, the individual levels are thus fairly mixed. Energy splitting is not plotted at scale. Zeeman splitting is caused only by an applied magnetic field.

      The description of the crystal-field splitting is done via an effective one-electron Hamiltonian:

        

      (1.11)

      is the contribution to the total Hamiltonian from electron i, Bkq is the crystal-field parameter of rank k (k ≤ 6) and projection qis the crystal-field operator acting on electron i. It is related to the spherical harmonics multiplied by a coefficient:

         (1.12)

      The operator in Eq. (1.12) acts on individual electrons of the last shell. It may be proved to be equivalent to a different form of the crystal-field Hamiltonian operator that acts on the ground J multiplet [41,43]:

        

      (1.13)

      are the real and the complex combinations of the spherical harmonics (Table 1.2), respectively, with the dimension 2J+1, Bkq, and Ckq corresponding with (real) crystal-field parameters.

      Table 1.2

      —real.

      It is clear that a direct application of Eq. (1.11) or Eq. (1.13) for a lanthanide in a low-symmetry environment requires knowledge of the entire set of 27 Bkq parameters. One approach to compute the Bkq parameters is to use the point-charge model (PCM) [40,44–46]. In this model, the Bkq parameters (Eq. 1.11) are given by the effective charge (Zi) on the neighboring ligand atoms according to their crystallographic positions (ri, θi, and φi) as follows:

         (1.14)

      Directly applied in this form, the PCM gives large deviations from available experimental data. One reason is that the charges on neighbor ligand atoms are not easily determined. Employment of their (chemical) charge only gives a qualitative description of the data.

      The crystal field theory is now mainly used as a phenomenological approach. In this model, the Hamiltonian in Eq. (1.13) is computed in the basis of |L, S, J, MJ⟩ spin-orbit eigenstates of the ground J term using some values of the Bkq parameters and diagonalized. The resulting 2J+1 eigenstates are used to compute some properties, for example, magnetic susceptibility, molar magnetization, some experimental (known) energy states, and EPR spectra. Bkq parameters are varied until the standard deviation between computed and measured data decreases below some chosen threshold. An alternative is to build the crystal-field matrix in the basis of the complete set of eigenstates originating from the 4fN configuration. In such case, the crystal field will also mix excited multiplets, allowing a slightly improved description of the thermodynamic properties (e.g., magnetic susceptibility). The latter method is of choice when optical properties are described.

      Some of the negative points of this phenomenological approach are (i) the overparameterization problem (impossibility to reliably fit a set of 27 independent parameters, since more than one set would provide the same quality of the description) and (ii) the common way of overcoming this difficulty by fitting only 3–4 parameters and disregarding the remaining 23–24 parameters. Symmetry considerations allow to effectively reduce the number of independent parameters. As Table 1.2 shows, the number of crystal-field parameters that need to be considered allows a reliable fit only for the highest point groups, cubic or hexagonal. Compounds with lower symmetry are practically intractable.

      Phenomenological approaches involving displacement of ligand charges out of the metal-ligand axis have also been proposed [47]. In some cases, these methods gave a better agreement with experiment. It is important to mention here that even if the method of obtaining the parameters of the crystal field is improved or optimized, the number of independent fitting parameters remains the same. Improvements in the point-charge model and related approaches require to explicitly account for more involved physical effects:

      •Effect of further distant ligand atoms

      •Spatial distribution of the ligand electron density, including metal-ligand exchange interaction

      •Nonorthogonality between metal and ligand's orbitals

      •Nonorthogonality between metal's core, 4f, and ligand's orbitals

      •Multiconfiguration approaches accounting for polarization, covalence, and screening effects

      Clearly, a more involved model description increases the number of parameters that need to be determined/provided. As an example, the screening effects of the 5s²5p⁶ closed shells on the crystal-field splitting of the 4fN shell is accounted for by a modified crystal-field Hamiltonian:

        

      (1.15)

      where σk is additional phenomenological parameters w.r.t. Eq. (1.11). The role of σk screening factors is mainly to change the ratio between different rank operators. Similarly, charge penetration effects could be accounted for by additional parameters ηk, which depend on the operator rank [41,48]. As an example, corrected crystal-field parameters are as follows:

         (1.16)

      Developments of the crystal field theory to include the (missing) covalent effects along the electrostatic contribution [49] and novel methods based on the parameterization of the metal-ligand covalence interaction, like the angular overlap model, have been developed over time [50,51]. These methods are also mainly phenomenological, since the number of parameters grows significantly in the case of nonequivalent ligands.

      There are many computer codes and programs that implement crystal field theory for the computation of electronic structure and properties of lanthanide compounds. Among the most popular ones, we could mention SIMPRE [52,53], PHI [54], CONDON [55], etc.

      A recent approach to determine the parameters of the crystal field is to use rigorous ab initio quantum chemistry methods [22,56–59]. This approach will be briefly introduced in a latter section.

      1.2 Theoretical description of optical behavior of lanthanides

      1.2.1 Optical transitions

      Lanthanide ions in various hosts display an interesting optical behavior manifested in relatively sharp and intense luminescence, making them important ingredients in the technological design of lasers and various optical sensors. This property of lanthanide ions was quite puzzling for many years, given the inability of existing theories at that time to provide a reasonable explanation of its origin.

      From the point of view of electronic structure, energy states in materials are quantized (discrete). Transitions between any two states are accompanied by the absorption or emission of electromagnetic radiation with an energy corresponding to the exact energy difference between the two states (Eq. 1.17 and Fig. 1.3):

         (1.17)

      Fig. 1.3 Ground and excited configurations of opposite parity of lanthanide ions. Transition dipole moment between these two states is allowed. Following Judd-Ofelt theory, the opening of the transition dipole moment between the low-lying states (with dominant 4 f N character) arises due to the small admixture of the states from excited configurations of opposite parity to the ground states, via crystal-field effect.

      There are many physical phenomena that may lead to transitions between two states: electric dipole (ED) transition, magnetic dipole (MD) transition, electric quadrupole (EQ) transition, etc. Eq. (1.18) gives the explicit forms of these operators:

         (1.18)

      The intensity of an electronic transition is proportional to the square of the matrix element of the corresponding operator expressed in the basis of the initial (j) and final (i. The transition is said to be forbidden whenever this matrix element is zero, and otherwise, it is allowed. Given the fact that all the operators that are responsible for the various transitions (Eq. 1.18) commute with the symmetry operators of the entire system, symmetry rules may be used to determine if a transition is allowed or not. The symmetry characteristics of each component of the operator (e.g., Cartesian axes x, y, or z . If this function spans the totally symmetrical representation of the respective group (denoted by A, A1, Ag, or A′, having characters of all group operators as 1), then the transition is allowed, and otherwise, it is forbidden. It is important to mention that, even though some transitions are electronically forbidden, in some cases, the experimental spectra may show those transitions, induced by various effects that were not included in the theoretical approach, for example, vibronic interactions. For a quantitative study of the intensity of transitions, all allowed transition moment matrix elements between all states need to be evaluated.

      It is instructive to briefly discuss the electric dipole transitions for lanthanide ions. As previously mentioned, the ground multiplet wave function is a linear combination of Slater determinants with various distributions of N electrons among the 4f orbitals, that is, arising from the 4fN ground configuration. For simplicity's sake, let us consider the Ci point group (inversion). All

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