Luminescence of Lanthanide Ions in Coordination Compounds and Nanomaterials

This comprehensive book presents the theoretical principles,
current applications and latest research developments in the field
of luminescent lanthanide complexes; a rapidly developing area of
research which is attracting increasing interest amongst the
scientific community.

Luminescence of Lanthanide Ions in Coordination Compounds and
Nanomaterials begins with an introduction to the basic theoretical
and practical aspects of lanthanide ion luminescence, and the
spectroscopic techniques used to evaluate the efficiency of
luminescence. Subsequent chapters introduce a variety of different
applications including:

• Circularly polarized luminescence

• Luminescence bioimaging with lanthanide
  complexes

• Two-photon absorption of lanthanide complexes

• Chemosensors

• Upconversion luminescence

• Excitation spectroscopy

• Heterometallic complexes containing lanthanides

Each chapter presents a detailed introduction to the
application, followed by a description of experimental techniques
specific to the area and an extensive review of recent
literature.

This book is a valuable introduction to the literature for
scientists new to the field, as well as providing the more
experienced researcher with a comprehensive resource covering the
most relevant information in the field; a 'one stop
shop' for all key references.

Auteur

Professor Ana de Bettencourt-Dias, University of Nevada, Inorganic and Materials Chemistry
Professor de Bettencourt-Dias' research interests lie in the development of new ligands (particularly organic and transition metal complexes) for highly emissive lanthanide ion complexes. She first became active in the field of the luminescent lanthanide ions in 2001 when she took her first academic position at Sycrause University, and her publications in this area include two well-received review articles which have been cited over 80 times. Professor de Bettencourt-Dias co-organised a symposium on 'Luminescence and Magnetism of Lanthanide-Containing Materials' at the ACS 2010 Fall Meeting, and she is program chair for the 2011 Rare Earth Research Conference.
In addition to her research, Professor de Bettencourt-Dias currently teaches classes in Advanced Inorganic Chemistry and Chemistry of the Less Common Elements.

Résumé
This comprehensive book presents the theoretical principles, current applications and latest research developments in the field of luminescent lanthanide complexes; a rapidly developing area of research which is attracting increasing interest amongst the scientific community.

Luminescence of Lanthanide Ions in Coordination Compounds and Nanomaterials begins with an introduction to the basic theoretical and practical aspects of lanthanide ion luminescence, and the spectroscopic techniques used to evaluate the efficiency of luminescence. Subsequent chapters introduce a variety of different applications including:

• Circularly polarized luminescence
• Luminescence bioimaging with lanthanide complexes
• Two-photon absorption of lanthanide complexes
• Chemosensors
• Upconversion luminescence
• Excitation spectroscopy
• Heterometallic complexes containing lanthanides

Each chapter presents a detailed introduction to the application, followed by a description of experimental techniques specific to the area and an extensive review of recent literature.

This book is a valuable introduction to the literature for scientists new to the field, as well as providing the more experienced researcher with a comprehensive resource covering the most relevant information in the field; a 'one stop shop' for all key references.

Contenu

List of Contributors xi

Preface xiii

1 Introduction to Lanthanide Ion Luminescence 1
Ana de Bettencourt-Dias

1.1 History of Lanthanide Ion Luminescence 1

1.2 Electronic Configuration of the +III Oxidation State 2

1.2.1 The 4f Orbitals 2

1.2.2 Energy Level Term Symbols 2

1.3 The Nature of the f-f Transitions 5

1.3.1 Hamiltonian in Central Field Approximation and Coulomb Interactions 5

1.3.2 SpinOrbit Coupling 10

1.3.3 Crystal Field or Stark Effects 13

1.3.4 The Crystal Field Parameters Bkq and Symmetry 14

1.3.5 Energies of Crystal Field Split Terms 18

1.3.6 Zeeman Effect 19

1.3.7 Point Charge Electrostatic Model 21

1.3.8 Other Methods to Estimate Crystal Field Parameters 25

1.3.9 Allowed and Forbidden f-f Transitions 27

1.3.10 Induced Electric Dipole Transitions and Their Intensity JuddOfelt Theory 34

1.3.11 Transition Probabilities and Branching Ratios 37

1.3.12 Hypersensitive Transitions 38

1.3.13 Emission Efficiency and Rate Constants 39

1.4 Sensitisation Mechanism 40

1.4.1 The Antenna Effect 40

1.4.2 Non-Radiative Quenching 44

2 Spectroscopic Techniques and Instrumentation 49
David E. Morris and Ana de Bettencourt-Dias

2.1 Introduction 49

2.2 Instrumentation in Luminescence Spectroscopy 52

2.2.1 Challenges in Design and Interpretation of Lanthanide Luminescence Experiments 52

2.2.2 Common Luminescence Experiments 57

2.2.3 Basic Design Elements and Configurations in Luminescence Spectrometers 61

2.2.4 Luminescence Spectrometer Components and Characteristics 63

2.2.5 Recent Advances in Luminescence Instrumentation 67

2.3 Measurement of Quantum Yields of Luminescence in the Solid State and in Solution 69

2.3.1 Measurement Against a Standard in Solution 70

2.3.2 Measurement Against a Standard in the Solid State 71

2.3.3 Absolute Measurement with an Integrating Sphere 72

2.4 Excited State Lifetimes 73

2.4.1 Number of Coordinated Solvent Molecules 73

3 Circularly Polarised Luminescence 77
Gilles Muller

3.1 Introduction 77

3.1.1 General Aspects: Molecular Chirality 77

3.1.2 Chiroptical Tools: from CD to CPL Spectroscopy 78

3.2 Theoretical Principles 79

3.2.1 General Theory 79

3.2.2 CPL Intensity Calculations, Selection Rules, Luminescence Selectivity, and SpectraStructure Relationship 82

3.3 CPL Measurements 84

3.3.1 Instrumentation 84

3.3.2 Calibration and Standards 88

3.3.3 Artifacts in CPL Measurements 90

3.3.4 Proposed Instrumental Improvements to Record Eu(III)-Based CPL Signals 91

3.4 Survey of CPL Applications 93

3.4.1 Ln(III)-Containing Systems 93

3.4.2 Ln(III) Complexes with Achiral Ligands 94

3.4.3 Ln(III) Complexes with Chiral Ligands 99

3.5 Chiral Ln(III) Complexes to Probe Biologically Relevant Systems 109

3.5.1 Sensing through Coordination to the Metal Centre 109

3.5.2 Sensing through Coordination to the Antenna/Receptor Groups 112

3.6 Concluding Remarks 114

4 Luminescence Bioimaging with Lanthanide Complexes 125
Jean-Claude G. Bünzli

4.1 Introduction 125

4.2 Luminescence Microscopy 127

4.2.1 Classical Optical Microscopy: a Short Survey 127

4.2.2 Principle of Luminescence Microscopy 128

4.2.3 Principle of Time-resolved Luminescence Microscopy 131

4.2.4 Early Instrumental Developments for Time-resolved Microscopy with LLBs 134

4.2.5 Optimisation of Time-resolved Microscopy Instrumentation 140

4.2.6 Commercial Instruments 143

4.3 Bioimaging with Lanthanide Luminescent Probes and Bioprobes 144

4.3.1 b-Diketonate Probes 144

4.3.2 Aliphatic Polyaminocarboxylate and Carboxylate Probes 154 <p&...