Luminescence of Lanthanide Ions in Coordination Compounds and Nanomaterials

Professor Ana de Bettencourt-Dias, University of Nevada, Inorganic and Materials ChemistryProfessor 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.

• List of Contributors xiPreface xiii1 Introduction to Lanthanide Ion Luminescence 1Ana de Bettencourt-Dias1.1 History of Lanthanide Ion Luminescence 11.2 Electronic Configuration of the +III Oxidation State 21.2.1 The 4f Orbitals 21.2.2 Energy Level Term Symbols 21.3 The Nature of the f-f Transitions 51.3.1 Hamiltonian in Central Field Approximation and Coulomb Interactions 51.3.2 Spin–Orbit Coupling 101.3.3 Crystal Field or Stark Effects 131.3.4 The Crystal Field Parameters Bkq and Symmetry 141.3.5 Energies of Crystal Field Split Terms 181.3.6 Zeeman Effect 191.3.7 Point Charge Electrostatic Model 211.3.8 Other Methods to Estimate Crystal Field Parameters 251.3.9 Allowed and Forbidden f-f Transitions 271.3.10 Induced Electric Dipole Transitions and Their Intensity – Judd–Ofelt Theory 341.3.11 Transition Probabilities and Branching Ratios 371.3.12 Hypersensitive Transitions 381.3.13 Emission Efficiency and Rate Constants 391.4 Sensitisation Mechanism 401.4.1 The Antenna Effect 401.4.2 Non-Radiative Quenching 442 Spectroscopic Techniques and Instrumentation 49David E. Morris and Ana de Bettencourt-Dias2.1 Introduction 492.2 Instrumentation in Luminescence Spectroscopy 522.2.1 Challenges in Design and Interpretation of Lanthanide Luminescence Experiments 522.2.2 Common Luminescence Experiments 572.2.3 Basic Design Elements and Configurations in Luminescence Spectrometers 612.2.4 Luminescence Spectrometer Components and Characteristics 632.2.5 Recent Advances in Luminescence Instrumentation 672.3 Measurement of Quantum Yields of Luminescence in the Solid State and in Solution 692.3.1 Measurement Against a Standard in Solution 702.3.2 Measurement Against a Standard in the Solid State 712.3.3 Absolute Measurement with an Integrating Sphere 722.4 Excited State Lifetimes 732.4.1 Number of Coordinated Solvent Molecules 733 Circularly Polarised Luminescence 77Gilles Muller3.1 Introduction 773.1.1 General Aspects: Molecular Chirality 773.1.2 Chiroptical Tools: from CD to CPL Spectroscopy 783.2 Theoretical Principles 793.2.1 General Theory 793.2.2 CPL Intensity Calculations, Selection Rules, Luminescence Selectivity, and Spectra–Structure Relationship 823.3 CPL Measurements 843.3.1 Instrumentation 843.3.2 Calibration and Standards 883.3.3 Artifacts in CPL Measurements 903.3.4 Proposed Instrumental Improvements to Record Eu(III)-Based CPL Signals 913.4 Survey of CPL Applications 933.4.1 Ln(III)-Containing Systems 933.4.2 Ln(III) Complexes with Achiral Ligands 943.4.3 Ln(III) Complexes with Chiral Ligands 993.5 Chiral Ln(III) Complexes to Probe Biologically Relevant Systems 1093.5.1 Sensing through Coordination to the Metal Centre 1093.5.2 Sensing through Coordination to the Antenna/Receptor Groups 1123.6 Concluding Remarks 1144 Luminescence Bioimaging with Lanthanide Complexes 125Jean-Claude G. Bünzli4.1 Introduction 1254.2 Luminescence Microscopy 1274.2.1 Classical Optical Microscopy: a Short Survey 1274.2.2 Principle of Luminescence Microscopy 1284.2.3 Principle of Time-resolved Luminescence Microscopy 1314.2.4 Early Instrumental Developments for Time-resolved Microscopy with LLBs 1344.2.5 Optimisation of Time-resolved Microscopy Instrumentation 1404.2.6 Commercial Instruments 1434.3 Bioimaging with Lanthanide Luminescent Probes and Bioprobes 1444.3.1 b-Diketonate Probes 1444.3.2 Aliphatic Polyaminocarboxylate and Carboxylate Probes 1544.3.3 Macrocyclic Probes 1634.3.4 Self-assembled Triple Helical Bioprobes 1714.3.5 Other Bioprobes 1774.4 Conclusions and Perspectives 1805 Two-photon Absorption of Lanthanide Complexes: from Fundamental Aspects to Biphotonic Imaging Applications 197Anthony D'Aleo, Chantal Andraud and Olivier Maury5.1 Introduction 1975.2 Two-photon Absorption, a Third Nonlinear Optical Phenomenon 1985.2.1 Theoretical and Historical Background 1985.2.2 Experimental Determination of the 2PA Efficiency of Molecules 1995.2.3 Two-photon Fluorescence Microscopy for Biological Imaging 2005.2.4 Molecular Engineering for Multiphonic Imaging 2015.3 Spectroscopic Evidence for the Two-photon Sensitisation of Lanthanide Luminescence 2055.3.1 1961: The Breakthrough Experiments 2055.3.2 Two-photon Excitation of f-f Transitions 2065.3.3 The Two-photon Antenna Effect 2075.3.4 The Charge Transfer State Mediated Sensitisation Process 2095.3.5 Optimising Molecular Two-photon Cross Section: the Brightness Trade-off 2115.3.6 Two-photon Excited Luminescence in Solid Matrix 2145.3.7 Two-photon Time-gated Spectroscopy 2145.4 Towards Biphotonic Microscopy Imaging 2155.4.1 Proof of Concept 2155.4.2 Towards the Design of an Optimised Bio-probe 2175.4.3 Design of Lanthanide containing Nano-probes, toward Single-object Imaging 2225.4.4 Towards NIR-to-NIR Imaging 2235.5 Conclusions 2256 Lanthanide Ion Complexes as Chemosensors 231Thorfinnur Gunnlaugsson and Simon J. A. Pope6.1 Photophysical Properties of LnIII Based Sensors 2316.1.1 Emission Based Sensors 2316.1.2 Luminescence Lifetime 2326.1.3 Spectral Form, Hypersensitivity and Ratiometric Peaks 2336.2 Sensor Design Principles 2336.2.1 The Design of Ln-receptor Sites and Antenna Components 2346.2.2 Covalent versus Self-assembled Ln-receptor Design 2356.2.3 Sensors for Cations 2376.2.4 Sensors for Anions 2496.3 Interactions with DNA and Biological Systems 2607 Upconversion of Ln3+ -based Nanoparticles for Optical Bio-imaging 269Frank C.J.M. van Veggel7.1 Introduction 2697.2 Physical Properties of Ln3+ Ions 2727.3 Basic Principles of Upconversion 2727.4 Synthesis of Core and Core–Shell Nanoparticles 2777.4.1 Syntheses in Organic Solvent 2777.4.2 Syntheses in Aqueous Media 2777.4.3 Surface Modification 2787.5 Characterisation 2787.5.1 Basic Techniques 2787.5.2 Advanced Techniques 2797.6 Bio-imaging 2837.6.1 Basics 2837.6.2 Cell Studies 2837.6.3 Animal Studies 2877.6.4 Discussion 2907.7 Upconversion and Magnetic Resonance Imaging 2937.8 Conclusions and Outlook 2958 Direct Excitation Ln(III) Luminescence Spectroscopy to Probe the Coordination Sphere of Ln(III) Catalysts, Optical Sensors and MRI Agents 303Janet R. Morrow and Sarina J. Dorazio8.1 Introduction 3038.1.1 Luminescence Spectroscopy for Defining the Ln(III) Coordination Sphere 3038.2 Direct Excitation Lanthanide Luminescence 3048.2.1 Luminescence Properties of the Lanthanide Ions 3048.2.2 Ln(III) Excitation Spectroscopy 3068.2.3 Ln(III) Emission Spectroscopy 3078.2.4 Time-Resolved Ln(III) Luminescence Spectroscopy 3088.2.5 Luminescence Resonance Energy Transfer 3108.3 Defining the Ln(III) Ion Coordination Sphere through Direct Eu(III) Excitation Luminescence Spectroscopy 3118.3.1 Eu(III) Complex Speciation in Solution: Number of Excitation Peaks 3118.3.2 Excitation Spectra of Geometric Isomers 3118.3.3 Innersphere Coordination of Anions 3128.3.4 Ligand Ionisation 3148.4 Luminescence Studies of Anion Binding in Catalysis and Sensing 3178.4.1 Phosphate Ester Binding and Cleavage 3178.4.2 Sensing Biologically Relevant Anions 3188.5 Luminescence Studies of Ln(III) MRI Contrast Agents 3208.5.1 Types of Ln(III) MRI Contrast Agents 3208.5.2 Luminescence Studies of Ln(III) ParaCEST Agents 3228.6 Conclusions 3269 Heterometallic Complexes Containing Lanthanides 331Stephen Faulkner and Manuel Tropiano9.1 Introduction 3319.2 Properties of a Heteromultimetallic Complex 3329.3 Lanthanide Assemblies in the Solid State 3359.4 Lanthanide Assemblies in Solution 3389.4.1 Lanthanide Helicates 3389.4.2 Non-helicate Structures 3419.5 Heterometallic Complexes Derived from Bridging and Multi-compartmental Ligands 3429.6 Energy Transfer in Assembled Systems 3479.7 Responsive Multimetallic Systems 3519.8 Summary and Prospects 353References 353Index 359