Luminescence of Lanthanide Ions in Coordination Compounds and Nanomaterials -- Contents -- List of Contributors -- Preface -- 1 Introduction to Lanthanide Ion Luminescence -- 1.1 History of Lanthanide Ion Luminescence -- 1.2 Electronic Configuration of the +III Oxidation State -- 1.2.1 The 4f Orbitals -- 1.2.2 Energy Level Term Symbols -- 1.3 The Nature of the f-f Transitions -- 1.3.1 Hamiltonian in Central Field Approximation and Coulomb Interactions -- 1.3.2 Spin-Orbit Coupling -- 1.3.3 Crystal Field or Stark Effects -- 1.3.4 The Crystal Field Parameters Bkq and Symmetry -- 1.3.5 Energies of Crystal Field Split Terms -- 1.3.6 Zeeman Effect -- 1.3.7 Point Charge Electrostatic Model -- 1.3.8 Other Methods to Estimate Crystal Field Parameters -- 1.3.9 Allowed and Forbidden f-f Transitions -- 1.3.10 Induced Electric Dipole Transitions and Their Intensity - Judd-Ofelt Theory -- 1.3.11 Transition Probabilities and Branching Ratios -- 1.3.12 Hypersensitive Transitions -- 1.3.13 Emission Efficiency and Rate Constants -- 1.4 Sensitisation Mechanism -- 1.4.1 The Antenna Effect -- 1.4.2 Non-Radiative Quenching -- References -- 2 Spectroscopic Techniques and Instrumentation -- 2.1 Introduction -- 2.2 Instrumentation in Luminescence Spectroscopy -- 2.2.1 Challenges in Design and Interpretation of Lanthanide Luminescence Experiments -- 2.2.2 Common Luminescence Experiments -- 2.2.3 Basic Design Elements and Configurations in Luminescence Spectrometers -- 2.2.4 Luminescence Spectrometer Components and Characteristics -- 2.2.5 Recent Advances in Luminescence Instrumentation -- 2.3 Measurement of Quantum Yields of Luminescence in the Solid State and in Solution -- 2.3.1 Measurement Against a Standard in Solution -- 2.3.2 Measurement Against a Standard in the Solid State -- 2.3.3 Absolute Measurement with an Integrating Sphere -- 2.4 Excited State Lifetimes.

2.4.1 Number of Coordinated Solvent Molecules -- References -- 3 Circularly Polarised Luminescence -- 3.1 Introduction -- 3.1.1 General Aspects: Molecular Chirality -- 3.1.2 Chiroptical Tools: from CD to CPL Spectroscopy -- 3.2 Theoretical Principles -- 3.2.1 General Theory -- 3.2.2 CPL Intensity Calculations, Selection Rules, Luminescence Selectivity, and Spectra-Structure Relationship -- 3.3 CPL Measurements -- 3.3.1 Instrumentation -- 3.3.2 Calibration and Standards -- 3.3.3 Artifacts in CPL Measurements -- 3.3.4 Proposed Instrumental Improvements to Record Eu(III)-Based CPL Signals -- 3.4 Survey of CPL Applications -- 3.4.1 Ln(III)-Containing Systems -- 3.4.2 Ln(III) Complexes with Achiral Ligands -- 3.4.3 Ln(III) Complexes with Chiral Ligands -- 3.5 Chiral Ln(III) Complexes to Probe Biologically Relevant Systems -- 3.5.1 Sensing through Coordination to the Metal Centre -- 3.5.2 Sensing through Coordination to the Antenna/Receptor Groups -- 3.6 Concluding Remarks -- References -- 4 Luminescence Bioimaging with Lanthanide Complexes -- 4.1 Introduction -- 4.2 Luminescence Microscopy -- 4.2.1 Classical Optical Microscopy: a Short Survey -- 4.2.2 Principle of Luminescence Microscopy -- 4.2.3 Principle of Time-resolved Luminescence Microscopy -- 4.2.4 Early Instrumental Developments for Time-resolved Microscopy with LLBs -- 4.2.5 Optimisation of Time-resolved Microscopy Instrumentation -- 4.2.6 Commercial Instruments -- 4.3 Bioimaging with Lanthanide Luminescent Probes and Bioprobes -- 4.3.1 β-Diketonate Probes -- 4.3.2 Aliphatic Polyaminocarboxylate and Carboxylate Probes -- 4.3.3 Macrocyclic Probes -- 4.3.4 Self-assembled Triple Helical Bioprobes -- 4.3.5 Other Bioprobes -- 4.4 Conclusions and Perspectives -- References -- 5 Two-photon Absorption of Lanthanide Complexes: from Fundamental Aspects to Biphotonic Imaging Applications -- 5.1 Introduction.

5.2 Two-photon Absorption, a Third Nonlinear Optical Phenomenon -- 5.2.1 Theoretical and Historical Background -- 5.2.2 Experimental Determination of the 2PA Efficiency of Molecules -- 5.2.3 Two-photon Fluorescence Microscopy for Biological Imaging -- 5.2.4 Molecular Engineering for Multiphonic Imaging -- 5.3 Spectroscopic Evidence for the Two-photon Sensitisation of Lanthanide Luminescence -- 5.3.1 1961: The Breakthrough Experiments -- 5.3.2 Two-photon Excitation of f-f Transitions -- 5.3.3 The Two-photon Antenna Effect -- 5.3.4 The Charge Transfer State Mediated Sensitisation Process -- 5.3.5 Optimising Molecular Two-photon Cross Section: the Brightness Trade-off -- 5.3.6 Two-photon Excited Luminescence in Solid Matrix -- 5.3.7 Two-photon Time-gated Spectroscopy -- 5.4 Towards Biphotonic Microscopy Imaging -- 5.4.1 Proof of Concept -- 5.4.2 Towards the Design of an Optimised Bio-probe -- 5.4.3 Design of Lanthanide containing Nano-probes, toward Single-object Imaging -- 5.4.4 Towards NIR-to-NIR Imaging -- 5.5 Conclusions -- References -- 6 Lanthanide Ion Complexes as Chemosensors -- 6.1 Photophysical Properties of LnIII Based Sensors -- 6.1.1 Emission Based Sensors -- 6.1.2 Luminescence Lifetime -- 6.1.3 Spectral Form, Hypersensitivity and Ratiometric Peaks -- 6.2 Sensor Design Principles -- 6.2.1 The Design of Ln-receptor Sites and Antenna Components -- 6.2.2 Covalent versus Self-assembled Ln-receptor Design -- 6.2.3 Sensors for Cations -- 6.2.4 Sensors for Anions -- 6.3 Interactions with DNA and Biological Systems -- References -- 7 Upconversion of Ln3+ -based Nanoparticles for Optical Bio-imaging -- 7.1 Introduction -- 7.2 Physical Properties of Ln3+ Ions -- 7.3 Basic Principles of Upconversion -- 7.4 Synthesis of Core and Core-Shell Nanoparticles -- 7.4.1 Syntheses in Organic Solvent -- 7.4.2 Syntheses in Aqueous Media.

7.4.3 Surface Modification -- 7.5 Characterisation -- 7.5.1 Basic Techniques -- 7.5.2 Advanced Techniques -- 7.6 Bio-imaging -- 7.6.1 Basics -- 7.6.2 Cell Studies -- 7.6.3 Animal Studies -- 7.6.4 Discussion -- 7.7 Upconversion and Magnetic Resonance Imaging -- 7.8 Conclusions and Outlook -- References -- 8 Direct Excitation Ln(III) Luminescence Spectroscopy to Probe the Coordination Sphere of Ln(III) Catalysts, Optical Sensors and MRI Agents -- 8.1 Introduction -- 8.1.1 Luminescence Spectroscopy for Defining the Ln(III) Coordination Sphere -- 8.2 Direct Excitation Lanthanide Luminescence -- 8.2.1 Luminescence Properties of the Lanthanide Ions -- 8.2.2 Ln(III) Excitation Spectroscopy -- 8.2.3 Ln(III) Emission Spectroscopy -- 8.2.4 Time-Resolved Ln(III) Luminescence Spectroscopy -- 8.2.5 Luminescence Resonance Energy Transfer -- 8.3 Defining the Ln(III) Ion Coordination Sphere through Direct Eu(III) Excitation Luminescence Spectroscopy -- 8.3.1 Eu(III) Complex Speciation in Solution: Number of Excitation Peaks -- 8.3.2 Excitation Spectra of Geometric Isomers -- 8.3.3 Innersphere Coordination of Anions -- 8.3.4 Ligand Ionisation -- 8.4 Luminescence Studies of Anion Binding in Catalysis and Sensing -- 8.4.1 Phosphate Ester Binding and Cleavage -- 8.4.2 Sensing Biologically Relevant Anions -- 8.5 Luminescence Studies of Ln(III) MRI Contrast Agents -- 8.5.1 Types of Ln(III) MRI Contrast Agents -- 8.5.2 Luminescence Studies of Ln(III) ParaCEST Agents -- 8.6 Conclusions -- References -- 9 Heterometallic Complexes Containing Lanthanides -- 9.1 Introduction -- 9.2 Properties of a Heteromultimetallic Complex -- 9.3 Lanthanide Assemblies in the Solid State -- 9.4 Lanthanide Assemblies in Solution -- 9.4.1 Lanthanide Helicates -- 9.4.2 Non-helicate Structures -- 9.5 Heterometallic Complexes Derived from Bridging and Multi-compartmental Ligands.

9.6 Energy Transfer in Assembled Systems -- 9.7 Responsive Multimetallic Systems -- 9.8 Summary and Prospects -- References -- Index -- End User License Agreement.