Spectroscopic properties and design of highly luminescent lanthanide coordination complexes

Present technological demands in disparate areas, such as microfluidics and nanofluidics, microelectronics and nanoelectronics, photonics and biomedicine, among others, have reached to a development such that conventional contact thermal probes are not accomplished anymore to perform accurate measurements with submicrometric spatial resolution. The development of novel noncontact thermal probes is, then, mandatory, contributing to an expansionary epoch of luminescence thermometry. Luminescence thermometry based on trivalent lanthanide ions has become very popular since 2010 due to the unique versatility, stability, and narrow emission band profiles of the ions that cover the entire electromagnetic spectrum with relatively high emission quantum yields. Here, a perspective overview on the field is given from the beginnings in the 1950s until the most recent cutting‐edge examples. The current movement toward usage of the technique as a new tool for thermal imaging, early tumor detection, and as a tool for unveiling the properties of the thermometers themselves or of their local neighborhoods is also summarized.

Lanthanide-based thermometers: At the cutting-edge of luminescence thermometry

Publisher Summary This chapter describes the symmetry aspects of the crystal field and the parametrization of the energy level scheme. It provides an overview of the experimental data of trivalent lanthanide ions doped into crystalline host matrices. The selection rules for induced electric dipole (ED) and magnetic dipole (MD) transitions for systems with even or odd numbers of f electrons in different site symmetries are presented. Methods for the assignment of crystal-field levels are discussed and the determination of phenomenological crystal-field parameters is described. Such a set of crystal-field parameters in combination with a suitable set of free-ion parameters allows calculating crystal-field energy levels and reconstructing the energy diagram of the 4fn configuration. In this way, it is not only possible to check the validity of the crystal-field model but also to get information about energy levels, which cannot be detected experimentally.

Chapter 155 Rationalization of crystal-field parametrization

List of contributors Preface Introduction 1 Crystal field splitting mechanisms D J Newman and Betty Ng 2 Empirical crystal fields D J Newman and Betty Ng 3 Fitting crystal field parameters D J Newman and Betty Ng 4 Lanthanide and actinide optical spectra G K Liu 5 Superposition model D J Newman and Betty Ng 6 Effects of electron correlation on crystal field splitting M F Reid and D J Newman 7 Ground state splittings in S-state ions D J Newman and Betty Ng 8 Invariants and moments Y Y Yeung 9 Semiclassical model K S Chan 10 Transition intensities M F Reid Appendix 1 Point symmetry D J Newman and Betty Ng Appendix 2 QBASIC programs D J Newman and Betty Ng Appendix 3 Accessible program packages Y Y Yeung, M F Reid and D J Newman Appendix 4 Computer package CST Cz Rudowicz Bibliography Index

/pdf/crystal-field-handbook-5enwtd2lao.pdf

Crystal Field Handbook

Luminescent ratiometric thermometers combining high spatial and temporal resolution at the micro- and nanoscale, where the conventional methods are ineffective, have emerged over the last decade as an effervescent field of research, essentially motivated by their potential applications in nanotechnology, photonics, and biomedicine. Among the distinct luminescent thermal probes, lanthanide-based materials play a central role in the field due to their unique thermometric response and intriguing emission features (eg, high quantum yield, narrow bandwidth, long-lived emission, large Stokes shifts, and ligand-dependent luminescence sensitization). This chapter offers a general overview of recent examples of single- and dual-center Ln3 +-based thermometers, emphasizing those working at nanometric scale, being focused on how to quantify their performance accordingly to the relevant parameters: relative sensitivity, temperature uncertainty, spatial and temporal resolution, repeatability (or test–retest reliability), and reproducibility. The emission mechanisms supporting single- and dual-center emissions are reviewed, together with the advantages and limitations of each approach. Illustrative examples of the rich variety of systems designed and developed to sense temperature are provided and explored. Finally, we discuss the challenges and opportunities in the development of highly sensitive luminescent ratiometric thermometers that are currently facing the scientists in this exciting research field.

Lanthanides in Luminescent Thermometry

Two types of correlations with experimental results are reported. For even-f-electron systems, a center of gravity was computed based on the energies of the observed states, and calculated optimized sets of atomic energy level parameters. For odd-electron systems complete crystal field calculations were performed in which parameters of both the atomic and crystal-field parts of the interaction were adjusted to experimental data. The result is a set of eigenvectors for all the ionic states in each configuration. Spectroscopic results for all lanthanides doped into LaF3 (In³⁺ +/:LaF3) except Pm³⁺ and Eu³⁺ are reported.

/pdf/energy-level-structure-and-transition-probabilities-in-the-gjmbal6l70.pdf

Energy level structure and transition probabilities in the spectra of the trivalent lanthanides in LaF

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Energy level structure and transition probabilities in the spectra of the trivalent lanthanides in LaF