Making sense of Lanthanide Luminescence

2005 ◽  
Vol 88 (2) ◽  
pp. 101-131 ◽  
Author(s):  
Martinus H.V. Werts
Keyword(s):  
Lanthanide Complexes ◽  
Near Infrared ◽  
Spectroscopic Studies ◽  
Medical Diagnostics ◽  
Lanthanide Ions ◽  
Luminescent Materials ◽  
Making Sense ◽  
Trivalent Lanthanide ◽  
Recent Developments ◽  
History Of

The luminescence of trivalent lanthanide ions has found applications in lighting, lasers, optical telecommunications, medical diagnostics, and various other fields. This introductory review presents the basics of organic and inorganic luminescent materials containing lanthanide ions, their applications, and some recent developments. After a brief history of the discovery, purification and early spectroscopic studies of the lanthanides, the radiative and nonradiative transitions of the 4f electrons in lanthanide ions are discussed. Lanthanide-doped phosphors, glasses and crystals as well as luminescent lanthanide complexes with organic ligands receive attention with respect to their preparation and their applications. Finally, two recent developments in the field of luminescent materials are addressed: near-infrared luminescent lanthanide complexes and lanthanide-doped nanoparticles.

Recent Highlights in the use of Lanthanide-directed Synthesis of Novel Supramolecular (Luminescent) Self-assembly Structures such as Coordination Bundles, Helicates and Sensors

2011 ◽  
Vol 64 (10) ◽  
pp. 1315 ◽  
Author(s):  
Christophe Lincheneau ◽  
Floriana Stomeo ◽  
Steve Comby ◽  
Thorfinnur Gunnlaugsson
Keyword(s):  
Self Assembly ◽  
Near Infrared ◽  
Luminescent Properties ◽  
Short Review ◽  
Organic Ligands ◽  
Lanthanide Ions ◽  
Directed Synthesis ◽  
Recent Developments ◽  
Coordination Requirements ◽  
Physical Features

In this short review, we focus on the recent developments within the field of coordination chemistry where mono- or multimetallic supramolecular self-assemblies are formed by employing structurally defined organic ligands, taking advantage of the high coordination requirements of the lanthanides. Such synthesis results in the formation of both structurally complex and beautiful self-assemblies. Moreover, as the lanthanide ions possess both unique magnetic (e.g. GdIII and DyIII) and luminescent properties, either in the visible (EuIII, SmIII and TbIII) or near-infrared regions (YbIII, NdIII, ErIII), these physical features are usually transferred to the self-assemblies themselves, allowing the formation of highly functional structures, such as coordination networks, as well as molecular bundles and helicates. Hence, examples of the use of lanthanide-directed synthesis of luminescent sensors, some of which are formed on solid surfaces such as gold (flat surface or nanoparticles), and imaging agents are presented. Moreover, we demonstrate that by using chiral organic ligands, lanthanide-directed synthesis can also give rise to the formation of enantiomerically pure self-assemblies, the structure of which can be probed using circularly polarized luminescence.

scholarly journals HOCl Responsive Lanthanide Complexes Using Hydroquinone Caging Units

Molecules ◽  
2020 ◽  
Vol 25 (8) ◽  
pp. 1959
Author(s):  
Elena Del Giorgio ◽  
Thomas Just Sørensen
Keyword(s):  
Lanthanide Complexes ◽  
Design Principle ◽  
Hypochlorous Acid ◽  
Molecular Probes ◽  
Lanthanide Ions ◽  
Redox Biology ◽  
Redox Active ◽  
Trivalent Lanthanide ◽  
Sustained Effort ◽  
Triton X

Redox biology is still looking for tools to monitor redox potential in cellular biology and, despite a large and sustained effort, reliable molecular probes have yet to emerge. In contrast, molecular probes for reactive oxygen and nitrogen have been widely explored. In this manuscript, three kinetically inert lanthanide complexes that selectively react with hypochlorous acid are prepared and characterized. The design is based on 1,4,7,10-tetraazacyclododecane-1,4,7-triacetic acid (DO3A) and 1,4,7,10-tetraazacyclododecane-1,7-diacetic acid (DO2A) ligands appended with one or two redox active hydroquinone derived arms, thereby forming octadentate ligands ideally suited to complex trivalent lanthanide ions. The three complexes are found to react selectively with hypochlorous acid to form highly symmetric lanthanide(III) 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacedic acid (DOTA) complexes. The conversion of the probe to [Ln.DOTA]− is followed by luminescence, absorption, and NMR spectroscopy in a model system comprised of a Triton-X modified HEPES buffer. It was concluded that the design principle works, and that simple caging units like hydroquinones can work well in conjugation with lanthanide(III) complexes.

Ab initio calculation of energy levels of trivalent lanthanide ions

2018 ◽  
Vol 20 (21) ◽  
pp. 14564-14577 ◽  
Author(s):  
Alexandra Ya. Freidzon ◽  
Ilia A. Kurbatov ◽  
Vitaliy I. Vovna
Keyword(s):  
Ab Initio ◽  
Ab Initio Calculation ◽  
Lanthanide Complexes ◽  
Energy Levels ◽  
Emission Spectra ◽  
Lanthanide Ions ◽  
Computational Scheme ◽  
Absorption And Emission ◽  
Absorption And Emission Spectra ◽  
Trivalent Lanthanide

A fully ab initio computational scheme employing CASSCF/XMCQDPT2/SO-CASSCF for the absorption and emission spectra of trivalent lanthanide complexes is presented.

scholarly journals Recent Developments in Lanthanide-Doped Alkaline Earth Aluminate Phosphors with Enhanced and Long-Persistent Luminescence

Nanomaterials ◽  
2021 ◽  
Vol 11 (3) ◽  
pp. 723
Author(s):  
Doory Kim
Keyword(s):  
Alkaline Earth ◽  
Review Article ◽  
Lanthanide Ions ◽  
Synthesis Methods ◽  
Luminescent Materials ◽  
Persistent Luminescence ◽  
Research Attention ◽  
The Past ◽  
Recent Developments

Lanthanide-activated alkaline earth aluminate phosphors are excellent luminescent materials that are designed to overcome the limitations of conventional sulfide-based phosphors. The increasing research attention on these phosphors over the past decade has led to a drastic improvement in their phosphorescence efficiencies and resulted in a wide variety of phosphorescence colors, which can facilitate applications in various areas. This review article discusses the development of lanthanide-activated alkaline earth aluminate phosphors with a focus on the various synthesis methods, persistent luminescence mechanisms, activator and coactivator effects, and the effects of compositions. Particular attention has been devoted to alkaline earth aluminate phosphors that are extensively used, such as strontium-, calcium-, and barium-based aluminates. The role of lanthanide ions as activators and coactivators in phosphorescence emissions was also emphasized. Finally, we address recent techniques involving nanomaterial engineering that have also produced lanthanide-activated alkaline earth aluminate phosphors with long-persistent luminescence.

scholarly journals Photoluminescence of Homoleptic Lanthanide Complexes With Tris(benzotriazol-1-yl)borate

2021 ◽  
Author(s):  
Marco Bortoluzzi ◽  
Valentina Ferraro ◽  
Federica Sartor
Keyword(s):  
Lanthanide Complexes ◽  
Europium Complex ◽  
Lanthanide Ions ◽  
Visible Range ◽  
Synthetic Approach ◽  
Antenna Effect ◽  
Plastic Materials ◽  
Trivalent Lanthanide ◽  
Intense Emission ◽  
Trigonal Prismatic

AbstractBright photoluminescent neutral complexes having general formula [Ln(tbtz)3] (Ln = Eu, Tb; tbtz = tris(benzotriazol-1-yl)borate) were obtained by reacting K[tbtz] with EuCl3 and TbCl3. The emissions in the visible range, related to the f-f transitions of the trivalent lanthanide ions, are observable upon excitation with wavelengths shorter than 350 nm. The most intense emission bands correspond to the 5D0 → 7F4 transition at 699 nm for the europium complex and to the 5D4 → 7F5 transition at 542 nm for the terbium derivative. The luminescence is in all the cases mostly associated with the antenna-effect from the coordinated tbtz ligands. The synthetic approach was successfully extended to the preparation of the analogous yttrium and gadolinium derivatives. Tricapped trigonal prismatic geometry was attributed to the complexes on the basis of luminescence data and DFT calculations. Highly photoluminescent plastic materials were obtained by embedding small amounts of [Eu(tbtz)3] or [Tb(tbtz)3] in poly(methyl methacrylate).

scholarly journals Synthesis and Near Infrared Luminescence Properties of a Series of Lanthanide Complexes with POSS Modified Ligands

Molecules ◽  
2019 ◽  
Vol 24 (7) ◽  
pp. 1253 ◽  
Author(s):  
Qingrui Zhang ◽  
Xiuyun Yang ◽  
Ruiping Deng ◽  
Liang Zhou ◽  
Yang Yu ◽  
...  
Keyword(s):  
Lanthanide Complexes ◽  
Near Infrared ◽  
Lanthanide Ions ◽  
Polyhedral Oligomeric Silsesquioxanes ◽  
Quenching Effect ◽  
Infrared Luminescence ◽  
Ft Ir ◽  
Excimer Formation ◽  
Nir Luminescence ◽  
Concentration Quenching Effect

A polyhedral oligomeric silsesquioxanes (POSS) modified 8-hydroxyquinoline derivative (denoted as Q-POSS) was synthesized and used as a ligand to coordinate with lanthanide ions to obtain a series of lanthanide complexes Ln(Q-POSS)3 (Ln = Er3+, Yb3+, Nd3+). The as-prepared lanthanide complexes have been characterized by FT-IR, UV–Vis, and elemental analysis. All these complexes showed the characteristic near-infrared (NIR) luminescence originated from the corresponding lanthanide ions under excitation. Compared with the unmodified counterparts LnQ3 (HQ = 8-hydroxyquinoline), the Ln(Q-POSS)3 complexes showed obviously increased emission intensity, which was ascribed mainly to the steric-hindrance effects of the POSS moiety in the ligands. It is believed that the POSS group could suppress undesired excimer formation and intermolecular aggregation, thus decreasing the concentration quenching effect of the corresponding lanthanide complexes.

scholarly journals DNA Intercalating Near-Infrared Luminescent Lanthanide Complexes Containing Dipyrido[3,2-a:2′,3′-c]phenazine (dppz) Ligands: Synthesis, Crystal Structures, Stability, Luminescence Properties and CT-DNA Interaction

Molecules ◽  
2020 ◽  
Vol 25 (22) ◽  
pp. 5309
Author(s):  
Aleksandar Savić ◽  
Anna M. Kaczmarek ◽  
Rik Van Deun ◽  
Kristof Van Hecke
Keyword(s):  
Lanthanide Complexes ◽  
Near Infrared ◽  
Broad Band ◽  
Dna Interaction ◽  
Lanthanide Ions ◽  
Dna Intercalation ◽  
Luminescence Properties ◽  
Triplet Energy ◽  
Excitation Spectra ◽  
Ct Dna

In order to create near-infrared (NIR) luminescent lanthanide complexes suitable for DNA-interaction, novel lanthanide dppz complexes with general formula [Ln(NO3)3(dppz)2] (Ln = Nd3+, Er3+ and Yb3+; dppz = dipyrido[3,2-a:2′,3′-c]phenazine) were synthesized, characterized and their luminescence properties were investigated. In addition, analogous compounds with other lanthanide ions (Ln = Ce3+, Pr3+, Sm3+, Eu3+, Tb3+, Dy3+, Ho3+, Tm3+, Lu3+) were prepared. All complexes were characterized by IR spectroscopy and elemental analysis. Single-crystal X-ray diffraction analysis of the complexes (Ln = La3+, Ce3+, Pr3+, Nd3+, Eu3+, Er3+, Yb3+, Lu3+) showed that the lanthanide’s first coordination sphere can be described as a bicapped dodecahedron, made up of two bidentate dppz ligands and three bidentate-coordinating nitrate anions. Efficient energy transfer was observed from the dppz ligand to the lanthanide ion (Nd3+, Er3+ and Yb3+), while relatively high luminescence lifetimes were detected for these complexes. In their excitation spectra, the maximum of the strong broad band is located at around 385 nm and this wavelength was further used for excitation of the chosen complexes. In their emission spectra, the following characteristic NIR emission peaks were observed: for a) Nd3+: 4F3/2 → 4I9/2 (870.8 nm), 4F3/2 → 4I11/2 (1052.7 nm) and 4F3/2 → 4I13/2 (1334.5 nm); b) Er3+: 4I13/2 → 4I15/2 (1529.0 nm) c) Yb3+: 2F5/2 → 2F7/2 (977.6 nm). While its low triplet energy level is ideally suited for efficient sensitization of Nd3+ and Er3+, the dppz ligand is considered not favorable as a sensitizer for most of the visible emitting lanthanide ions, due to its low-lying triplet level, which is too low for the accepting levels of most visible emitting lanthanides. Furthermore, the DNA intercalation ability of the [Nd(NO3)3(dppz)2] complex with calf thymus DNA (CT-DNA) was confirmed using fluorescence spectroscopy.

Hybrid lanthanide complexes based on a novel β-diketone functionalized polyhedral oligomeric silsesquioxane (POSS) and their nanocomposites with PMMA via in situ polymerization

RSC Advances ◽  
2014 ◽  
Vol 4 (74) ◽  
pp. 39132-39139 ◽  
Author(s):  
Liguo Li ◽  
Shengyu Feng ◽  
Hongzhi Liu
Keyword(s):  
Lanthanide Complexes ◽  
In Situ Polymerization ◽  
Polyhedral Oligomeric Silsesquioxane ◽  
Lanthanide Ions ◽  
Luminescent Materials ◽  
Oligomeric Silsesquioxane

β-diketone-functionalized POSS dendrimer acted as a ligand to coordinate with lanthanide ions (Eu3+ and Tb3+) to form hybrid luminescent materials.

Sign in / Sign up

Export Citation Format

Share Document