Highly luminescent organic-inorganic hybrid materials have been prepared by combining task-specific polymerized ionic liquids (PILs) based on the 1-alkyl-3-vinylimidazolium cation ([CnVim]+ (with n = 2-6)) with suitable halides of trivalent lanthanides such as europium and terbium. The resulting materials have been characterized by 1H nuclear magnetic resonance, Fourier transform infrared, UV-Vis and photoluminescence spectroscopy. They show bright and intense luminescence over a wide range of excitation wavelengths, which particularly for the Eu3+ containing compounds, benefits from efficient energy transfer from the organic aromatic moieties in the PIL to the emitting level of the lanthanide(iii) ion. In the case of the Tb3+ ion, the emission benefits from excitation into the Tb3+ d levels. The emission colour can be tuned from green to red for Tb and Eu respectively. This includes bright white emission for Eu that can be achieved by altering the excitation wavelength. The easy processability of these novel PILs renders them interesting for a wide range of optical applications.

Since the discovery of AlQ3 (Q = 8-quinolinolato) quinolinato complexes, they have been extensively scrutinized as emitter materials for organic lighting. Herein, we report on the first representatives of a series of tetrabutylphosphonium tetrakis(8-quinolinolato)lanthanidate complexes [P4444][Ln(Q)4]·2X (Ln = Dy-Lu and Y; X = H2O for Ln = Dy-Tm, Lu and Y and (CH3)2CO for Ln = Yb), which are synthesised by a simple metathesis reaction of the respective potassium tetrakis(8-quinolinolato)lanthanidate salts with tetrabutylphosphonium bromide in acetone at room temperature. Single-crystal X-ray diffraction reveals that Ln(iii) is coordinated by four bidentate 8-quinolinato ligands in the form of a distorted square antiprism. The distinct [Ln(Q)4]− anions interact with the [P4444]+ cations through secondary bonding interactions, such as CH-π and van der Waals interactions, in addition to electrostatic coulombic interactions. Although these compounds contain crystal water/solvent molecules (and their synthesis does not require an inert atmosphere), they do not enter the metal coordination sphere but form pairwise intramolecular hydrogen bonds with the two 8-quinolinato ligands of the complex lanthanide anions. Combined differential scanning calorimetry-thermogravimetric analysis indicates that crystal water is lost at around 100 °C and [P4444][Ln(Q)4] is formed, which is stable up to 300 °C, where further degradation occurs. All compounds feature strong emission in the green region, originating from the π* → π transitions within the 8-quinolinato ligand, with lifetimes in the nanosecond range. The luminescence colour changes from blue-green to yellow-green depending on Ln3+, which opens up additional directions in the colour tuning of emitters for organic lighting applications.

Emerging organic light-emitting devices, such as light-emitting electrochemical cells (LECs), offer a multitude of advantages but currently suffer from that most efficient phosphorescent emitters are based on expensive and rare metals. Herein, it is demonstrated that a rare metal-free salt, bis(benzyltriphenylphosphonium)tetrabromidomanganate(II) ([Ph₃PBn]₂[MnBr₄]), can function as the phosphorescent emitter in an LEC, and that a careful device design results in the fact that such a rare metal-free phosphorescent LEC delivers broadband white emission with a high color rendering index (CRI) of 89. It is further shown that broadband emission is effectuated by an electric-field-driven structural transformation of the original green-light emitter structure into a red-emitting structure. 

Light-emitting materials based on earth-abundant metals, such as manganese hold great promise as emitters for organic lighting devices. In order to apply such emitter materials and, in particular, to overcome the problem of self-quenching due to cross-relaxation, we investigated a series of tetrabromidomanganate ([MnBr₄]²⁻) salts with bulky tetraalkylphosphonium counter cations [P_nnn]⁺, namely [P_nnnn]₂[MnBr₄] (n = 4 (1), 6 (2) and 8 (3)), which can be obtained by a straightforward reaction of the respective phosphonium bromide and MnBr₂. Variation of the cation size allows control of the properties of the resulting ionic materials. 1 and 3 qualify as ionic liquids (ILs), where 1 features a melting point of 68 °C, and 3 is liquid at room temperature and even at very low temperatures. Furthermore, 1 and 2 show the formation of higher-ordered thermotropic mesophases. For 1 a transition to a thermodynamically metastable smectic liquid crystalline phase can be observed at room temperature upon reheating from the metastable glassy state; 2 appears to form a plastic crystalline phase at ∼63 °C, which persists up to the melting point of 235 °C. The photoemission is greatly affected by phase behaviour and ion dynamics. A photoluminescence quantum yield of 61% could be achieved, by balancing the increase in Mn²⁺-Mn²⁺ separation and reducing self-quenching through increasingly large organic cations which leads to adverse increased vibrational quenching. Compared to analogous ammonium compounds, which have been promoted as @#x0308;inorganic hybrid perovskite, the phosphonium salts show superior performance, with respect to photoluminescent quantum yield and thermal and air/humidity stability. As the presented compounds are not sensitive to the atmosphere, in particular moisture, and show strong visible electroluminescence in the green region of light, they are important emitter materials for use in organic light-emitting devices.

Albeit tris(8-hydroxyquinolinato) aluminum (Alq₃) and its derivatives are prominent emitter materials for organic lighting devices, and the optical transitions occur among ligand-centered states, the use of metal-free 8-hydroxyquinoline is impractical as it suffers from strong nonradiative quenching, mainly through fast proton transfer. Herein, it is shown that the problem of rapid proton exchange and vibration quenching of light emission can be overcome not only by complexation, but also by organization of the 8-hydroxyquinolinium cations into a solid rigid network with appropriate counter-anions (here bis(trifluoromethanesulfonyl)imide). The resulting structure is stiffened by secondary bonding interactions such as π-stacking and hydrogen bonds, which efficiently block rapid proton transfer quenching and reduce vibrational deactivation. Additionally, the optical properties are tuned through methyl substitution from deep blue (455 nm) to blue-green (488 nm). Time-dependent density functional theory (TDFT) calculations reveal the emission to occur from which an unexpectedly long-lived S₁ level, unusual for organic fluorophores. All compounds show comparable, even superior photoluminescence compared to Alq₃ and related materials, both as solids and thin films with quantum yields (QYs) up to 40–50%. In addition, all compounds show appreciable thermal stability with decomposition temperatures above 310 °C.

In the search for new multifunctional materials, particularly for application in solid-state lighting, a set of terbium salicylato (Sal) complexes of general composition [Cat][Tb(Sal)4] with the commonly ionic liquid-forming (IL) cations [Cat] = (2-hydroxyethyl)trimethylammonium (choline) (Chol+), diallyldimethylammonium (DADMA+), 1-ethyl-3-methylimidazolium (C2C1Im+), 1-butyl-3-methylimidazolium (C4C1Im+), 1-ethyl-3-vinylimidazolium (C2Vim+), and tetrabutylphosphonium (P4444+) were synthesized. All Tb compounds exhibit strong green photoluminescence of high color purity by energy transfer from the ligand in comparison with what the analogous La compounds show, and quantum yields can reach up to 63% upon ligand excitation. When excited with an HF generator, the compounds show strong green electroluminescence with the same features of mission. The findings promise a high potential of application as emitter materials in solid-state lighting. As an additional feature, the Tb compounds show a strong response to applied external fields, rendering them multifunctional materials.

Many crystalline materials form polymorphs and undergo solid–solid transitions between different forms as a function of temperature or pressure. However, there is still a poor understanding of the mechanism of transformation. Conclusions about the transformation process are typically drawn by comparing the crystal structures before and after the conversion, but gaining detailed mechanistic knowledge is strongly impeded by the generally fast rate of these transitions. When the crystal morphology does not change, it is assumed that crystallinity is maintained throughout the process. Here we report transformation between polymorphs of ZnCl2(1,3-diethylimidazole-2-thione)2 which are sufficiently slow to allow unambiguous assignment of single crystal to single crystal transformation with shape preservation proceeding through an amorphous intermediate phase. This result fundamentally challenges the commonly accepted views of polymorphic phase transition mechanisms.

Rare-earth-based Ca₉RE(PO₄)₇ (RE = Nd, Gd, Dy) materials were synthesized by solid-state reaction at T = 1200 °C. The obtained tricalcium phosphate (TCP) materials are efficient light emitters due to the presence of RE³⁺ ions, although these ions are present at high concentrations. Moreover, in these host structures, these ions can be used as optical probes to study their local environments. Thus, photoluminescence (PL) emission spectra of the powder samples clearly indicated, for Dy³⁺ and Gd³⁺ ions, the presence of the RE³⁺ ion in low-symmetry sites with some local structural disorder, and the spectra show the presence of vibrational features (in the case of Gd³⁺). For the Nd³⁺ phase, emission bands are present around 900, 1050, and 1330 nm, originating from the ⁴F_3/2 level. In general, these RE-TCP samples are interesting luminescent materials in the visible (Dy), UV (Gd), and NIR (Nd) regions, due to weak concentration quenching even for high concentrations of the emitting ion.

Pale yellow crystals of LnSb(2)O(4)Br (Ln = Eu-Tb) were synthesized via high temperature solid-state reactions from antimony sesquioxide, the respective lanthanoid sesquioxides and tribromides. Single-crystal X-ray diffraction studies revealed a layered structure in the monoclinic space group P2(1)/c. In contrast to hitherto reported quaternary lanthanoid(III) halide oxoantimonates(III), in LnSb(2)O(4)Br the lanthanoid(III) cations are exclusively coordinated by oxygen atoms in the form of square hemiprisms. These [LnO(8)](13-) polyhedra form layers parallel to (100) by sharing common edges. All antimony(III) cations are coordinated by three oxygen atoms forming psi(1)-tetrahedral [SbO3](3-) units, which have oxygen atoms in common building up meandering strands along [001] according to {[SbO2/2vO1/1t]-}infinity 1 (v = vertex-sharing, t = terminal). The bromide anions are located between two layers of these parallel running oxoantimonate(III) strands and have no bonding contacts with the Ln(3+) cations. Since Sb3+ is known to be an efficient sensitizer for Ln(3+) emission, photoluminescence studies were carried out to characterize the optical properties and assess their suitability as light phosphors. Indeed, for both, GdSb2O4Br and TbSb2O4Br doped with about 1.0-1.5 at-% Eu3+ efficient sensitization of the Eu3+ emission could be detected. For TbSb2O4Br, in addition, a remarkably high energy transfer from Tb3+ to Eu3+ could be detected that leads to a substantially increased Eu3+ emission intensity, rendering it an efficient red light emitting material.

In this study the optical spectroscopy, the excited state dynamics, and in particular the Tb3+ -> Eu3+ energy transfer, have been investigated in detail both from the theoretical and experimental point of view in eulytite double phosphate hosts A(3)Tb(PO4)(3) (A = Sr, Ba) doped with Eu3+. It has been found that the energy transfer is strongly assisted by fast migration in the donor Tb3+ subset. Moreover, the transfer rates and efficiencies depend significantly on the nature of the divalent elements present in the structure and hence on the distances between Tb3+-Eu3+ nearest neighbors. It is shown that the competition between quadrupole-quadrupole and exchange interaction is crucial in accounting for the transfer rates.