Charge Transfer Luminescence Research Articles

Organic Excitonic State Management by Surface Metallic Coupling of Inorganic Lanthanide Nanocrystals

AbstractThe ability to harness charges and spins for control of organic excitonic states is critical in developing high‐performance organic luminophores and optoelectronic devices. Here we report a facile strategy to efficiently manipulate the electronic energy states of various organic phosphors by coupling them with inorganic lanthanide nanocrystals. We show that the metallic atoms exposed on the nanocrystal surface can introduce strong coupling effects to 9‐(4‐ethoxy‐6‐phenyl‐1,3,5‐triazin‐2‐yl)‐9H‐carbazole (OCzT) and some organic chromophores with carbazole functional groups when the organics are approaching the nanocrystals. This unconventional organic–inorganic hybridization enables a nearly 100 % conversion of the singlet excitation to fast charge transfer luminescence that does not exist in pristine organics, which broadens the utility of organic phosphors in hybrid systems.

Organic Excitonic State Management by Surface Metallic Coupling of Inorganic Lanthanide Nanocrystals.

The ability to harness charges and spins for control of organic excitonic states is critical in developing high-performance organic luminophores and optoelectronic devices. Here we report a facile strategy to efficiently manipulate the electronic energy states of various organic phosphors by coupling them with inorganic lanthanide nanocrystals. We show that the metallic atoms exposed on the nanocrystal surface can introduce strong coupling effects to 9-(4-ethoxy-6-phenyl-1,3,5-triazin-2-yl)-9H-carbazole (OCzT) and some organic chromophores with carbazole functional groups when the organics are approaching the nanocrystals. This unconventional organic-inorganic hybridization enables a nearly 100 % conversion of the singlet excitation to fast charge transfer luminescence that does not exist in pristine organics, which broadens the utility of organic phosphors in hybrid systems.

Multi-Responsive Eight-State Bis(acridinium-Zn(II) porphyrin) Receptor.

A multi-responsive receptor consisting of two (acridinium-Zn(II) porphyrin) conjugates has been designed. The binding constant between this receptor and a ditopic guest has been modulated (i) upon addition of nucleophiles converting acridinium moieties into the non-aromatic acridane derivatives and (ii) upon oxidation of the porphyrin units. A total of eight states has been probed for this receptor resulting from the cascade of the recognition and responsive events. Moreover, the acridinium/acridane conversion leads to a significant change of the photophysical properties, switching from electron to energy transfer processes. Interestingly, for the bis(acridinium-Zn(II) porphyrin) receptor, charge-transfer luminescence in the near-infrared has been observed.

Theoretical studies on thermodynamic stabilities and luminescent mechanisms of defects and lanthanide ions in BaZrSi3O9

Theoretical studies on thermodynamic stabilities and luminescent properties for the defects and lanthanide ions in the BaZrSi3O9 are performed in order to better understand luminescence mechanisms of undoped and lanthanide-doped BaZrSi3O9. The defect formation energies derived from density functional theory (DFT) calculations with the hybrid PBE0 functional are devoted to analyze thermodynamic stabilities of intrinsic (i.e., the vacancies and antisite defects) and Ti-related defects in the host. The experimental excitation spectra of Ce3+- and Eu2+-doped BaZrSi3O9 phosphors are assigned according to 4f → 5d transition energies obtained from ab-initio calculations at the complete-active-space self-consistent field/complete-active-space second-order perturbation theory/restricted-active-space state-interaction spin-orbit (CASSCF/CASPT2/RASSI−SO) level. Moreover, the mechanisms of the charge transfer (CT), thermoluminescence (TL) and long-lasting luminescence (LLL) in the undoped and lanthanide-doped BaZrSi3O9 are reasonably interpreted on the basis of the thermodynamic transition energy levels of the defects in the host.

Novel Ultrafast Lu2O3:Yb Ceramics for Future HEP Applications

Inorganic scintillators activated by charge transfer luminescence Yb3+ are considered promising ultrafast material to break the ps timing barrier for future high energy physics applications. Inorganic scintillators in ceramic form are potentially more cost-effective than crystals because of their lower fabrication temperature and no need for aftergrowth mechanical processing. This paper reports an investigation on Lu2O3:Yb and Lu2xY2(1−x)O3:Yb scintillating ceramic samples fabricated by Radiation Monitoring Devices Inc. All samples show X-ray excited luminescence peaked at 370 nm. Ultrafast decay time of 1.1 ns was observed by using a microchannel plate-photomultiplier tube-based test bench at Caltech. Considering its intrinsic high density (9.4 g/cm3), Lu2O3:Yb ceramics are promising for future time of fight application for high energy physics experiments.

On the nature of CT luminescence in Yb3+:YAG single crystal under low photon energy

The charge transfer luminescence process has been extensively studied due to its influence on the optical properties of various phosphors such as photodarkening process which is a limiting factor for the lifetime of high-power fiber lasers. In this work, we report CT luminescence in Yb3+:YAG single crystals at 3.3 eV excitation. It was found that this luminescence is caused by CT processes between Yb3+ ions and perturbed F+ centers formed during crystal growth due to the incorporation of some portion of Y3+ ions into Al3+ sites. CT luminescence in such systems can be produced at low photon energies equal to 3.3 eV excitation, with Stokes shift less than 500 cm−1.

Nonlinear phenomena in femtosecond laser systems based on Yb: YAG thin-rod amplifiers

Nonlinear effects in a high-power laser amplification system based on thin-rod active elements are experimentally investigated. It is shown that the most important nonlinear effect is the Kerr effect leading to self-focusing and self-phase modulation of laser radiation. The observed luminescence in Yb : YAG crystals in the visible region of the spectrum is caused by the charge transfer luminescence effect, which, in turn, is due to multiphoton absorption of laser radiation. Second-order nonlinearity in the crystal is used to effectively convert femtosecond pulses to second harmonic and sum-frequency waves which exhibit radiations of green and UV spectra.

Fmoc-protected amino acids as luminescent and circularly polarized luminescence materials based on charge transfer interaction

Fluorenylmethyloxycarbonyl (Fmoc)-protected amino acids are effective building blocks in self-assembled architectures at hierarchical levels, which however show limited luminescent properties and chiroptical activities. Here we introduce a charge-transfer strategy to build two-component luminescent materials with emerged circularly polarized luminescence properties. A library of Fmoc-amino acids was built, which selectively form charge-transfer complexes with the electron-deficient acceptor. Embedding in amorphous polymer matrix or physical grinding could trigger the charge-transfer luminescence with adjusted wavelengths in a general manner. X-ray diffraction results suggest the multiple binding modes between donor and acceptor. And, the solution-processed coassembly could selectively exhibit circularly polarized luminescence with high dissymmetry g-factors. This work illustrates a noncovalent charge-transfer strategy to construct luminescent and chiroptical organic composites based on the easy-accessible and economic chiral N-terminal aromatic amino acids.

Characterization of the charge transfer luminescence of the [WO6]6- octahedron in Ca3WO6 and the [WO5]4- square pyramid in Ca3WO5Cl2.

Charge transfer (CT) luminescence of different types of polyhedra, [WO5]4- in Ca3WO5Cl2 and [WO6]6- in Ca3WO6, is characterized by spectroscopic experiments and ab initio calculations. According to the geometry optimization, W6+ ions form five-fold [WO5]4- square pyramids in Ca3WO5Cl2 because of a large interatomic distance between W6+ and Cl- of 3.266 Å. The analysis of the density of electronic states reveals the ionic character of Cl- ions to the W6+ ions in the Ca3WO5Cl2 lattice, resulting in the observed broad luminescence band peak at 488 nm of the single-crystal Ca3WO5Cl2 sample being assigned to the CT transition in the [WO5]4- square pyramid. Compared with the [WO6]6- octahedron in Ca3WO6, the [WO5]4- square pyramid shows an inconsistent CT energy shift: higher CT absorption and lower luminescence energies. The larger bandgap brings about higher absorption energy due to the structural and compositional features of the orthorhombic Ca3WO5Cl2. The redshifted CT luminescence band and small activation energy for the thermal quenching of the Ca3WO5Cl2 sample are explained, assuming that the CT states of the anisotropic [WO5]4- square pyramid take a larger offset in the configurational coordinate diagram than the [WO6]6- octahedron.

Intermolecular Charge-Transfer Luminescence by Self-Assembly of Pyridinium Luminophores in Solutions.

Designing a luminophore for application both in solution and in the solid state is a highly challenging task given the distinct nature of intermolecular interactions in these phases. In this context, we demonstrate that self‐assembly of non‐emissive charged pyridinium luminophores enables luminescence in solutions through a mechanism that is characteristic for the crystal state. Specifically, protonation of pyridine luminophore subunits in a solution promotes oligomer formation through intermolecular π+‐π interactions, leading to an intermolecular charge‐transfer type luminescence. The luminescence turn‐on by protonation is utilized for a highly efficient solution‐state luminescent sensing of hydrogen chloride and sulfonic acids (TfOH, TsOH and MsOH) with detection limits spanning the range from 0.06 to 0.33 ppm. The protonation followed by self‐assembly results in a bathochromic shift of the emission from 420 nm to 550 nm.

Charge transfer characteristics and luminescence properties of Eu3+ activated Ba2YMoO6 and BaY2(MoO4)4 phosphors

Octahedrally and tetrahedrally connected Mo-O complexes in two different crystal phases were comparatively investigated. The material Ba2YMoO6:Eu3+ exhibits the cubic perovskite structure for which the Mo-O groups are coordinated octahedrally, while BaY2(MoO4)4:Eu3+ has a monoclinic crystal phase for which the Mo-O complexes are connected tetrahedrally. The photoluminescence (PL) excitation spectra show that, the intensity, position and shape of the charge transfer (CT) transitions in the two different materials depended strongly on the surrounding environment. The PL emission properties of Ba2YMoO6:Eu3+ and BaY2(MoO4)4:Eu3+ phosphors as a function of various doping content of Eu3+ ions excited at different wavelengths were explored in detail. The critical concentration of Eu3+ and the critical distance between Eu3+ ions, as well as the concentration quenching effects were discussed. The absolute quantum yield for the monoclinic phase BaY2(MoO4)4:Eu3+ phosphor was about an order of magnitude higher than that of the cubic phase Ba2YMoO6:Eu3+ phosphor.

Manganese(I) complexes with metal-to-ligand charge transfer luminescence and photoreactivity.

Precious metal complexes with the d6 valence electron configuration often exhibit luminescent metal-to-ligand charge transfer (MLCT) excited states, which form the basis for many applications in lighting, sensing, solar cells and synthetic photochemistry. Iron(II) has received much attention as a possible Earth-abundant alternative, but to date no iron(II) complex has been reported to show MLCT emission upon continuous-wave excitation. Manganese(I) has the same electron configuration as that of iron(II), but until now has typically been overlooked in the search for cheap MLCT luminophores. Here we report that isocyanide chelate ligands give access to air-stable manganese(I) complexes that exhibit MLCT luminescence in solution at room temperature. These compounds were successfully used as photosensitizers for energy- and electron-transfer reactions and were shown to promote the photoisomerization of trans-stilbene. The observable electron transfer photoreactivity occurred from the emissive MLCT state, whereas the triplet energy transfer photoreactivity originated from a ligand-centred 3π-π* state.

Ultrafast excited state dynamics and light-switching of [Ru(phen)2(dppz)]2+ in G-quadruplex DNA

The triplet metal to ligand charge transfer (3MLCT) luminescence of ruthenium (II) polypyridyl complexes offers attractive imaging properties, specifically towards the development of sensitive and structure-specific DNA probes. However, rapidly-deactivating dark state formation may compete with 3MLCT luminescence depending on different DNA structures. In this work, by combining femtosecond and nanosecond pump-probe spectroscopy, the 3MLCT relaxation dynamics of [Ru(phen)2(dppz)]2+ (phen = 1,10-phenanthroline, dppz = dipyridophenazine) in two iconic G-quadruplexes has been scrutinized. The binding modes of stacking of dppz ligand on the terminal G-quartet fully and partially are clearly identified based on the biexponential decay dynamics of the 3MLCT luminescence at 620 nm. Interestingly, the inhibited dark state channel in ds-DNA is open in G-quadruplex, featuring an ultrafast picosecond depopulation process from 3MLCT to a dark state. The dark state formation rates are found to be sensitive to the content of water molecules in local G-quadruplex structures, indicating different patterns of bound water. The unique excited state dynamics of [Ru(phen)2(dppz)]2+ in G-quadruplex is deciphered, providing mechanistic basis for the rational design of photoactive ruthenium metal complexes in biological applications.

Inorganic luminescent pigments

Abstract Inorganic luminescent pigments (luminescent materials, luminophores, phosphors) as synthetically generated crystalline compositions absorb energy followed by emission of light with lower energy, respectively, longer wavelengths. The light emission occurs often in the visible spectral range. External energy is necessary to enable luminescent materials to generate light. Luminescent pigments are divided into fluorescent and phosphorescent pigments. This classification goes back to different energy transitions. Emission based on allowed optical transitions, with decay times in the order of µs or faster is defined as fluorescence. Emission with longer decay times is called phosphorescence. The occurrence of fluorescence or phosphorescence as well as the decay time depend on structure and composition of a specific luminophore. There are four luminescence mechanisms discussed for inorganic luminescent materials: center luminescence, charge-transfer luminescence, donor–acceptor pair luminescence, and long-afterglow phosphorescence. The emission of luminescent light can have its origin in different excitation mechanisms such as optical excitation (UV radiation or even visible light), high-voltage or low-voltage electroluminescence and excitation with high energy particles (X-rays, γ-rays). Inorganic luminescent pigments are used mainly in fluorescent lamps, cathode-ray tubes, projection television tubes, plasma display panels, light-emitting diodes (LEDs) and for X-ray and γ-ray detection. The pigment particles are dispersed for the applications in specific binder systems. They are applied in form of thin layers and by means of luminophore/solvent suspensions, containing adhesive agents, on a substrate.

Strategy for Achieving Long-Wavelength Near-Infrared Luminescence of Diimineplatinum(II) Complexes.

Although many strategies have been used to help design effective near-infrared (NIR) luminescent materials, it is still a huge challenge to realize long-wavelength NIR luminescence of diimineplatinum(II) complexes in the solid state. Herein, we have successfully achieved long-wavelength NIR luminescence of a family of diimineplatinum(II) complexes based on a new strategy that combines a one-dimensional (1D) "Pt wire" structure with the electronic effect of the substituent. The structures of six solvated diimineplatinum(II) complexes based on 4,4-dichloro-2,2'-bipyridine or 4,4-dibromo-2,2'-bipyridine and 4-substituted phenylacetylene ligands have been determined, namely, 1·1/2toluene, 2·1/2THF, 3·1/8toluene, 4·1/2THF, 5·1/8CH2Cl2, and 6·1/4toluene. All of them crystallize in the monoclinic space group C2/c or C2/m and stack in the 1D "Pt wire" structure. In the solid state, six complexes exhibited unusual long-wavelength metal-metal-to-ligand charge-transfer luminescence that peaked at 984, 1044, 972, 990, 1022, and 935 nm, respectively. Interestingly, 2·1/2THF has the shortest Pt···Pt distance and the longest emission wavelength among the six complexes. As far as we know, the luminescence of 2·1/2THF at 1044 nm is the longest emission wavelength among known diimineplatinum(II) complexes. Systematic studies revealed that good molecular planarity, suitable substituent position, weak hydrogen-bond-forming ability of the substituents, appropriate molecular bending, and weakening of the interaction between solvated molecules and platinum molecules are conducive to the construction of a 1D "Pt wire" structure of the diimineplatinum(II) complex. Furthermore, the emission energy of the complex is mainly determined by the strength of the Pt-Pt interaction and electronic effect of the substituent.

Confining electron donor and acceptor in space to realize high efficiency charge-transfer luminescence

Confining electron donor and acceptor in space to realize high efficiency charge-transfer luminescence

Broadband infrared LEDs based on europium-to-terbium charge transfer luminescence

Efficient broadband infrared (IR) light-emitting diodes (LEDs) are needed for emerging applications that exploit near-IR spectroscopy, ranging from hand-held electronics to medicine. Here we report broadband IR luminescence, cooperatively originating from Eu2+ and Tb3+ dopants in CaS. This peculiar emission overlaps with the red Eu2+ emission, ranges up to 1200 nm (full-width-at-half-maximum of 195 nm) and is efficiently excited with visible light. Experimental evidence for metal-to-metal charge transfer (MMCT) luminescence is collected, comprising data from luminescence spectroscopy, microscopy and X-ray spectroscopy. State-of-the-art multiconfigurational ab initio calculations attribute the IR emission to the radiative decay of a metastable MMCT state of a Eu2+-Tb3+ pair. The calculations explain why no MMCT emission is found in the similar compound SrS:Eu,Tb and are used to anticipate how to fine-tune the characteristics of the MMCT luminescence. Finally, a near-IR LED for versatile spectroscopic use is manufactured based on the MMCT emission.

Excited-State Relaxation in Luminescent Molybdenum(0) Complexes with Isocyanide Chelate Ligands

Diisocyanide ligands with a m-terphenyl backbone provide access to Mo0 complexes exhibiting the same type of metal-to-ligand charge transfer (MLCT) luminescence as the well-known class of isoelectronic RuII polypyridines. The luminescence quantum yields and lifetimes of the homoleptic tris(diisocyanide) Mo0 complexes depend strongly on whether methyl- or tert-butyl substituents are placed in α-position to the isocyanide groups. The bulkier tert-butyl substituents lead to a molecular structure in which the three individual diisocyanides ligated to one Mo0 center are interlocked more strongly into one another than the ligands with the sterically less demanding methyl substituents. This rigidification limits the distortion of the complex in the emissive excited-state, causing a decrease of the nonradiative relaxation rate by one order of magnitude. Compared to RuII polypyridines, the molecular distortions in the luminescent 3MLCT state relative to the electronic ground state seem to be smaller in the Mo0 complexes, presumably due to delocalization of the MLCT-excited electron over greater portions of the ligands. Temperature-dependent studies indicate that thermally activated nonradiative relaxation via metal-centered excited states is more significant in these homoleptic Mo0 tris(diisocyanide) complexes than in [Ru(2,2′-bipyridine)3]2+.

Tuned Hydrogen Bonding in Rare-Earth Metal-Organic Frameworks for Design of Optical and Electronic Properties: An Exemplar Study of Y-2,5-Dihydroxyterephthalic Acid.

Organic linkers in metal-organic framework (MOF) materials exhibit differences in hydrogen bonding (H-bonding), which can alter the geometric, electronic, and optical properties of the MOF. Density functional theory (DFT) simulations were performed on a photoluminescent Y-2,5-dihydroxyterephthalic acid (DOBDC) MOF with H-bonding concentrations between 0 and 100%; the H-bonds were located on both bidentate- and monodentate-bound DOBDC linkers. At 0% H-bond concentration in the framework, the lattice parameters contracted, the density increased, and simulated X-ray diffraction patterns shifted. Comparison with published experimental data identified that Y-DOBDC MOF structures must have a degree of H-bond concentration. The concentration of H-bonds in the system shifted the calculated band gap energy from 2.25 eV at 100% to 3.00 eV at 0%. The band gap energies also indicate a distinction of H-bonds formed on bidentate-coordinated linkers compared to those on monodentate linkers. Additionally, when the calculated optical spectra are compared with experimental data, the ligand-to-ligand charge-transfer luminescence in Y-DOBDC MOFs is expected to result from an average of 20-40% H-bonding with at least 50% of the bidentate linkers containing H-bonding. Therefore, the type of H-bonding within the DOBDC linker determines the electronic structure and the optical absorption of the MOF framework structure. Tuning of the H-bonding in rare-earth MOFs provides an opportunity to control the specific optical and adsorption properties of the MOF framework on the basis of reactions between the linker and the environment.

Afterglow Effects as a Tool to Screen Emissive Nongeminate Charge Recombination Processes in Organic Photovoltaic Composites.

Disentangling temporally overlapping charge carrier recombination events in organic bulk heterojunctions by optical spectroscopy is challenging. Here, a new methodology for employing delayed luminescence spectroscopy is presented. The proposed method is capable of distinguishing between recombination of spatially separated charge carriers and trap-assisted charge recombination simply by monitoring the delayed luminescence (afterglow) of bulk heterojunctions with a quasi time-integrated detection scheme. Applied on the model composite of the donor poly(6,12-dihydro-6,6,12,12-tetraoctyl-indeno[1,2-b]fluorene-alt-benzothiadiazole) (PIF8BT) polymer and the acceptor ethyl-propyl perylene diimide (PDI) derivative, that is, PIF8BT:PDI, the luminescence of charge-transfer (CT) states created by nongeminate charge recombination on the ns to μs timescale is observed. Fluence-dependent, quasi time-integrated detection of the CT luminescence monitors exclusively emissive charge recombination events, while rejecting the contribution of other early-time emissive processes. Trap-assisted and bimolecular charge recombination channels are identified based on their distinct dependence on fluence. The importance of the two recombination channels is correlated with the layer's order and electrical properties of the corresponding devices. Four different microstructures of the PIF8BT:PDI composite obtained by thermal annealing are investigated. Thermal annealing of PIF8BT:PDI shrinks the PDI domains in parallel with the growth of the PIF8BT domains in the blend. Common to all states studied, the delayed CT luminescence signal is dominated by trap-assisted recombination. Yet, the minor fraction of fully separated charge recombination in the overall CT emission increases as the difference in the size of the donor and acceptor domains in the PIF8BT:PDI blend becomes larger. Electric field-induced quenching measurements on complete PIF8BT:PDI devices confirm quantitatively the dominance of emissive trap-limited charge recombination and demonstrates that only 40% of the PIF8BT/PDI CT luminescence comes from the recombination of fully-separated charges, taking place within 200 ns after photoexcitation. The method is applicable to other nonfullerene acceptor blends beyond the system discussed here, if their CT state luminescence can be monitored.