Emission Quenching in Tetraphenylfuran Crystal: Why This Propeller-Shaped Molecule Does Not Emit in the Condensed Phase?

Due to their substantial fluorescence quantum yields in the crystalline phase, propeller-shaped molecules have recently gained significant attention as potential emissive materials for optoelectronic applications. For the family of cyclopentadiene derivatives, light-emission is highly dependent on the nature of heteroatomic substitutions. In this paper, we investigate excited state relaxation pathways in the tetraphenyl-furan molecule (TPF), which in contrast with other molecules in the family, shows emission quenching in the solid-state. For the singlet manifold, our calculations show nonradiative pathways associated with C-O elongation are blocked in both vacuum and the solid state. A fraction of the population can be transferred to the triplet manifold and, subsequently, to the ground state in both phases. This process is expected to be relatively slow due to the small spin-orbit couplings between the relevant singlet-triplet states. Emission quenching in crystalline TPF seems to be in line with more efficient exciton hopping rates. Our simulations help clarify the role of conical intersections, population of the triplet states and crystalline structure in the emissive response of propeller-shaped molecules.

Photophysical Details and O2-Sensing Analysis of a Eu(III) Complex in Polymer Composite Nanofibers Prepared by Electrospinning

An as-synthesized Eu(III) complex, denoted as Eu(N-DPNQ)(TTD)3, was prepared and characterized, and the antenna mechanism between these ligands and central metal emitter was studied. Here DPNQ means 10-ethyl-10H-indolo [2′,3':5,6]pyrazino[2,3-f][1,10]phenanthroline and TTD is 4,4,4-trifluoro-1-(thiophen-2-yl)butane-1,3-dione. We find that Eu(N-DPNQ)(TTD)3 emission intensity dependents on oxygen concentration, and O2-sensing skill of Eu(N-DPNQ)(TTD)3 in polymer composite nanofibers of poly (vinylpyrrolidone) (PVP) prepared by electrospinning is investigated. Results reveal that the emission quenching of Eu(N-DPNQ)(TTD)3 is caused by the ground state (triplet) oxygen quenching on antenna ligands triplet state. The Eu(N-DPNQ)(TTD)3 doped composite nanofiber with a loading level of 6 wt% exhibits the best result with sensitivity of 2.43 and response time of 10 s, along with linear response.

Paper Sensors Based on Fluorescence Changes of Carbon Nanodots for Optical Detection of Nanomaterials

A paper sensor was designed in order to detect the presence of nanomaterials, such as ZnO and silica nanoparticles, as well as graphene nanoplatelets (GnP), based on fluorescence changes of carbon nanodots. Paper strips were functionalized with carbon nanodots using polyvinyl alcohol (PVA) as binder. The carbon nanodots were highly fluorescent and, hence, rendered the (cellulosic) paper stripes emissive. In the presence of silica and ZnO nanoparticles, the fluorescence emission of the carbon nanodots was quenched and the emission decay was shortened, whereas in the presence of GnP only emission quenching occurred. These different photoluminescence (PL) quenching mechanisms, which are evident from lifetime measurements, convey selectivity to the sensor. The change in fluorescence of the carbon dot-functionalized paper is also evident to the naked eye under illumination with a UV lamp, which enables easy detection of the nanomaterials. The sensor was able to detect the nanomaterials upon direct contact, either by dipping it in their aqueous dispersions, or by sweeping it over their powders. The use of the proposed optical sensor permits the detection of nanomaterials in a straightforward manner, opening new ways for the development of optical sensors for practical applications.

Optical Quality of InAs/InP Quantum Dots on Distributed Bragg Reflector Emitting at 3rd Telecom Window Grown by Molecular Beam Epitaxy

We present an experimental study on the optical quality of InAs/InP quantum dots (QDs). Investigated structures have application relevance due to emission in the 3rd telecommunication window. The nanostructures are grown by ripening-assisted molecular beam epitaxy. This leads to their unique properties, i.e., low spatial density and in-plane shape symmetry. These are advantageous for non-classical light generation for quantum technologies applications. As a measure of the internal quantum efficiency, the discrepancy between calculated and experimentally determined photon extraction efficiency is used. The investigated nanostructures exhibit close to ideal emission efficiency proving their high structural quality. The thermal stability of emission is investigated by means of microphotoluminescence. This allows to determine the maximal operation temperature of the device and reveal the main emission quenching channels. Emission quenching is predominantly caused by the transition of holes and electrons to higher QD’s levels. Additionally, these carriers could further leave the confinement potential via the dense ladder of QD states. Single QD emission is observed up to temperatures of about 100 K, comparable to the best results obtained for epitaxial QDs in this spectral range. The fundamental limit for the emission rate is the excitation radiative lifetime, which spreads from below 0.5 to almost 1.9 ns (GHz operation) without any clear spectral dispersion. Furthermore, carrier dynamics is also determined using time-correlated single-photon counting.

Two Luminescent Iridium Complexes with Phosphorous Ligands and Their Photophysical Comparison in Solution, Solid and Electrospun Fibers: Decreased Aggregation-Caused Emission Quenching by Steric Hindrance

In this paper, we prepared two phosphorescent Ir complexes with ligands of 2-phenyl pyridine (ppy), and two phosphorous ligands with large steric hindrance, hoping to allow enough time for the transformation of the highly phosphorescent 3MLLCT (metal-to-ligand-ligand-charge-transfer) excited state. Their large steric hindrance minimized the π-π interaction between complex molecules, so that the aggregation-induced phosphorescence emission (AIPE) influence could be minimized. Their single crystals indicated that they took a distorted octahedral coordination mode. Photophysical comparison between these Ir complexes in solution, in the solid state and in electrospun fibers was performed to confirm the realization of limited aggregation-caused quenching (ACQ). The potential surface crossing and energy transfer from 3MLBPECT/3MLBPELppyCT to 3MLppyCT in these Ir complexes were revealed by density functional theory calculation and temperature-dependent emission. It was confirmed that these two phosphorous ligands offered large steric hindrance, which decreased the ACQ effect, allowing the efficient emissive decay of the 3MLppyCT excited state. This is one of the several luminescent Ir complexes with a high emission yield (Φ = 0.27) and long emission lifetime (0.43 μs) in the solid state.

4,6-Bis((E)-2-(4′-N,N-diphenylamino-[1,1′-biphenyl]-4-yl)vinyl)-2-phenylpyrimidine

In this contribution, we designed a 4,6-distyrylpyrimidine chromophore with diphenylamino electron-donating groups and biphenylenevinylene extended π-conjugated linkers. This compound has been synthesized in two steps from 4,6-dimethyl-2-phenylpyrimidine by a double Knoevenagel reaction with 4-bromobenzaldehyde followed by a double Suzuki–Miyaura cross coupling reaction with 4-(N,N-diphenylamino)phenylboronic acid. This compound exhibits intense emission in moderately polar solvents as well as in solid state. This compound is characterized by an intense emission solvatochromism with emission ranging from blue in non polar n-heptane to orange in dichloromethane. This chromophore is also sensible to the presence of acid with a bathochromic shift of the charge transfer absorption band and emission quenching.

Internal OH− induced cascade quenching of upconversion luminescence in NaYF4:Yb/Er nanocrystals

Internal hydroxyl impurity is known as one of the main detrimental factors affecting the upconversion (UC) efficiency of upconversion luminescence (UCL) nanomaterials. Different from surface/ligand-related emission quenching which can be effectively diminished by, e.g., core/shell structure, internal hydroxyl is easy to be introduced in synthesis but difficult to be quantified and controlled. Therefore, it becomes an obstacle to fully understand the relevant UC mechanism and improve UC efficiency of nanomaterials. Here we report a progress in quantifying and large-range adjustment of the internal hydroxyl impurity in NaYF4 nanocrystals. By combining the spectroscopy study and model simulation, we have quantitatively unraveled the microscopic interactions underlying UCL quenching between internal hydroxyl and the sensitizers and activators, respectively. Furthermore, the internal hydroxyl-involved UC dynamical process is interpreted with a vivid concept of “Survivor effect,” i.e., the shorter the migration path of an excited state, the larger the possibility of its surviving from hydroxyl-induced quenching. Apart from the consistent experimental results, this concept can be further evidenced by Monte Carlo simulation, which monitors the variation of energy migration step distribution before and after the hydroxyl introduction. The new quantitative insights shall promote the construction of highly efficient UC materials.