Quantum Yield Measurements Research Articles

Polymeric copper(I)-NHC complexes with bulky bidentate (N^C) ligands: synthesis and solid-state luminescence.

Starting from imidazolium chlorides bearing bulky nitrogen donors, a series of four complexes, mainly [Cu(C^N)Cl]n coordination polymers were obtained directly as luminescent species by simple filtration from the aqueous reaction medium, highlighting a simple, eco-friendly, robust and reproducible synthetic procedure. Additionally, we have shown on the most efficient example that chloride could be exchanged very easily by other halides/pseudohalides (Br-, I-, NCS-, N3-) allowing to slightly modulate the emitted colour while conserving the polymeric structure, except for azide for which a dimer was obtained. The combination of chemical analyses, of photoluminescence studies in the solid state including quantum yield measurement and X-ray diffraction on single crystals and as-synthesized microcrystalline powders highlighted that the polymeric luminescent species was indeed obtained directly by simple filtration and that no major alteration of the structure was observed upon recrystallisation. Samples of all polymeric complexes displayed remarkable stability towards air oxidation remaining unchanged upon storage for several months and partially retaining their photoluminescence properties even after a thermal treatment at 100 °C for 24 h.

Coumarin‐Based Reversible Fluorescent Chemosensors for the Sequential Detection of Copper and Citrate Ions

AbstractTwo novel coumarin‐based Schiff‐base chemosensors are presented. Courtesy to an extended conjugation between the coumarin ring and the attached π‐containing groups, both chemosensors display noteworthy photo‐physical properties including emission maxima at >550 nm. Both chemosensors function as the selective sensors for the ‘turn‐off’ detection of copper ion with the significant nanomolar detection limits. The sensing event was investigated through proton NMR and mass spectroscopy; pH studies; life‐time and quantum yield measurements and DFT studies. The solution‐generated [chemosensor‐Cu] species illustrated remarkably selective secondary ‘turn‐on’ detection of the citrate ion. The sequential detection of the copper and citrate ions have been utilized for the construction of logic gates as well as several low‐cost detection methods.

Luminance and Brightness: Application to Lanthanide-Based Coordination Polymers.

Measuring the luminance of lanthanide-based coordination polymers under UV excitation is of prime importance for many technological applications. This study highlights that the quantum yield gives no information about the luminescence intensity of a solid-state compound. Indeed, compounds with high quantum yield can actually be poorly luminescent. Therefore, a brightness calculation or a luminance measurement are mandatory for a quantitative estimation of the luminescence intensity. The calculated brightness appears to be a convenient quantitative parameter for the estimation of the luminescence intensity in the infrared domain, in which luminance is senseless. It is also a useful parameter in the visible domain, but one must keep in mind that only compounds with similar colorimetric coordinates can be compared. For comparing the luminescence intensities of compounds that exhibit different emission colors, the luminance measurement seems to be the most efficient method. A home-made setup that allows this measurement with high reproducibility is described in detail. The luminance of several lanthanide-based coordination polymers with benzene-poly-carboxylate ligands is measured, and the results are compared with brightness and quantum yield measurements. A standard is suggested for calibration.

Mitigation of Open‐Circuit Voltage Losses in Perovskite Solar Cells Processed over Micrometer‐Sized‐Textured Si Substrates

AbstractThe recent development of solution‐processed perovskite thin films over micrometer‐sized textured silicon bottom solar cells enables tandem solar cells with power conversion efficiencies > 30%. Next to improved light harvesting, textured silicon wafers are the industrial standard. To achieve high performance, the open‐circuit voltage losses that occur when fabricating perovskite solar cells over such textures need to be mitigated. This study provides a practical guideline to discriminate and address the voltage losses at the interfaces as well as in the bulk of solution‐processed double cation perovskite thin films using photoluminescence quantum yield measurements. Furthermore, the origin of these losses is investigated via morphological, microstructural, and compositional analysis and present possible mitigation strategies. The guideline will be beneficial for scientists working on randomly textured surfaces and provides a deeper understanding on this timely research topic.

Photoinduced B-Cl Bond Fission in Aldehyde-BCl3 Complexes as a Mechanistic Scenario for C-H Bond Activation.

In concert with carbonyl compounds, Lewis acids have been identified as a versatile class of photocatalysts. Thus far, research has focused on activation of the substrate, either by changing its photophysical properties or by modifying its photochemistry. In this work, we expand the established mode of action by demonstrating that UV photoexcitation of a Lewis acid-base complex can lead to homolytic cleavage of a covalent bond in the Lewis acid. In a study on the complex of benzaldehyde and the Lewis acid BCl3, we found evidence for homolytic B-Cl bond cleavage leading to formation of a borylated ketyl radical and a free chlorine atom only hundreds of femtoseconds after excitation. Both time-dependent density functional theory and transient absorption experiments identify a benzaldehyde-BCl2 cation as the dominant species formed on the nanosecond time scale. The experimentally validated B-Cl bond homolysis was synthetically exploited for a BCl3-mediated hydroalkylation reaction of aromatic aldehydes (19 examples, 42-76% yield). It was found that hydrocarbons undergo addition to the C═O double bond via a radical pathway. The photogenerated chlorine radical abstracts a hydrogen atom from the alkane, and the resulting carbon-centered radical either recombines with the borylated ketyl radical or adds to the ground-state aldehyde-BCl3 complex, releasing a chlorine atom. The existence of a radical chain was corroborated by quantum yield measurements and by theory. The photolytic mechanism described here is based on electron transfer between a bound chlorine and an aromatic π-system on the substrate. Thereby, it avoids the use of redox-active transition metals.

Substituted boron subphthalocyanines – Prospective compounds for theranostics: Synthesis, photochemical properties and in vitro cytotoxicity

Boron subphthalocyanines bearing a wide range of functional groups were tested as prospective photosensitizers and fluorophores. Synthetic protocols to novel 4-ethoxycarbonylphenoxy-substituted subphthalocyanine and phenoxy-substituted subphthalocyanine boron phenolate were presented. Differential triplet-triplet absorption spectra of subphthalocyanines were registered and triplet state lifetimes (τT = 0.6 ÷ 3.1 ms) were obtained. The results of flash photolysis measurements predicted the good ability of target subphthalocyanines to produce singlet oxygen and it was supported by the measurements of 1O2 quantum yields (ΦΔ = 0.47 ÷ 0.85). At the same time, satisfactory yields of fluorescence (Φf = 0.13 ÷ 0.50) were observed for most of the subphthalocyanines. The fluorescence decay kinetics were studied to determine the fluorescence lifetimes (τf = 0.30 ÷ 3.05 ns) and confirm the regularities obtained for fluorescence yields. Pronounced fluorescent properties allowed investigating the distribution of subphthalocyanines in the endoplasmic reticulum. In addition, the binding constants with human serum albumin were determined. tert-Butyl- and iodo-substituted subphthalocyanines demonstrated remarkable photocytotoxicity in human epidermoid carcinoma cells at micromolar concentrations. At the same time, target boron subphthalocyanines exhibited low dark cytotoxicity. All mentioned above make boron subphthalocyanines promising candidates as highly effective photosensitizers for photodynamic therapy and fluorescent labels for diagnostic.

Hybrid composites based on aerogels: Preparation, structure and tunable luminescence

The luminescence of silica aerogel-like composites, containing 1,10 – phenanthroline complexes of Tb(III) and Eu(III) as a model system for red-green-blue (RGB) sensor applications is described. The composites are obtained using an improved two-step colloidal approach, allowing the in situ formation of optical centers in the pores of the silica matrix. Quantum yield measurements, luminescence and excitation spectra suggest a dependence of the luminescence on the degree of hydrophobicity of the initial aerogel powders. A structural disorder, taking place during the in situ formation of the lanthanide complexes is detected using X-ray diffraction and a luminescence spectra – structure symmetry analysis.

Visible Light-Mediated Enantioselective Addition of α-Aminoalkyl Radicals to Ketones Catalyzed by Chiral Oxazaborolidinium Ion.

The development of a visible light-mediated synthetic method for chiral 1,2-amino tertiary alcohols is described. In the presence of a chiral oxazaborolidinium ion catalyst and photosensitizer, the enantioselective addition of an α-aminoalkyl radical to aryl methyl ketones under visible light provides chiral 1,2-amino tertiary alcohol derivatives in high yields (up to 88%) with excellent enantioselectivities (up to 98% ee). With mechanistic studies such as radical trapping analysis, radical clock analysis, and the measurement of quantum yield, a plausible catalytic cycle is proposed.

Bonding in nitrile photo-dissociating ruthenium drug candidates-A local vibrational mode study.

In this work, we investigated bonding features of 15 ruthenium(II) nitrile complexes of the type [Ru(tpy)(L)-(CH3CN)]n+, containing the tridentate tpy ligand (tpy = 2,2':6',2″-terpyridine) and various bidentate ancillary ligands L; 12 compounds originally synthesized by Loftus et al. [J. Phys. Chem. C 123, 10291-10299 (2019)] and three new complexes. We utilized local vibrational force constants derived from the local mode theory as a quantitative measure of bond strength complemented with the topological analysis of the electron density and the natural bond orbital analysis. Loftus et al. suggested that nitrile dissociation occurs after light induced singlet-triplet transition of the original complexes and they used as a measure of nitrile release efficiency quantum yields for ligand exchange in water. They observed larger quantum yields for complexes with smaller singlet-triplet energy gaps. The major goal of this work was to assess how the Ru-NC and Ru-L bond strengths in these 15 compounds relate to and explain the experimental data of Loftus et al., particularly focusing on the question whether there is a direct correlation between Ru-NC bond strength and measured quantum yield. Our study provides the interesting result that the compounds with the highest quantum yields also have the strongest Ru-NC bonds suggesting that breaking the Ru-NC bond is not the driving force for the delivery process rather than the change of the metal framework as revealed by first results of a unified reaction valley approach investigation of the mechanism. Compounds with the highest quantum yield show larger electronic structure changes upon singlet-triplet excitation, i.e., larger changes in bond strength, covalency, and difference between the singlet and triplet HOMOs, with exception of the compound 12. In summary, this work provides new insights into the interplay of local properties and experimental quantum yields forming in synergy a useful tool for fine tuning of existing and future design of new nitrile releasing ruthenium compounds. We hope that this work will bring theoretical and experimental studies closer together and serves as an incubator for future collaboration between computational chemists and their experimental colleagues.

Defect Passivation Using a Phosphonic Acid Surface Modifier for Efficient RP Perovskite Blue-Light-Emitting Diodes.

Defect management strategies are vital for enhancing the performance of perovskite-based optoelectronic devices, such as perovskite-based light-emitting diodes (PeLEDs). As additives can fucntion both as acrystallization modifier and/or defect passivator, a thorough study on the roles of additives is essential, especially for blue emissive Pe-LEDs, where the emission is strictly controlled by the n-domain distribution of the Ruddlesden-Popper (RP, L2An-1PbnX3n+1, where L refers to a bulky cation, while A and X are monovalent cation, and halide anion, respectively) perovskite films. Of the various additives that are available, octyl phosphonic acid (OPA) is of immense interest because of its ability to bind with uncoordinated Pb2+ ( notorious for nonradiative recombination) and therefore passivates them. Here, with the help of various spectroscopic techniques, such as X-ray photon-spectroscopy (XPS), Fourier-transform infrared spectroscopy (FTIR), and photoluminescence quantum yield (PLQY) measurements, we demonstrate the capability of OPA to bind and passivate unpaired Pb2+ defect sites. Modification to crystallization promoting higher n-domain formation is also observed from steady-state and transient absorption (TA) measurements. With OPA treatment, both the PLQY and EQE of the corresponding PeLED showed improvements up to 53% and 3.7% at peak emission wavelength of 485 nm, respectively.

Dopamine Photochemical Behaviour under UV Irradiation.

To understand the photochemical behaviour of the polydopamine polymer in detail, one would also need to know the behaviour of its building blocks. The electronic absorption, as well as the fluorescence emission and excitation spectra of the dopamine were experimentally and theoretically investigated considering time-resolved fluorescence spectroscopy and first-principles quantum theory methods. The shape of the experimental absorption spectra obtained for different dopamine species with standard, zwitterionic, protonated, and deprotonated geometries was interpreted by considering the advanced equation-of-motion coupled-cluster theory of DLPNO-STEOM. Dynamical properties such as fluorescence lifetimes or quantum yield were also experimentally investigated and compared with theoretically predicted transition rates based on Fermi’s Golden Rule-like equation. The results show that the photochemical behaviour of dopamine is strongly dependent on the concentration of dopamine, whereas in the case of a high concentration, the zwitterionic form significantly affects the shape of the spectrum. On the other hand, the solvent pH is also a determining factor for the absorption, but especially for the fluorescence spectrum, where at lower pH (5.5), the protonated and, at higher pH (8.0), the deprotonated forms influence the shape of the spectra. Quantum yield measurements showed that, besides the radiative deactivation mechanism characterized by a relatively small QY value, non-radiative deactivation channels are very important in the relaxation process of the electronic excited states of different dopamine species.

Tetrachlorophthalimides as Organocatalytic Acceptors for Electron Donor-Acceptor Complex Photoactivation.

Excitation of photoactive electron donor-acceptor (EDA) complexes is an effective way to generate radicals. Applications in a catalytic regime typically use catalytic donors. Herein, we report that readily available electron-poor tetrachlorophthalimides can act as effective organocatalytic acceptors to trigger the formation of EDA complexes with a variety of radical precursors not amenable to previous catalytic methods. Excitation with visible light generates carbon radicals under mild conditions. The versatility of this EDA complex catalytic platform allowed us to develop mechanistically distinct radical reactions, including in combination with a cobalt-based catalytic system. Quantum yield measurements established that a closed catalytic cycle is operational, which hints at the ability of tetrachlorophthalimides to readily turn over and govern each catalytic cycle.

Multi-variable compensated quantum yield measurements of upconverting nanoparticles with high dynamic range: a systematic approach.

Non-linear materials such as upconverting nanoparticles (UCNPs) are emerging technology with fast-growing applications in various fields. The power density dependence of the emission quantum yield (QY) of these non-linear materials makes them challenging to characterize using currently available commercial QY systems. We propose a multimodal system to measure QY over a wide dynamic range (1:104), which takes into account and compensates for various distorting parameters (scattering, beam profile, inner filter effect and bandwidth of emission lines). For this, a beam shaping approach enabling speckle free beam profiles of two different sizes (530 µm or 106 µm) was employed. This provides low noise high-resolution QY curves. In particular, at low power densities, a signal-to-noise ratio of >50 was found. A Tm-based core-shell UCNP with excitation at 976 nm and emission at 804 nm was investigated with the system.

How to measure quantum yield of hydroxyl radical during photolysis of natural Fe(III) carboxylates?

The efficiency of oxidative species generation is one of the crucial parameters for the application of any system based on advanced oxidation processes (AOPs). This paper presents an approach to the correct determination of quantum yields of the hydroxyl radical upon UV photolysis of natural Fe(III) carboxylates, which are widely used in the works devoted to Environmental Chemistry and Water Treatment. The approach is based on the use of [FeOH]2+ hydroxocomplex as a reference system with the well-known quantum yield of hydroxyl radical and benzene as a selective trap for the •OH radical. For the first time, the quantum yields of the •OH radical have been determined for the most popular Fe(III) oxalate photosystem in the wide range of initial parameters (pH, excitation wavelength, concentration of oxalate and Fe(III) ions). Also the oxidation potential of Fe(III) oxalate photosystem was tested on a set of persistent organic herbicides, and quantum yields of the photodegradation of herbicides were compared with the quantum yield of the •OH radical. The Fe(III) oxalate photosystem is recommended as a suitable system for the generation of •OH radical at neutral pH under UV radiation.

Positron annihilation study of lattice defects and nanoporous structures in Mn4+ doped K2SiF6 nanophosphors exhibiting high quantum yield

The present paper reports an application positron annihilation spectroscopy (PAS) to systematically study the formation of lattice defects, nanoporous structures and sites of Mn4+ ions doped into the K2SiF6 (KSFM) nanophosphors prepared using four different solvents. Three main techniques of PAS, including positron annihilation lifetime (PAL), Doppler broadening (DB) and electron momentum distribution (EMD) measurements, were simultaneously carried out under the same vacuum condition. The structural characteristics and quantum yield (QY) of KSFM nanophosphors were investigated using X-ray diffraction (XRD), scanning electron microscopy (SEM), coupled plasma mass spectroscopy (ICP-MS), photonic multichannel analyzer-spectrophotometer (PMAS) and fluorescence spectrophotometer (PLS). The obtained results indicated that decreasing the dielectric constant of the solvents led to the reduction of the particle sizes in KSFM. The occupation of Mn4+ to the sites of Si4+ in the SiF62– octahedron structures of KSFM as well as the high concentration of lattice defects and nanopores (average size of 0.390–0.621 nm) in the doped materials that used isopropanol and diethyl ether solvents were indicated by PAS. Moreover, increasing the concentration of doped Mn4+ caused a decrease of the occupation of Mn4+ to the adjacent Si-vacancy and K-divacancy and at the same time, the number of Si-vacancies in KSFM increased. Combining PAS and QY measurements, we found that the QY of KSFM nanophosphors depended on not only the porous structures (nanopores) but also the concentration of doped Mn4+ in the sites of Si as well as the concentration of Si-vacancies.

Synthesis, characterization, and in vitro DPPH radical scavenging assay study of PEG-capped carbon nanoparticles derived from Butea monosperma flower extract

In this work, the core carbon nanoparticles (BM CNs) and polyethylene glycol 400 (PEG400)-capped BM CNs were synthesised from Butea monosperma flower extract via the facile direct heating method. They were investigated for their intriguing properties and in vitro antioxidation activity in comparison with Carica papaya seed (CPS) extract via DPPH assay. The CNs were characterised by DLS, XRD, HR-TEM, TGA, FT-IR, UV–vis spectral analysis and quantum yield measurement. The PEGylated CNs demonstrated decent quantum yield, favourable size, and turbostratic carbon phase apart from better stability and dispersion nature as compared to the uncapped entity. The mildly stable uncapped sample with zeta potential −17.9 mV featured its extensively aggregated form, unlike the capped sample with −23.0 mV zeta potential, which sheds light on its enhanced stability by PEG400. Antiradical capacities of the CNs in comparison with CPS extract demonstrated the PEG400-bound nanomaterial of its superior antiradical activity against the other two controls. This study provides an insight into the novel polymer-CNs’ potent antioxidant property which can be further explored for its incorporation in targeted drug delivery and other biomedical applications.

Spectral studies of Dy3+:zincphosphate glasses for white light source emission applications: A comparative study

Recently, much efforts have been focused on Dy3+-doped glasses due to their optical and luminescent properties for several applications such as display devices, white light emitting diodes, waveguides for optical telecommunication, etc. In the present study, the Dy3+-doped zinc phosphate (Dy3+:PZKAN (P2O5+ZnO+K2O+Al2O3+Na2O+Dy2O3)) glasses have been prepared by melt quenching technique and characterized through absorption (optical band gap, Urbach energies and Judd-Ofelt (JO) theory), photoluminescence (yellow (Y) to blue (B) luminescence intensity ratios (Y/B) and CIE color coordinates), decay time and quantum yield measurements. With the help of optical absorption, transition intensities and the well proposed JO theory, three phenomenological JO fitted parameters were estimated and in turn adopted to evaluate the required radiative parameters for specific excited luminescent levels of Dy3+ ion. The luminescence transitions exhibit de-excitation (refers radiative-emission) levels in the optical region of 450-750 nm. Also while increasing Dy3+ ion content, the de-excitation intensities were quenched due to presence of higher content of Dy3+ ions. The fluorescence decay curve for all the glass samples have been recorded with 350 nm pumping and observed the de-excitation at 575 nm that belongs to the 4F9/2 → 6H13/2 level. The CIE color coordinates were estimated with the help of CIE chromaticity diagram and the quantities were in close proximity of the optimised white light (towards yellow) region for all the glasses. The lifetime (952 μs to 358 μs) and quantum yield (67 to 11) values decreases with increasing concentration (Dy3+:0.05 mol % to 3.0 mol %). The present results have been compared and discussed with those of 72 reported Dy3+:glasses besides uniform labeling of glass compositions. From these results, it is concluded that the Dy3+:PZKAN glasses could also be useful for optical display devices and yellow laser applications.

Boost in Solid‐State Photon Upconversion Efficiency through Combined Approach of Melt‐Processing and Purification

Realization of efficient photon upconversion (UC) mediated by triplet–triplet annihilation (TTA) in a solid state is a great challenge, even though order of magnitude higher efficiencies are routinely reported in a solution/liquid state. To address this issue in a typical emitter/sensitizer UC system, a combined approach is introduced based on 1) thorough emitter purification for reduced exciton quenching and 2) UC film fabrication via melt‐processing for attaining large emitter concentrations with suppressed aggregation. Emitter purification via vacuum sublimation is shown to reduce the number of both singlet and triplet quenchers as confirmed by fluorescence and UC quantum yield measurements along with the respective transient measurements performed on nanosecond and millisecond time domains. Application of this approach to the benchmark TTA‐UC system DPA/PtOEP is demonstrated to yield a record‐high UC efficiency (=8 ± 1%, out of maximum 50%) achieved at 40 wt% of DPA homogeneously dispersed in the PMMA host. Importantly, such high efficiency is accomplished in large‐area amorphous films, the most preferred for practical applications, and featuring low UC threshold (=5 mW cm−2) that is close to the solar irradiance. The presented approach describes the guidelines for boosting UC efficiency in the solid state, and generally, is applicable to any conventional TTA‐UC system.

Determination of the Photoisomerization Quantum Yield of a Hydrazone Photoswitch.

Photoswitching organic molecules that undergo light-driven structural transformations are key components to construct adaptive molecular systems, and they are utilized in a wide variety of applications. In most studies employing photoswitches, several important photophysical properties such as maximum wavelengths of absorption and emission, molar attenuation coefficient, fluorescence lifetime, and photoisomerization quantum yield are carefully determined to investigate their electronic states and transition processes. However, measurement of the photoisomerization quantum yield, the efficiency of photoisomerization with respect to the absorbed photons, in a typical laboratory setting is often complicated and prone to error because it requires the implementation of rigorous spectroscopic measurements and calculations based on an appropriate integration method. This article introduces a set of procedures to measure the photoisomerization quantum yield of a bistable photoswitch using a photochromic hydrazone. We anticipate that this article will be a useful guide for the investigation of bistable photoswitches that are being increasingly developed.

Indocyanine green assembled free oxygen-nanobubbles towards enhanced near-infrared induced photodynamic therapy.

Photodynamic therapy (PDT) has shown a promising capability for cancer treatment with minimal side effects. Indocyanine green (ICG), the only clinically approved near-infrared (NIR) fluorophore, has been used as a photosensitizer for PDT in clinical application. However, the main obstacle of directly utilizing ICG in the clinic lies in its low singlet oxygen (1O2) quantum yield (QY) and instability in aqueous solution. To improve the PDT efficacy of ICG, free ICG molecules were assembled with free oxygen nanobubbles (NBs-O2) to fabricate ICG-NBs-O2 by hydrophilic-hydrophobe interactions on the gas—liquid interface. Interestingly, 1O2 QY of ICG-NBs-O2 solution was significantly increased to 1.6%, which was estimated to be 8 times as high as that of free ICG solution. Meanwhile, ICG-NBs-O2 exhibited better aqueous solution stability compared with free ICG. Furthermore, through establishing tumor models in nude mice, the therapeutic efficacy of ICG-NBs-O2 was also assessed in the PDT treatment of oral cancer. The tumor volume in ICG-NBs-O2 treated group on day 14 decreased to 0.56 of the initial tumor size on day 1, while the tumor volume in free ICG treated group increased to 2.4 times. The results demonstrated that ICG-NBs-O2 showed excellent tumor ablation in vivo. Therefore, this facile method provided an effective strategy for enhanced PDT treatment of ICG and showed great potential in clinical application.Electronic Supplementary MaterialSupplementary material (measurements of the singlet oxygen quantum yield of ICG-NBs-O2, time-dependent temperature changes during the laser irradiation, photographs of Cal27 tumor-bearing nude mice and complete blood count of health male balb/c mice analysis) is available in the online version of this article at 10.1007/s12274-022-4085-0.