Luminescence Quantum Yield Research Articles

FUNCTIONAL OPTICAL MATERIALS BASED ON AEROGELS

Sol-chemistry is an efficient physico-chemical method for the preparation of porous glassy or nanocrystalline materials with tailored electrical, thermal or optical properties. This paper focuses on the dependence preparation–structure-properties of hydrophobic silica aerogel granules, powders and composites with a potential application as optical materials. Using the technique of subcritical preparation of silica aerogel powders, multicolour emitting composites containing Eu(phen)2(NO3 )3 or Tb(phen)2(NO3 )3 nanocrystals are obtained and characterized with luminescence spectroscopy, quantum yield determination and texture measurements. A dependence of the luminescence quantum yield on the degree of hydrophobicity α of the silica aerogel powders is described.

Electrostatic Self‐Assembly of Ag‐NPs Mediated by Eu3+ Complexes for Physically Unclonable Function Labels

ABSTRACTPhysically unclonable functions (PUFs) are essential for anticounterfeiting. Creating high‐stability, multimode, and secure labels remains challenging. Herein, we present a novel self‐assembly method for modulating the optical signals of rare‐earth (RE) complexes via interactions with Ag nanoparticles (Ag‐NPs). Initially, we engineered a positively charged Eu3+ complex ([EuL3]3+), which promotes the self‐assembly of negatively charged Ag‐NPs to form Eu/Ag‐NPs composites. The assembly of Ag‐NPs induces a surface plasmon effect that boosts the luminescent quantum yield and Raman signal intensities, and modifies the luminescence lifetime of the [EuL3]3+. Crucially, these micron‐scale Eu/Ag‐NPs can be applied to substrates, facilitating high‐resolution signal acquisition and diverse information encoding within limited space. Validation experiments reveal that PUF labels crafted using Eu/Ag‐NPs exhibit inherent randomness and uniqueness, along with stable and repeatable signal output. The strategic self‐assembly of Ag‐NPs, mediated by [EuL3]3+, along with the effective modulation of material properties, paves the way for advancing high‐resolution, high‐information‐density solutions in anticounterfeiting technologies.

Lantern‐Shaped Structure Induced by Racemic Ligands in Red‐Light‐Emitting Metal Halide with Near 100 % Quantum Yield and Multiple‐Stimulus Response

AbstractOrganic‐inorganic metal halides (OIMHs) have become a research hotspot in recent years due to their excellent luminescent properties and tunable emission wavelengths. However, the development of efficient red‐light‐emitting OIMHs remains a significant challenge. This work reports three Mn‐based OIMHs derived from 1‐methyl‐1,2,3,4‐tetrahydroisoquinoline hydrobromide: racemic one (Rac‐TBM) and chiral ones (R‐TBM and S‐TBM). As a result of the synergism of chiral organic ligands inducing a unique lantern‐shaped hybrid structure containing both tetrahedra and octahedra, Rac‐TBM exhibits red‐light emission with near‐unity luminescence quantum yield. In comparison, the chiral counterparts R/S‐TBM display strong green emission and circularly polarized luminescence (CPL) with a glum value up to ±2.5×10−2. Interestingly, a mixture of R‐ and S‐TBM can transform into Rac‐TBM, successfully achieving a sensitive and reversible switch between red light of octahedra and green light of tetrahedra under external stimuli. The outstanding luminescent properties allow Rac‐TBM to be utilized not only for X‐ray radioluminescence with a detection limit down to 46.29 nGys−1, but also for advanced information encryption systems to achieve leak‐proof decryption.

Lantern-Shaped Structure Induced by Racemic Ligands in Red-Light-Emitting Metal Halide with Near 100 % Quantum Yield and Multiple-Stimulus Response.

Organic-inorganic metal halides (OIMHs) have become a research hotspot in recent years due to their excellent luminescent properties and tunable emission wavelengths. However, the development of efficient red-light-emitting OIMHs remains a significant challenge. This work reports three Mn-based OIMHs derived from 1-methyl-1,2,3,4-tetrahydroisoquinoline hydrobromide: racemic one (Rac-TBM) and chiral ones (R-TBM and S-TBM). As a result of the synergism of chiral organic ligands inducing a unique lantern-shaped hybrid structure containing both tetrahedra and octahedra, Rac-TBM exhibits red-light emission with near-unity luminescence quantum yield. In comparison, the chiral counterparts R/S-TBM display strong green emission and circularly polarized luminescence (CPL) with a glum value up to ±2.5×10-2. Interestingly, a mixture of R- and S-TBM can transform into Rac-TBM, successfully achieving a sensitive and reversible switch between red light of octahedra and green light of tetrahedra under external stimuli. The outstanding luminescent properties allow Rac-TBM to be utilized not only for X-ray radioluminescence with a detection limit down to 46.29 nGys-1, but also for advanced information encryption systems to achieve leak-proof decryption.

Multi‐Channel Optical Encryption Film With Strong Circularly Polarized Luminescence and High Quantum Yield

AbstractDeveloping a sustainable security module with multiple optical states is important to deter counterfeits, but is challenging. This work designs a kind of chiral luminescent film through the co‐assembly of the CNCs and d‐glucose, simultaneously doped with the lanthanide complex and organic dye. Superior mechanical performance makes it undertake various deformations, including twist, and tension without breaking. Meanwhile, this film has unique optical characteristics. On the one hand, the chiroptical signals can be manipulated through the matching of the photonic bandgap and fluorescence peak. On the other hand, due to the co‐assembly with two luminophores, the film displays the excitation wavelength (Ex)‐dependent circularly polarized luminescence properties. Under the Ex of 275 nm, the film simultaneously integrates a large dissymmetry factor of −0.3898, a high quantum yield of 69.19%, and a considerable lifetime of 1381 µs, which has exceeded most reported chiral luminescent assemblies. These multimodal and convertible optics endow the film with practical applications in the anti‐counterfeit. It can be designed as a security label or used as a written paper to encrypt the information. Even in humid surroundings, this security effect is still ensured.

Nonradiative Deactivation of the Fluorescent Ag16-DNA and Ag10-DNA Emitters: The Role of Water.

The luminescent quantum yield of silver-cluster emitters stabilized by short oligonucleotides (AgN-DNA) may be efficiently tuned by replacing nucleobases in their stabilization DNA matrices with analogues. In the present study, we proposed a valuable and straightforward theoretical methodology for assessing the photophysical behaviors emerging in AgN-DNA emitters after excitation. Using green Ag10-DNA and near-IR Ag16-DNA emitters we demonstrate how point guanine/inosine replacement could affect the photophysical rate constants of radiative/nonradiative processes. The main deactivation channel of the fluorescence of Ag16-DNA is intersystem crossing, which is in line with experimental data, whereas for Ag10-DNA the calculations overestimate the intersystem crossing rate possibly due to pure solvent contributions.

Temperature Changes in Luminescence of Mixed Complexes of Terbium and Samarium with Organic Ligands Based on 2,2-bipyridyldicarboxamides

Solutions in acetonitrile of three mixed complexes of rare earth elements (terbium and samarium) with organic ligands with various pyridine substituents were studied in this work. The ratios of ligands and metals in the resulting complexes were determined, and the stability constants of samarium complexes were calculated using the spectrophotometric titration method. Measurements of absorption, emission and excitation spectra of luminescence, luminescence kinetics of solutions of mixed complexes of rare earth elements with an excess of metal relative to the ligand were carried out at various temperatures in the range 298–328 K. An increase of luminescence intensity of a samarium ion in complex upon heating has been discovered for the first time. The dependences of the luminescence quantum yield and lifetime of mixed complexes on temperature were obtained. A thermometric parameter — the ratio of the integral luminescence intensities of samarium and terbium ions — was proposed, and the temperature sensitivity coefficient of this parameter was determined for different complexes.

The interplay between structural features and the efficiency of the energy transfer process in terbium complexes with triarylcyclopentadienyl ligands

Terbium and gadolinium complexes with triarylcyclopentadienyl ligands having electron-donating methoxy substituents in the ortho- (CpPh2Ar−o) and para- (CpPh2Ar−p) positions of one of the phenyl rings have been synthesized. Different structural types, including tetranuclear [{CpPh2Ar−oTb (THF)}2 (μ2-Cl)2(μ3-Cl)3K (THF)]2 (Tb1), [{CpPh2Ar−oTb}2 (μ2-Cl)2 (μ3-Cl)3K]2 (Tb3), [{(CpPh2Ar−oTb)2 (μ2-Cl)3}2 (μ2-Cl)2] (Tb5), [{CpPh2Ar−pTb (THF)}2 (μ2-Cl)2 (μ3-Cl)3K (THF)]2 (Tb6), binuclear [{CpPh2Ar−oTb (THF)Cl}2 (μ2-Cl)2] (Tb4), [{CpPh2Ar−pTb (THF)}2 (μ2-Cl)2 (μ3-Cl)3K (THF)]2 (Tb7), [CpPh2Ar−p2Tb (μ2-Cl) (μ3-Cl)K]2 (Tb8) and mononuclear [CpPh2Ar−o2TbCl] (Tb2) complexes have been obtained and confirmed by single crystal X-ray diffraction analysis. All designed terbium complexes exhibit high quantum yields of the photoluminescence (up to 65 %). The introduction of a methoxy group into one of the phenyl rings of the triarylcyclopentadienyl ligand leads to a more than twofold increase in the quantum yield of the terbium ion luminescence. The estimated values of radiative rate krad of the terbium ion vary in the range of 0.23–0.69 ms. The presence of the methoxy group as well as the mutual disposition of the phenyl rings promotes the appearance of an intraligand charge transfer states involved in the energy transfer process. Due to a lowering of the energy of the interconfigurational 4f −5d transitions caused by the relatively strong crystal field of the Cp ligand in bis(cyclopentadienyl) terbium complexes, the quantum yield of the photoluminescence is high at the short lifetimes of the 5D4 level of the terbium ion.

Controlling the luminescence of CdSe quantum dots in the fluorinephosphate glass

A series of fluorophosphate glasses with CdSe and CdSe+ZnSe are successfully synthesized. After heat treatment above the glass transition temperature, CdSe quantum dots with sizes 1.5–5.5 nm are formed. The luminescence spectra of CdSe quantum dots are analyzed at various temperatures, excitation energies and chemical composition of glass. The influence of selenium content on the growth features of quantum dots is shown. The size dependence of luminescence quantum yield on the QDs size is found. The 2.0–2.5 nm-sized QDs demonstrate trap emission in the region of 1.7–1.85 eV with a maximum quantum yield of 60 %. It is found that only a broad band due to the transition from the low state of the conduction band and the shallow donor trap states to the deep accepter trap levels is observed. This broad emission band is observed at any selenium cadmium ratio and zinc introduction.

Preparation and Properties Study of CsPbX3@PMMA Luminescent Resin.

Perovskite as an emerging semiconductor luminescent material has attracted widespread attention due to its simple preparation, high luminescence quantum yield, high color purity, tunable spectrum, and ability to cover the entire visible light band. However, due to the influence of water or other highly polar solvents, oxygen, temperature, and radiation, perovskite nanocrystals will aggregate or collapse in the lattice, eventually leading to luminescence quenching. This study starts from the postprocessing of perovskite, uses methyl methacrylate as the monomer and TPO as the photoinitiator, and encapsulates the perovskite powder prepared by the hot injection method through ultraviolet light initiation. A method is proposed to improve the luminescence and crystal structure stability of perovskite. By eliminating the influence of environmental factors on perovskite nanocrystals through the dense structure formed by organic polymers, the resistance of perovskite to strong polar solvents such as water will be greatly improved, and it has great potential in the protection of perovskite. Finally, by changing the proportion of halogen elements in the perovskite resin to change the color of the luminescent resin, a fluorescent coating emitting light in all visible light bands is prepared. Fluorescent coatings are widely used in life and industry fields such as plastics, sol, and paper.

Thermally Activated Delayed Fluorescence and Beyond. Photophysics and Material Design Strategies.

This review focuses on thermally activated delayed fluorescence (TADF). Photophysical properties of Cu(I) complexes and unique organic molecules are addressed. Investigations, based on temperature‐dependent emission studies, micro‐ to femto‐second time‐resolved spectroscopy investigations, quantum mechanical considerations, state‐of‐art calculations, and organic light‐emitting diodes (OLED) device studies, address exciton harvesting mechanisms and photophysical impact of the energy gap ΔE(S1–T1) and spin‐orbit coupling (SOC). We disclose relationship between (i) ΔE(S1–T1) and transition rate k(S1–S0); (ii) SOC, phosphorescence, and intersystem crossing (ISC); (iii) internal/external rigidity, luminescence quantum yield, excitation self‐trapping, and concentration quenching; (iv) environment polarity and state energy tuning, as well as (v) SOC and combined ambient‐temperature TADF/phosphorescence, zero‐field splitting, and spin‐lattice relaxation (at T = 1.2 K). These studies guide us to milestone Cu(I) complexes. Moreover, we demonstrate that fast ISC in organic molecules requires state mixing with an additional, energetically close triplet state. Thus, a guide structure for unique organic TADF molecules with ultra‐fast ISC and reverse‐ISC rates (>109 s−1) combined with ΔE(S1–T1)<10 cm−1 (<1 meV) is presented allowing for ultra‐fast singlet‐triplet equilibrated fluorescence with sub‐microsecond decay. First OLEDs fabricated show high external quantum efficiency of ≈19%. Based on this breakthrough material class, a new exciton harvesting mechanism, the direct singlet harvesting (DSH), is presented.

Improvement of fluorescence properties by surface modification of CdS-ZnS quantum dots by thiol compounds and its application as a sensitive fluorescence probe for copper ion detection.

The capped CdS-ZnS quantum dots (QDs) were synthesized with various thiol capping agents of glycolic acid (TGA), mercaptosuccinic acid (MSA), and L-cysteine (LCY) and used as fluorescence probe for determination of Cu (II) ions. The method of two-level three-factor full-factorial experiment design was used to achieve the best optical fluorescence emission. Results revealed that Cu (II) ions can effectively quench the emission of QDs, and the fluorescence intensity is linearly decreased with increasing Cu (II) ion concentration. The limit of detection for CdS-ZnS@ QDs capped with TGA, MSA, and LCY was obtained at 1.15 ×10-7, 1.32 ×10-7, and 2.19 ×10-7mol L-1, respectively, with linear dynamic range of 3.13 ×10-6 to 1.41 ×10-4mol L-1. Luminescence quantum yields of CdS-ZnS@LCY, CdS-ZnS@MSA, and CdS-ZnS@TGA were obtained at 4.17, 1.92, and 2.47, respectively. Results indicated that no significant quenching occurred in the presence of the other metal ions. The binding constant (Kb) of capped CdS-ZnS@ QDs with Cu2+ and the other metal ions was also investigated and discussed. The Kb value for Cu2+ was obtained considerably more than that the other ions. This work presents a new and sensitive method for determination of Cu2+ ion.

Facile Synthesis of Ln-Doped Hydrogen-Bonded Organic Frameworks with Rare-Earth-Characteristic Long Persistent Luminescence.

Tunable luminescence-assisted information storage and encryption holds increasing significance in today's society. A promising approach to incorporating the benefits of both organic long persistent luminescent (LPL) materials and rare-earth (RE) luminescence lies in utilizing organic host materials to sensitize RE luminescence, as well as hydrogen-bonded organic framework (HOF) phosphorescence Förster resonance energy transfer to RE compound luminescence. This work introduces a one-pot, in situ pyrolytic condensation method, achieved through high-temperature melting calcination, to synthesize lanthanide ion-doped HOF materials. This method circumvents the drawback of molecular triplet energy annihilation, enabling the creation of organic LPL materials with RE characteristics. The HOF material serves as the host, exhibiting blue phosphorescence and cyan LPL. By fine-tuning the doping amount, the composite material U-Tb-100 achieves green LPL with a luminescent quantum yield of 56.4%, and an LPL duration of approximately 2-3 s, demonstrating tunable persistence. Single-crystal X-ray diffraction, spectral analysis, and theoretical calculation unveil that U-Tb-100 exhibits exceptional quantum yield and long-lived luminescence primarily due to the efficient sensitization of U monomer to RE ions and the PRET process between U and RE complexes. This ingenious strategy not only expands the repertoire of HOF materials but also facilitates the design of multifunctional LPL materials.

High quantum yield luminescence and scintillation properties of high-Ce-doped MgF2–Al2O3–B2O3 glasses and their glass structure

Ce-doped inorganic single crystals are currently used in scintillators in various instruments because of their outstanding luminescence properties. However, these crystals are expensive to manufacture and are inefficient in terms of their energy consumption. In this study, xCeF3-doped 40MgF2–20Al2O3–40B2O3 glasses (x = 0−30 mol%) were prepared by a melt-quenching method in N2 atmosphere, and their photoluminescence, scintillation, and dosimetry properties were investigated. The X-ray absorption fine edge spectroscopy of the Ce L3-edge indicated that the doped Ce exists in the form of Ce3+ ions, and that Ce4+ does not form because of the low basicity of the glass. The glasses underwent photoluminescence at 380 nm due to the 5d-4f transition of Ce3+, with a very high quantum yield of up to ∼100 % and low concentration quenching. The peak shape of the X-ray-induced luminescence was similar to that of the PL with a decay time of 110−70 ns. The light yields for gamma rays (137Cs source) were obtained from the pulse-height spectra, and the highest light yield among the present samples was 1071 photons/MeV with the energy resolution of 17 %. The thermoluminescence glow curves had peaks at 365 and 460 K and a good linear relationship existed in the range of 0.5–1000 mGy, with the dose response being comparable to that of a commercial dosimeter. The origin of the high quantum yield was probed by analyzing the glass structure using molecular dynamics simulation based on a graph neural network. A strong tendency to selectively bind cations and anion pairs was found: Mg preferably binds to F, B preferably binds to O, and Al binds to O and F, which can be explained by soft and hard acid and base theories. Because of this selectivity the glass forms fluoride- and oxide-rich domains, which seem to be responsible for the more effective dispersal of the luminescent center. The results of this study are expected to contribute to the development of glasses with enhanced photoluminescence and scintillation luminescence properties.

A Single‐Component Sb/Ho: Cs2Na0.9Ag0.1(In/Bi)Cl6 White Phosphor with a Record Color Rendering Index of 97.4

AbstractThe study on phosphors‐converted white light‐emitting diodes (pc‐WLEDs) using lead‐free double perovskites (DPs) as single‐component white phosphors is widely concerned. However, the photoluminescence quantum yields (PLQY) of white luminescence and color rendering index (CRI) of WLED are not satisfactory. Herein, a new Sb/Ho: Cs2Na0.9Ag0.1(In/Bi)Cl6 single‐component white phosphor with the highest PLQY of 93% and a record CRI of 97.4 is reported. Experimental data and theoretical calculations evidence that in addition to broadband yellow emission of the self‐trapped exciton (STE) recombination, the material also exhibits blue emission from Sb3+: 3P1→1S0 transition and red one assigned to Ho3+: 5F5→5I8 transition. Steady‐state and time‐resolved PL spectra verify the existence of two energy transfer channels from both Sb3+ and STE to Ho3+ dopants. As a demo, Sb/Ho: Cs2Na0.9Ag0.1(In/Bi) Cl6‐based WLED is constructed, showing excellent comprehensive optical performance with specially improved saturation red index R9 and blue one R12. This work provides a novel single‐component rare‐earth doped DP white phosphor for high CRI full‐spectrum solid‐state lighting.

Solid solutions in EuSc3(BO3)4-GdSc3(BO3)4 system: Phase diagram, synthesis, crystal growth, structure and luminescence

Solid solutions based on (Eu,Gd)Sc3(BO3)4 (C2/c) and Gd0.25Sc0.75BO3 (R3¯) in the EuSc3(BO3)4-GdSc3(BO3)4 system were studied. Synthesis at 1250 °C provides wide homogeneity regions which are stable at room temperature. Melt-solution crystallization of both compounds from LiBO2-LiF flux was shown. All the obtained samples have luminescence characteristic of Eu3+ with a largest peak at 615 nm corresponding to the 5D0 → 7F2 transition. In this series the luminescence intensity monotonically increases with an increase of Eu content. The largest quantum yield of luminescence (53 %) in the EuSc3(BO3)4-GdSc3(BO3)4 system is demonstrated by EuSc3(BO3)4 sample.

Intramolecular energy transfer and its influence on the overall quantum yields of Eu3+ and Tb3+ chelates with dimethyl(phenylsulfonyl)amidophosphate ligands

Lanthanide chelates with dimethyl(phenylsulfonyl)amidophosphate (labeled as HSP) and Lewis base ligands (bpy = 2,2;-bipyridine and phen = 1,10-phenanthroline) of formula Na[Ln(SP)4] (1Ln), [Ln(SP)3bpy] (2Ln); [Ln(SP)3phen] (3Ln) (Ln = Eu3+, Gd3+, Tb3+ and Lu3+) were obtained and characterized by the X-ray, photoluminescence spectroscopy at 293 and 77 K as well as by intrinsic (QLnLn) and overall (QLnL) luminescence quantum yields. These phosphors manifest a very strong emission after excitation in the UV range of the molecular singlet states (S1) and two of them have very high QLnL values (Eu3+ and Tb3+ chelates of the type 2Ln and 3Ln). The dynamics of the excited states are discussed based on the intramolecular energy transfer theory, considering the dipole–dipole, the dipole-multipole and the exchange mechanisms. From the calculated energy transfer rates, a rate equation model was constructed and, thus, the theoretical QLnL can be obtained. A good correlation between the experimentally determined and theoretically calculated QLnL values was achieved, with the triplet state (T1) playing a predominant role in the energy transfer process for Eu3+ compounds, while the sensitization for Tb3+ compounds is dominated by the energy transfer rates from the singlet state (S1).

Preparation and properties of circularly polarized long-lived fluorescent liquid crystal materials based on TS-FRET mechanism

Circularly polarized long-lived fluorescent materials show unique application values in circularly polarized organic light-emitting diodes, advanced anti-counterfeiting materials, and so forth. However, the circularly polarized long-lived fluorescent materials with large luminescence dissymmetry factor (glum) values and long fluorescence lifetime are rarely reported. In this article, we propose to prepare circularly polarized long-lived fluorescent materials based on triplet-to-singlet Förster-resonance energy transfer (TS-FRET) mechanism. We have prepared circularly polarized long-lived fluorescent luminescent materials with large glum values, long fluorescence lifetime, high luminescent quantum yield and large Stokes shift by blending chiral room temperature phosphorescent liquid crystal Chol-C6-DF with achiral fluorescent component Br–C6-Nap. Attributed to the effective TS-FRET process between Chol-C6-DF and Br–C6-Nap, the obtained doped films show long fluorescence lifetime. When the doping amount of Br–C6-Nap is 2 wt%, the fluorescence lifetime can achieve 103 ms. All obtained doped films exhibit high glum values attributed to selective reflection of chiral liquid crystals. As the doping amount of Br–C6-Nap increases, the |glum| value first increases and then decreases, with a maximum of 1.45. In addition, the doped films also possess high solid-state luminescence quantum yield and large Stokes shift, with a maximum value of 54 % and 284 nm, respectively.

Photophysical properties of benzo[i]dipyrido[3,2-a:2′,3′-c] phenazine (dppn) – A prospective ligand for light-activated anticancer complexes

Benzo[i]dipyrido[3,2-a:2′,3′c]phenazine (dppn) is a prospective ligand for constructing light-activated anticancer complexes of platinum metals. In spite of practical importance, only scarce information on the dppn photophysics and photochemistry was found in the literature. In this work photophysical properties of dppn in acetonitrile solutions were studied by means of stationary and laser flash photolysis, time-resolved luminescence, time-resolved singlet oxygen detection and ultrafast TA spectroscopy. Quantitative characteristics of luminescence (quantum yield 0.26, lifetime 52 ns in deaerated solutions) were measured. Triplet state of the initial compound 3dppn* is formed with the quantum yield estimated as 0.4 from the singlet oxygen production; the main channels of 3dppn* are quenching by dissolved oxygen and self-quenching by the ground state of dppn. Combining the data of ultrafast TA absorption and time-resolved luminescence, we detected the formation of “dark” (not emissive) excited state of dppn with the decay time ca. 150 ps. Two hypotheses on the nature of the dark state were put forward.

Waste Polyethylene-Derived Carbon Dots: Administration of Metal-Free Oxidizing Agents for Tunable Properties and Photocatalytic Hyperactivity.

The possibility of converting waste plastics into carbon dots (CDs) with 100% efficiencies using KMnO4 has emerged as a significant discovery in mitigating plastic pollution and upcycling. However, the lack of tunability of their properties, viz. aerial O2 harvesting, light-induced autophagy, and photoactivity using air as a free oxidant, has remained a bottleneck. Besides, the toxicity of KMnO4 makes the process less sustainable. Attempting to bridge these gaps, herein, we demonstrate the preparation of CDs using polyethylene with enormous controllability of their properties by utilizing less-toxic and metal-residue-free oxidizers, e.g., H2O2, HNO3, HClO4, and NaClO. We obtain structurally diverse CDs with controllable luminescent quantum yields (∼0.5-8%), excitonic lifetimes (1.3-2.3 ns), and binding energies (147-290 meV). These CDs exhibit a hugely extended range of molecular O2 harvesting (∼405-650 μM) with different amounts of strongly and weakly surface-bound O2 molecules within an estimated ratio of ∼0.77-2.51. Autophagy varied from 14 days to a nearly "no-autophagy" show. We efficiently utilized their oxygen harvesting and photocatalytic abilities to synthesize imine compounds from the corresponding amines in the open air (rate constant of ∼0.055 min-1), surpassing the literature efficiencies achieved using an O2 flow and noble metals. Notably, due to oxygen harvesting by CDs, no additional rate enhancement was observed after O2 purging, establishing the role of CDs in making free air an excellent oxidizing agent.