Nonradiative Decay Processes Research Articles

AIE Active Polymeric Fluorescent Nanoaggregates from Glycogen for Sensitive Detection of Tetracycline.

Detection and monitoring of environmental contaminants such as antibiotic residues in aquatic environments is challenging. To address this, a variety of detection methods has been developed; out of which optical sensing using fluorescence is found as one of the most robust methods. However, most of the reported sensors are made from metal ions using tedious synthetic processes, on the other hand, optical sensors using biosourced polymers are rarely reported. Herein, an anionic glycogen functionalized aggregation induced emission (AIE) active system; NCMCTPN was prepared using a simple Schiff base condensation reaction of tetraphenylethene amine (TPENH2) and carboxymethyl cellulose dialdehyde (NCMCA) and its self-assembled polymeric nanoaggregates were explored for sensitive and selective turn-off fluorescence detection of a broad-spectrum tetracycline antibiotic, in an aqueous medium with a limit of detection of 127.5 ppb. The combination of factors such as inner filter effect and photoinduced electron transfer from the polymeric nanoaggregates to tetracycline through activation of a non-radiative decay process is possibly responsible for the high sensitivity of the fluorescent nanoprobe towards the antibiotic.

NIR Diradical-Featured Croconaine Nanoagent for Cancer Photoacoustic Imaging and Photothermal Therapy.

Radical-featured organic materials usually demonstrate significantly narrower bandgap than that of regular organic materials, which is beneficial for near-infrared (NIR) absorption and non-radiative decay process, making them good candidates for photothermal agents (PTAs) of photothermal therapy (PTT). However, most organic radicals are too short-lived to be separated and stable. Herein, a stable pyrylium-croconaine (CR) dye CR845 with high diradical character was synthesized and assembled into CR845 nanoparticles (NPs) to explore the photoacoustic imaging (PAI) and photothermal therapeutic performance under NIR irradiation in vitroand in vivo. CR845 exhibited a stable NIR absorption at 845 nm (ε= 3.37 × 105L mol-1cm-1) and a relatively high photothermal conversion efficiency (PCE) of 58.8%. When assembled into nanoparticles, CR845 NPs showed good photostability, good biocompatibility, favorable NIR photoacoustic potential, effective cancer cell killing and complete tumor elimination upon 850 nm laser irradiation. The work demonstrates a diradical-featured CR PTA with favorable PAI/PTT effects, which can help to provide new ideas for the development of NIR PTAs, and further promote the application of organic radical materials in the field of biomedicine.

The formation of exciplex and triplet-triplet transfer in organic room temperature phosphorescent guest-host materials.

Organic materials typically do not phosphoresce at room temperature because both intersystem crossing (ISC) and phosphorescence back to the electronic ground state are slow, compared to the nonradiative decay processes. A group of organic guest-host molecules breaks this rule. Their phosphorescence at room temperature can last seconds with a quantum efficiency of over 10%. This extraordinary phenomenon is investigated with comprehensive static and transient spectroscopic techniques. Time-resolved vibrational and fluorescence spectral results suggest that a singlet guest-host exciplex quickly forms after excitation. The formation of exciplex reduces the singlet-triplet energy gap and helps facilitate charge separation that can further diffuse into the host matrix. The heavy atoms (P or As) of the host molecule can also help enhance the spin orbital coupling of the guest molecule. Both boost the rate of ISC. After the singlet exciplex transforms into the triplet exciplex through the ISC process, UV-visible transient absorption spectroscopic measurements support that the triplet exciplex quickly transforms into the guest molecule triplet state that is at a lower energy level, thereby reducing the reverse ISC-induced triplet population loss. Finally, the long-lasting separated charges that diffused into the host matrix can diffuse back to the guest hole to form new triplets, and the dilution effect of the host molecules can effectively reduce the triplet quenching. All these factors contribute to the dramatic enhancement of phosphorescence at room temperature.

Alternating Donor-Acceptor Ladder-Type Heteroarene for Efficient Photothermal Conversion via Boosting Non-Radiative Decay.

The development of novel ladder-type conjugated molecules is crucial for advancing supramolecular chemistry and material science. In this study, we report a straightforward synthesis of new alternating donor-acceptor (D-A) ladder-type heteroarene, FCDTDPP, and demonstrate its application as photothermal agent for imaging and cancer therapy. FCDTDPP is constructed by vinylene bridge between cyclopentadithiophene (D) and diketopyrrolopyrrole (A) through intramolecular Friedel-Crafts type reaction. FCDTDPP exhibits unique combination of good molecular planarity, efficient intra/inter-molecular mixed D-A interactions, and local aromaticity. These features collectively contribute to its broad and intense absorptions with narrow bandgap in red band of the spectra, coupled with multiple vibrational absorption feature, thereby enhancing non-radiative decay process and resulting in efficient photothermal conversion property. FCDTDPP and its nanoparticles (NPs) exhibit superior photothermal conversion performance and stability under 660 nm laser irradiation. Moreover, in vitro studies reveal that FCDTDPP NPs possess excellent biocompatibility, low cytotoxicity, and robust photothermal therapeutic efficacy, a finding further corroborated by preliminary in vivo experiments in tumor-bearing mice. This work charts a novel course for the molecular engineering of organic photothermal conversion systems, propelling relevant research forward.

Benzo-Fused BOPAM Fluorophores: Synthesis, Post-functionalization, Photophysical Properties and Acid sensing Applications.

A novel category of asymmetric boron chromophores with the attachment of two BF2 moieties denoted as BOPAM has been successfully synthesized via a one-pot three-step reaction starting from N-phenylbenzothioamide. This synthetic route results in the production of [a] and [b]benzo-fused BOPAMs along with post-functionalization of the [a]benzo-fused BOPAMs. The photophysical properties of these compounds have been systematically investigated through steady-state absorption and fluorescence emission measurements in solvents at both ambient and cryogenic temperatures, as well as in the solid state. Computational methods have been employed to elucidate the emissive characteristics of the benzo-fused BOPAMs, revealing distinctive photophysical attributes, including solvent-dependent fluorescence intensity. Remarkably, certain BOPAM derivatives exhibit noteworthy photophysical phenomena, such as the induction of off-on fluorescence emission under specific solvent conditions and the manifestation of intermolecular charge transfer states in solid-state matrices. Through post-functionalization strategies involving the introduction of electron-donating groups onto the [a]benzo-fused BOPAM scaffold, an intramolecular charge transfer (ICT) pathway is activated, leading to substantial fluorescence quenching via non-radiative decay processes. Notably, one [a]benzo-fused BOPAM variant exhibits a pronounced fluorescence enhancement upon exposure to acidic conditions, thereby underscoring its potential utility in pH-sensing applications.

Supramolecular photothermal agents mediated by black hole hosts

High-performance organic photothermal agents (PTAs) hinges primarily on manipulating non-radiative decay processes, which typically necessitates intricate and time-intensive molecular engineering. The main challenge is how to bring dye and quencher into close molecular contact at a sub-nanometer distance for effective quenching. A host-guest strategy is presented to fabricate supramolecular PTAs by non-radiative electron transfer. Through strong complexation of dye with a “black hole host”, quaternary-ammonium modified calix[4]arene tetraoctyloxy ether (QC4A-8C), photothermal performances of ten distinct dyes were optimized to an unprecedented degree. The potential of supramolecular PTAs in biological application was evaluated photothermal therapy in vitro and in vivo using zinc tetrasulfonate phthalocyanine@QC4A-8C. This study provides insights into leveraging existing dyes to augment photothermal effects through electron transfer, offering a streamlined pathway for the development of safe and efficient supramolecular PTAs.

Nonradiative Spin-Forbidden Decay Processes in π- and Multiresonance-Acceptor-Based TADF Molecules

Nonradiative Spin-Forbidden Decay Processes in π- and Multiresonance-Acceptor-Based TADF Molecules

Dithieno[3,2-b; 2',3'-f]phosphepinium-Based Near-Infrared Fluorophores: px-π* Conjugation Inherent to Seven-Membered Phosphacycles.

Positively charged phosphorus-containing heterocycles are characteristic core skeletons for functional molecules. While various phosphonium-containing five- or six-membered-ring compounds have been reported, the seven-membered-ring phosphepinium have not been fully studied yet. In this study, dithieno[3,2-b; 2',3'-f]phosphepinium ions containing electron-donating aminophenyl groups were synthesized. An X-ray crystallographic analysis of the resulting donor-acceptor-donor dyes revealed a bent conformation of the central seven-membered ring. These compounds exhibit fluorescence in the near-infrared region with a bathochromic shift of ca. 70 nm compared to a phosphepine oxide congener and a large Stokes shift. High fluorescence quantum yields were obtained even in polar solvents due to the suppression of the nonradiative decay process. A theoretical study revealed that the phosphepinium skeleton is highly electron-accepting owing to the orbital interaction between a px orbital of the phosphonium moiety and a π* orbital of the 1,3,5-hexatriene moiety. Due to the lower-lying px orbital in the phosphonium moiety compared to that of the phosphine oxide and the bent conformation of the seven-membered ring, the phosphepinium ring permits effective px-π* conjugation. A large structural relaxation with a contribution of a quinoidal resonance structure is suggested in the excited state, which should be responsible for the bright emission with a large Stokes shift.

Cations Induced Fluorescence Enhancement in Keggin-Al13 for Quantitative Detection.

The Keggin-Al13 hydroxide clusters serve as pivotal models for elucidating molecular pathways in geochemical reactions. In this study, we presented a strategy aiming at the quantitative detection of ε-Al13 Keggin clusters using photoluminescent spectra. Specifically, we manipulate the electronic structure of ε-Al13 by introducing Na ions onto the ε-Al13 surface, encapsulated within a Na-O3 motif. The Na-ion-modified ε-Al13 (Na-ε-Al13) cluster demonstrates incredible photoluminescent qualities, with fluorescence excitation and emission peaks centered at 365 and 436 nm, respectively. In addition, the fluorescence intensities display a linear dependence on the concentrations of Na-ε-Al13, with a detection limit of 15.4 μM. This correlation facilitates the quantitative and precise determination of Na-ε-Al13 concentrations via fluorescence. Both experimental characterizations and theoretical calculations underscore the importance of decorated Na ions in regulating the electronic structure of the ε-Al13 cluster. Lastly, the influence of external anions/cations on the photoluminescent properties of ε-Al13 primarily mirrors modifications to the nonradiative decay process, which is regulated via electrostatic interactions. This work demonstrates an effective strategy for quantitative detection of the ε-Al13 Keggin clusters through photoluminescent spectra.

Dithieno[3,2‐b; 2′,3′‐f]phosphepinium‐Based Near‐Infrared Fluorophores: px–π* Conjugation Inherent to Seven‐Membered Phosphacycles

AbstractPositively charged phosphorus‐containing heterocycles are characteristic core skeletons for functional molecules. While various phosphonium‐containing five‐ or six‐membered‐ring compounds have been reported, the seven‐membered‐ring phosphepinium have not been fully studied yet. In this study, dithieno[3,2‐b; 2′,3′‐f]phosphepinium ions containing electron‐donating aminophenyl groups were synthesized. An X‐ray crystallographic analysis of the resulting donor–acceptor–donor dyes revealed a bent conformation of the central seven‐membered ring. These compounds exhibit fluorescence in the near‐infrared region with a bathochromic shift of ca. 70 nm compared to a phosphepine oxide congener and a large Stokes shift. High fluorescence quantum yields were obtained even in polar solvents due to the suppression of the nonradiative decay process. A theoretical study revealed that the phosphepinium skeleton is highly electron‐accepting owing to the orbital interaction between a px orbital of the phosphonium moiety and a π* orbital of the 1,3,5‐hexatriene moiety. Due to the lower‐lying px orbital in the phosphonium moiety compared to that of the phosphine oxide and the bent conformation of the seven‐membered ring, the phosphepinium ring permits effective px–π* conjugation. A large structural relaxation with a contribution of a quinoidal resonance structure is suggested in the excited state, which should be responsible for the bright emission with a large Stokes shift.

Mechanical Tuning of Fluorescence Lifetime and Bandgap in an Elastically Flexible Molecular Semiconductor Crystal.

Despite having superior transport properties, lack of mechanical flexibility is a major drawback of crystalline molecular semiconductors as compared to their polymer analogues. Here single crystals of an organic semiconductor are reported that are not only flexible but exhibit systematic tuning of bandgaps, fluorescence lifetime, and emission wavelengths upon elastically bending. Spatially resolved fluorescence lifetime imaging and confocal fluorescence microscopy reveals systematic trends in the lifetime decay across the bent crystal region along with shifts in the emission wavelength. From the outer arc to the inner arc of the bent crystal, a significant decrease in the lifetime of ≈1.9ns is observed, with a gradual bathochromic shift of ≈10nm in the emission wavelength. For the crystal having a bandgap of 2.73eV, the directional stress arising from bending leads to molecular reorientation effects and variations in the extent of intermolecular interactions- which are correlated to the lowering of bandgap and the evolution of the projected density of states. The systematic changes in the interactions quantified using electron density topological analysis in the compressed inner arc and elongated outer arc region are correlated to the non-radiative decay processes, thus rationalizing the tuning of fluorescence lifetime.

Efficient Near‐Infrared Fluorescence in Deuterated Host–Guest System for Near‐Infrared Organic Light‐Emitting Diodes

AbstractNear‐infrared organic light‐emitting diodes (NIR‐OLEDs) possess substantial potential for future valuable applications, such as a light source for sensing applications. However, the low photoluminescence quantum yield (PLQY) of NIR‐emitting molecules represents a significant impediment to these applications. In this study, the impact of the deuteration of both of host (mCP‐d20: 1,3‐Dicarbazole‐benzene‐d20) and guest (BBT‐TPA‐d28: 4,8‐bis[4‐(N,N‐diphenylamino)phenyl]benzo[1,2‐c:4,5‐c']bis[1,2,5]thiadiazole‐d28) on NIR PL properties in the host–guest codeposited film is reported. The 1 wt%‐BBT‐TPA‐d28:mCP‐d20 codeposited film exhibited PLQY of 15 ± 2% with an emission peak wavelength at ≈900 nm, which is about three times higher than that of the film composed of undeuterated molecules. Importantly, the deuteration of only the host or guest does not yield the PLQY up to 15%, underlining the importance of the deuteration of both host and guest molecules in suppressing nonradiative decay processes. The NIR‐OLED with the deuterated codeposited film as an emissive layer demonstrates a maximum external electroluminescence quantum efficiency of 2.3 ± 0.2%.

Supramolecular Control of the Temperature Responsiveness of Fluorescent Macrocyclic Molecular Rotamers.

To fully harness the potential of molecular machines, it is crucial to develop methods by which to exert control over their speed of motion through the application of external stimuli. A conformationally strained macrocyclic fluorescent rotamer, CarROT, displays a reproducible and linear fluorescence decrease towards temperature over the physiological temperature range. Through the external addition of anions, cations or through deprotonation, the compound can access four discreet rotational speeds via supramolecular interactions (very slow, slow, fast and very fast) which in turn stop, reduce or enhance the thermoluminescent properties due to increasing or decreasing non-radiative decay processes, thereby providing a means to externally control the temperature sensitivity of the system. Through comparison with analogues with a higher degree of conformational freedom, the high thermosensitivity of CarROT over the physiological temperature range was determined to be due to conformational strain, which causes a high energy barrier to rotation over this range. Analogues with a higher degree of conformational freedom display lower sensitivities towards temperature over the same temperature range. This study provides an example of an information rich small molecule, in which programable rotational speed states can be observed with facile read-out.

Host-guest interaction induced room-temperature phosphorescence enhancement of organic dyes: a computational study.

To achieve the effective regulation of organic room temperature phosphorescence (RTP) in supramolecular systems, the elucidation of host-guest interactions in RTP is of vital importance. Herein, we employed two organic dyes (PYCl and PYBr) and their four host-guest complexes with CB[6] and CB[7] and explored the mechanism of host-guest interaction induced RTP enhancement using quantum mechanics/molecular mechanics (QM/MM) approach. For the two organic dyes, we found that the better RTP performance of PYBr than PYCl is attributed to intersystem crossing (ISC) augmentation induced by the heavy atom effect. Binding to CB[6] through host-guest interactions can simultaneously accelerate the radiative decay process by increasing the transition dipole moment of T1 → S0 (μT1→S0), block the nonradiative decay process, and promote the ISC process, eventually leading to a remarkably boosted RTP. Upon complexation, the conversion of S1 from 1(n, π*) to 1(π, π*) is key to μT1→S0 enhancement; reduced reorganization energies reflect the suppression of the nonradiative decay process by restricting the rotation of rings A and B in organic dyes. In addition, the promoted ISC process is due to the activation of more ISC channels between S1 and high-lying triplet states with large spin-orbital coupling constants and small energy gap. The case of CB[7]-type complexes is much different, because of the extremely large cavity size of CB[7] for encapsulation. This work proposes the mechanism of host-guest interaction-induced RTP enhancement of organic dyes, thus laying a solid foundation for the rational design of advanced RTP materials based on supramolecular assemblies.

Excited-state dynamics of 3-hydroxychromone in gas phase.

In recent years, 3-hydroxychromone (3-HC) and its derivatives have attracted much interest for their applications as molecular photoswitches and fluorescent probes. A clear understanding of their excited-state dynamics is essential for their applications and further development of new functional 3-HC derivatives. However, the deactivation mechanism of the photoexcited 3-HC family is still puzzling as their spectral properties are sensitive to the surrounding medium and substituents. The excited-state relaxation channels of 3-HC have been a matter of intense debate. In the current work, we thoroughly investigated the excited-state decay process of the 3-HC system in the gas phase using high-level electronic structure calculations and on-the-fly excited-state dynamic simulations intending to provide insight into the intrinsic photochemical properties of the 3-HC system. A new deactivation mechanism is proposed in the gas phase, which is different from that in solvents. The excited-state intramolecular proton transfer (ESIPT) process that occurs in solutions is not preferred in the gas phase due to the existence of a sizable energy barrier (∼0.8 eV), and thus, no dual fluorescence is found. On the contrary, the non-radiative decay process is the dominant decay channel, which is driven by photoisomerization combined with ring-puckering and ring-opening processes. The results coincide with the observations of an experiment performed in a supersonic jet by Itoh (M. Itoh, Pure Appl. Chem., 1993, 65(8), 1629-1634). The current work indicates that the solution environment plays an important role in regulating the excited-state dynamic behaviour of the 3-HC system. This study thus provides theoretical guidance for the rational design and improvement of the photochemical properties of the 3-HC system and paves the way for further investigation into its photochemical properties in complex environments.

Photochemical mechanistic study of hexafluorobenzene involving the low-lying states.

The photochemical isomerization and nonradiative decay processes of hexafluorobenzene (HFB) were investigated theoretically to gain insights into its photochemical mechanism and the perfluoro effect. A complete mechanistic scheme is presented through the characterization of all the possible minima and transition states of the S0, S1, and S2 states at the CASPT2/6-311G**//CAS(6,7)/6-31G* level. On the S0 potential energy surface, HFB could isomerize to three different products [Dewar-HFB (S0-P1), benzvalene-HFB (S0-P2), and fulvene-HFB (S0-P3)]. Following excitation to the S2 state with the perpendicular π → σ* transition, a chair-type minimum with Cs symmetry was found on the S2 potential energy surface. The adjacent S2/S1 conical intersection was immediately accessible from the S2 minimum. The nature of the S1 state was confirmed to have a π → π* character. Both the S2 and S1 photochemistries of HFB yielded Dewar-HFB via the S1/S0 conical intersection. The regeneration of the S0 state from the S1 and T2 states via intersystem crossing or internal conversion was also revealed.

Theoretical perspective for hydrostatic pressure responsive mechanism of room temperature phosphorescence molecules

Stimulus-responsive organic room temperature phosphorescence (RTP) materials are a class of materials that show emission property changes when subjected to diverse environmental stimuli. The change of molecular stacking modes and intermolecular interactions can result in mechanical stimulus-induced emission switching behaviour. The underlying mechanism of mechanoresponsive luminescent material is still unclear. Herein, based on density functional theory and time-dependent density functional theory calculations, the photophysical properties with response to hydrostatic pressure of RTP molecules in crystal are theoretically studied. Excited state dynamic processes are investigated by using quantum mechanics and molecular mechanics method coupled with thermal vibration correlation function method. Results show that the increase of pressure can blue-shift the RTP emissions which is mainly caused by the change of molecular conformation and the increase of bending vibration frequency. Under 2 Gpa, large spin–orbit coupling effect is determined, remarkable radiative and non-radiative decay processes are achieved. At 0.6 Gpa, a small non-radiative decay rate from T 1 to S 0 is obtained, high efficiency and long lifetime (more than 10 times the other pressures) are realised. Through further analysing the staking modes, reorganisation energies and SOC constants, relationships between molecular structures and RTP properties are determined, hydrostatic pressure responsive mechanism is revealed.

Hexanuclear Ln6 L6 Complex Formation by Using an Unsymmetric Ligand.

Multinuclear, self-assembled lanthanide complexes present clear opportunities as sensors and imaging agents. Despite the widely acknowledged potential of this class of supramolecule, synthetic and characterization challenges continue to limit systematic studies into their self-assembly restricting the number and variety of lanthanide architectures reported relative to their transition metal counterparts. Here we present the first study evaluating the effect of ligand backbone symmetry on multinuclear lanthanide complex self-assembly. Replacement of a symmetric ethylene linker with an unsymmetric amide at the center of a homoditopic ligand governs formation of an unusual Ln6 L6 complex with coordinatively unsaturated metal centers. The choice of triflate as a counterion, and the effect of ionic radii are shown to be critical for formation of the Ln6 L6 complex. The atypical Ln6 L6 architecture is characterized using a combination of mass spectrometry, luminescence, DOSY NMR and EPR spectroscopy measurements. Luminescence experiments support clear differences between comparable Eu6 L6 and Eu2 L3 complexes, with relatively short luminescent lifetimes and low quantum yields observed for the Eu6 L6 structure indicative of non-radiative decay processes. Synthesis of the Gd6 L6 analogue allows three distinct Gd⋯Gd distance measurements to be extracted using homo-RIDME EPR experiments.

Theoretical Insight into the Effect of Phosphorus Oxygenation on Nonradiative Decays: Comparative Analysis of P-Bridged Stilbene Analogs.

Incorporation of the phosphorus element into a π-conjugated skeleton offers valuable prospects for adjusting the electronic structure of the resulting functional π-electron systems. Trivalent phosphorus has the potential to decrease the LUMO level through σ*-π* interaction, which is further enhanced by its oxygenation to the pentavalent P center. This study shows that utilizing our computational analysis to examine excited-state dynamics based on radiative/nonradiative rate constants and fluorescence quantum yield (ΦF) is effective for analyzing the photophysical properties of P-containing organic dyes. We theoretically investigate how the trivalent phosphanyl group and pentavalent phosphine oxide moieties affect radiative and nonradiative decay processes. We evaluate four variations of P-bridged stilbene analogs. Our analysis reveals that the primary decay pathway for photoexcited bis-phosphanyl-bridged stilbene is the intersystem crossing (ISC) to the triplet state and nonradiative. The oxidation of the phosphine moiety, however, suppresses the ISC due to the relative destabilization of the triplet states. The calculated rate constants match an increase in experimental ΦF from 0.07 to 0.98, as simulated from 0.23 to 0.94. The reduced HOMO-LUMO gap supports a red shift in the fluorescence spectra relative to the phosphine analog. The thiophene-fused variant with the nonoxidized trivalent P center exhibits intense emission with a high ΦF, 0.95. Our prediction indicates that the ISC transfer is obstructed owing to the relatively destabilized triplet state induced by the thiophene substitution. Conversely, the thiophene-fused analog with the phosphine oxide moieties triggers a high-rate internal conversion mediated by conical intersection, leading to a decreased ΦF.

Facet-Defect Tolerant Bi-Doped Cs2AgxNa1-xInCl6 Nanoplatelets with a Near-Unity Photoluminescence Quantum Yield.

We report the colloidal synthesis of Bi-doped Cs2AgxNa1-xInCl6 double perovskite nanoplatelets (NPLs) exhibiting a near-unity photoluminescence quantum yield (PLQY), a record emission efficiency for nanoscale lead-free metal halides. A combination of optical spectroscopies revealed that nonradiative decay processes in the NPL were suppressed, indicating a well-passivated surface. By comparison, nanocubes with the same composition and surface ligands as the NPLs had a PLQY of only 40%. According to our calculations, the type of trap states arising from the presence of surface defects depends on their specific location: defects located on the facets of nanocubes generate only shallow traps, while those at the edges result in deep traps. In NPLs, due to their extended basal facets, most of the surface defects are facet defects. This so-called facet-defect tolerant behavior of double perovskites explains the more efficient optical emission of NPLs compared to that of nanocubes.