Stable Organic Radicals Research Articles

Magnetic Circular Dichroism of Luminescent Triarylmethyl Radicals.

Stable triarylmethyl radicals are the most common carbon radical building blocks and have recently attracted much attention for their luminescent properties. However, magnetic circular dichroism (MCD) discovered by Michael Faraday and magnetic circularly polarized luminescence (MCPL) have not been observed for simple triarylmethyl radicals, probably due to their photodegradability. Here we report the first observation of MCD and MCPL of triarylmethyl radicals in solution using racemic mixtures of (3,5-dichloro-4-pyridyl)bis(2,4,6-trichlorophenyl)methyl radical (PyBTM) and (3,5-difluoro-4-pyridyl)bis(2,4,6-trichlorophenyl)methyl radical (F2PyBTM), which are much more photostable than simple triphenylmethyl radical derivatives. Faraday B terms, which are at the origin of magnetic dichroism in nondegenerate systems, were calculated using TD-DFT, and the line shape of MCD spectra was well reproduced. This study provides new circular dichroism properties for luminescent triarylmethyl radicals in solution without separating enantiomers and also clarifies the origin of magnetic circular dichroism properties of stable organic radicals for the first time.

Diradicaloid-Loaded Polypeptide Nanoparticles for Two-Photon NIR Phototheranostics.

Stable organic radicals, with unique electronic transitions from the ground state (D0) to the doublet excited state (D1), show promise as high-fluorescence quantum yield dyes. While organic small-molecule photosensitizers (PSs) have advanced for tumor photodynamic therapy (PDT), opportunities exist to enhance their performance and functionality. Herein, we synthesized Thiele's fluorocarbon derivative diradicaloid TFC-I with nearly 100% PLQY and integrated it into amphiphilic polypeptide nanoparticles, P-TI, using a precursor-doping approach. P-TI demonstrated notable features including high photostability, aggregation-induced emission, bright near-infrared fluorescence, substantial quantum yield (37% PLQY), robust near-infrared two-photon absorption (∼400 GM cross section), and superior ROS generation compared to commercial PSs. In vitro and in vivo experiments confirmed that P-TI performed well in mitochondria-targeted PDT, two-photon fluorescence imaging, and biosafety. This work highlights the use of organic stable radicals with precursor-doping for efficient PDT and deep tumor tissue imaging.

Photo-Induced Ultrafast Charge Transfer and Air-Stable Radical Formation in Tetraphenylpyrene Derivatives.

Stable organic radicals generated by photo-excitation hold applications in molecular switching devices and information storage. It remains challenging to develop photo-generated radical materials with rapid response and air stability in the solid state. Here, we report a structure based on 1,3,6,8-tetraphenylpyrene derivative (Py-TTAc) displaying photo-induced radicals with air stability in the solid state. Photo-induced electron transfer, exposed to a 365 nm ultraviolet lamp for 1 minute, affords radicals in Py-TTAc powder as confirmed by electron paramagnetic resonance (EPR) spectroscopy. The maximum radical concentration reaches 2.21 % after continuous irradiation for 1 hour and recurs more than 10 times without any chemical degradation. The mechanistic study according to the femtosecond transient absorption (fsTA) and X-ray technology suggests that the radicals are derived from photo-induced symmetry-breaking charge separation (SB-CS) and stabilized through non-covalent interactions. The photo-generated stable radical system is employed in anti-counterfeiting paper and optoelectronic device applications. This study will provide insights into the development of photoactive organic radical materials.

Spirocyclic pyrrolidinyl nitroxides with exo-methylene substituents.

Nitroxides are stable organic radicals with exceptionally long lifetimes, which render them uniquely suitable as observable probes or polarising agents for spectroscopic investigation of biomolecular structure and dynamics. Radical-based probes for biological applications are ideally characterized by both robustness towards reductive degradation and beneficial electron spin relaxation parameters. These properties are largely influenced by the molecular structure of the nitroxide scaffold, and also by the conformations it prefers to adopt. In this study we present the synthesis of the first nitroxides based on a spirocyclic pyrrolidine scaffold with an exocyclic methylene substituent. The conformations adopted by these nitroxides were evaluated by X-ray crystallography, both with single nitroxide crystals and by inclusion of nitroxides in a microporous crystalline sponge. The kinetic and thermodynamic stability of the new nitroxides towards reduction was investigated by electron paramagnetic resonance (EPR) spectroscopy and cyclic voltammetry (CV). In combination with EPR measurements of electron spin relaxation properties, these results suggest that this new family of nitroxides can provide access to multifunctionalized probes and polarising agents suitable for use in biological environments at elevated temperatures.

Stable aryl-armed dihydrophenazines-based radicals

Stable organic radicals have long been desired for applications in quantum information science and optoelectronic semiconductor. Weakening the reactivity of unpaired electrons is an efficient strategy for fabrication stable radicals. The dual aryl/alkyl-substituted dihydrophenazine (DArPZ/DAlPz) derivatives have attracted a lot of attention due to their potential radical stability characteristics. In this work, three stable DArPZ-based radical cation compounds are obtained through tuning peripheral substituted groups with different electron donating/withdrawing effect to discuss their reactive activity changes in different solvent and aggregate state. Employing systematic experiments from crystallography, spectroscopy and theoretical calculation analyses, some referenceable molecular structure design strategy and the analytical model of evaluating radical behavior are formed and summarized. In addition, radical cations have good masking ability without continuous electrical circulating, implying their application in light-shading electrochromic devices. This work is referable on the design of stable radicals, the establishment of dynamic evaluation strategies and theoretical analysis models for their reactivity.

Stable Radicals in Dihydrophenazine Derivatives-Doped Epoxy Resin for High Photothermal Conversion.

Organic radicals exhibit great potential in photothermal applications, however, their innate high reactivity with oxygen renders the preparation of stable organic radicals highly challenging. In this work, a series of co-doped radical polymers ares prepared by doping dihydrophenazine derivatives (DPPs) into the epoxy resin matrix. DPPs can form radical species through the electron transfer process, which are further stabilized by the complex 3D network structure of epoxy resin. Experimental results show that the photothermal conversion efficiency is as high as 79.9%, and the temperature can quickly rise to ≈130°C within 60 s. Due to the excellent visible light transmittance and mechanical properties of co-doped systems, this study further demonstrates their practical applications in energy-saving solar windows and thermoelectric power generation.

Self-enhanced regulation of stable organic radicals with polypeptide nanoparticles for mild second near-infrared phototheranostics

Stable organic radicals have emerged as a promising option to enhance fluorescence quantum yield (QY), gaining traction in medical treatment due to their unique electronic transitions from the ground state (D0) to the doublet excited state (D1). We synthesized a stable dicyanomethyl radical with a NIR-II fluorescence QY of 0.86 %, surpassing many NIR-II organic dyes. Subsequently, amphiphilic polymer-encapsulated nanoparticles (NPs) containing the radical were created, achieving a NIR-II fluorescence QY of 0.32 %, facilitating high-contrast bio-imaging. These CNPPs exhibit self-enhanced photothermal properties, elevating photothermal conversion efficiency (PCE) from 43.5 % to 57.5 % under 915 nm laser irradiation. This advancement enables more efficient photothermal therapy (PTT) with lower dye concentrations and reduced laser power, enhancing both feasibility and safety. Through regular fractionated mild photothermal therapy, we observed the release of damage-associated molecular patterns (DAMPs) and an increase in cytokine expression, culminating in combined mild phototherapy (m-PTT)-mediated immunogenic cell death (ICD). Consequently, we developed an immunostimulatory tumor vaccine, showcasing a novel approach for refining photothermal agents (PTA) and optimizing the PTT process.

Robust Supercooled Liquid Formation Enables All-Optical Switching Between Liquid and Solid Phases of TEMPO.

Organic molecules that undergo supercooling can provide the basis for novel stimuli-responsive materials, but the number of such compounds is limited. Results in this paper show that the stable organic radical 2,2,6,6-tetramethyl-1-piperidine-1-oxyl (TEMPO) can form a stable supercooled liquid (SCL). Upon melting and cooling back to room temperature, the TEMPO SCL can persist for months, even after mild physical agitation. Its high vapor pressure can enable crystal growth at remote locations within the sample container over the course of days. Optical, electron paramagnetic resonance, and birefringence measurements show no evidence of new chemical species or partially ordered phases in the supercooled liquid. TEMPO's free radical character permits absorption of visible light that can drive photothermal melting to form the SCL, while a single nanosecond light pulse can initiate recrystallization of the SCL at some later time. This capability enables all-optical switching between the solid and the SCL phases. The physical origin of TEMPO's remarkable stability as an SCL remains an open question, but these results suggest that organic radicals comprise a new class of molecules that can form SCLs with potentially useful properties.

Using a Stable Radical as an “Electron Donor” to Develop a Radical Photosensitizer for Efficient Type-I Photodynamic Therapy

Among type I photosensitizers, stable organic radicals are superior candidate molecules for hypoxia-overcoming photodynamic therapy. While their wide applications are limited by complicated preparation processes and poor stabilities. Herein, a...

Understanding trends in conductivity in four isostructural multifunctional crystals of Se substituted bis-dithiazolyl radicals

To understand the trends in conductivity in bisdithiazolyl-type radical-based molecular materials, one needs to master a holistic view of the parameters governing the charge transport process (namely, λ, HDA, topology of conduction paths, and ρc).

Unusual reactivity of 2,2-diphenyl-1-picrylhydrazyl (DPPH) with Fe3+ controlled by competing reactions.

2,2-Diphenyl-1-picrylhydrazyl (DPPH) is a stable organic free radical widely used in various fields as a model free radical. There is scarce information about the stability of this compound in the chemical environments in which it is used. Side reactions between DPPH and other species can alter the precision of experiments that use DPPH, such as the evaluation of antioxidant properties amongst others. Following recent investigations highlighting reactions between DPPH and metal cations or Lewis acids, a quantitative reaction between DPPH and Fe3+ in acetonitrile was studied in the present work. UV-Vis spectroscopy and electrochemistry were used to monitor the reaction. The results obtained indicate a fast and multistep reaction between Fe3+ and DPPH that can be simplified as a simple redox reaction with the formation of Fe2+ and DPPH+. The reaction mechanism proposed follows complex steps involving two competing phenomena: a disproportionation which accelerates the reaction and an oxidation process that slows it down through DPPH regeneration.

Cyano modified triphenylmethyl radical skeletons: higher stability and efficiency.

We introduced cyano groups to replace chlorine atoms in the tris(2,4,6-trichlorophenyl)methyl (TTM) radical skeleton, resulting in two cyano-modified TTM skeletons. The incorporation of cyano groups effectively suppresses nonradiative transition processes and lowers the frontier molecular orbital energy levels compared to those of the TTM radical. Consequently, enhanced photoluminescence quantum efficiency (PLQE) and a shift towards longer-wavelength emission in solution were achieved. Furthermore, the cyano-modified TTM skeletons exhibited improved stabilities. The development of these two skeletons adds diversity to stable organic luminescent radical skeletons.

Kinetics of Charge Transfer at Carbon-Based Counter Electrodes for Dye-Sensitized Solar Cells with Aqueous Electrolytes

Dye-sensitized solar cells (DSSCs) might provide a highly sustainable alternative for next generation photovoltaics. This is due to their low-energy production from abundant materials, short energy payback time, high efficiency under low illumination intensities (i.e., diffuse light or indoor conditions), and versatile concepts of applications. However, some commonly used electrolyte components are environmentally problematic. Acetonitrile or other volatile organic solvents, e.g., as well as carcinogenic cobalt complexes should not leak from DSSCs. Sealing foils, however, which are typically used to prevent such leakage, carry a risk of long-term failure.Replacing the organic solvent by water offers several advantages, as it is environmentally benign, less volatile and the cell function, further, cannot be damaged by the intrusion of water vapor. Instead of Co-complexes, e.g., the stable organic radical TEMPO (2,2,6,6-tretramethylpiperidine-1-oxyl) can serve as an alternative redox mediator with a highly positive redox potential (0.71 V vs. NHE). Using TEMPO, power conversion efficiencies (PCE) of up to 4.3% and high open-circuit voltages (V oc = 0.955 V) have been reported.[1] However, the use of TEMPO is limited by its solubility in water (C max < 0.15 M). Its derivative 4-hydroxy-TEMPO (OH-TEMPO) possesses a significantly higher solubility in water (C max > 2 M) and a more positive redox potential (0.81 V vs. NHE), making it a promising candidate as a redox mediator.In this work, we built DSSCs with TEMPO and OH-TEMPO based aqueous electrolytes, Y123-sensitized TiO2 photoanodes, and counter electrodes coated with poly(3,4-ethylenedioxythiphene) (PEDOT). For OH-TEMPO, the short-circuit current density (j sc) and open-circuit voltage were higher than with TEMPO, but the fill factor (FF) and the PCE were significantly lower. By impedance studies, large charge transfer resistances at the counter electrode (R CE) were obtained for OH-TEMPO in combination with additives such as 1-methylbenzimidazole (MBI), indicating a strong kinetic limitation of the OH-TEMPO+ reduction. However, we found that such additives as MBI or other organic compounds, are necessary to suppress recombination at the photoanode/electrolyte interface. Thus, we subsequently studied different counter electrode materials, such as platinum (reference), conducting polymers, and carbon materials, in contact to OH-TEMPO electrolytes with MBI to determine R CE and find suitable materials for the application in DSSCs.[1] Yang, W., Söderberg, M., Eriksson, A. I. K. & Boschloo, G. Efficient aqueous dye-sensitized solar cell electrolytes based on a TEMPO/TEMPO+ redox couple. RSC Advances 5, 26706–26709 (2015).

Developing stable organic radical anions to achieve long persistent luminescence for afterglow lighting

Developing stable organic radical anions to achieve long persistent luminescence for afterglow lighting

Bipolar Radicals as Active Material for Symmetrical Redox Flow Batteries

Redox-active organic molecules are increasingly investigated as charge-storage materials for redox-flow batteries (RFBs), but material crossover between posolyte/negolyte and chemical degradation are limiting factors in the performance of all-organic RFBs. Bipolar organic radicals can in principle be used to construct batteries with symmetrical electrolyte composition, which mitigates issues due to crossover. This presentation will describe studies to correlate molecular features with battery cycling stability using representative stable organic radicals (Blatter- and verdazyl-type compounds). We illustrate how an understanding of the reaction pathways that contribute to capacity fade can be used to improve battery longevity.

Pyrene-TEMPO-Modified Carbon Electrodes for Organic Radical Lithium-Ion Batteries

Organic radical batteries (ORBs) are a promising alternative to traditional lithium-ion batteries (LIBs) because of their environmentally friendly materials and potential to be low-cost, light weight, and mechanically flexible. Among ORB materials, stable organic radical polymers have great potential as high energy density and high power density cathode materials due to their small molecular weight and fast, reversible redox reactions. A stable radical polymer for LIB applications contains an organic radical unit with redox potentials suitable for the LIB anode or cathode that is immobilized on an electrode via a main chain polymer. Conductive and light-weight polymer main chains are necessary to ensure fast electron transfer to the current collector, without adding significant weight to the cell. Despite extensive research, organic radical materials present some key challenges which limit their present use in electrochemical cells. Many polymer backbones are non-conductive, leading to increased electrode resistance and poor cell performance at high charge/discharge rates. Many organic radical materials also have relatively low thermal stability and low packing density. Moreover, many organic radicals are soluble in typical organic battery electrolytes, resulting in capacity fading.In this research, we apply pyrene as a polymer backbone to 2,2,6,6-tetramethyl-piperidine-1-oxyl radical (TEMPO) for the first time in LIB applications to reduce the solubility of the active organic radical and enable π−π stacking interactions with aromatic carbons. We prepared a surface-immobilized p–TEMPO on fullerene C60 and graphene foam (GF) electrodes via π−π stacking interactions to increase electrode conductivity. Pyrene is used to modify certain carbon allotropes via π−π stacking interactions. It was hypothesized that this approach would enable strong bond formation of the TEMPO radical with the electrode, while providing a non-destructive and simple modification approach of conductive carbon surfaces. The successful conjugation of pyrene and TEMPO molecules was established by NMR spectroscopy. The redox activity of p-TEMPO in LIB electrolytes was validated in solution. The non-covalent attachment of p-TEMPO to fullerene C60 and GF electrodes was established by XPS. The mechanisms and reversibility of the TEMPO redox reaction was then explored for p-TEMPO immobilized on the carbon electrodes. While both electrodes showed diffusion-limited current, and quasi-reversible reactions, C60-p-TEMPO has better reversibility and less resistance than GF-p-TEMPO. C60-p-TEMPO electrodes exhibit exceptional cycling stability over 600 cycles. These results are outstanding as the C60 has a high tendency to dissolve in LIB electrolytes. LIB half-cell testing identified challenges and opportunities for the p-TEMPO-modified electrodes. C60-p-TEMPO discharge capacity at ~5C rate is comparable to PTMA-based literature, however no distinct TEMPO response was observed in the charge or discharge curves. GF-p-TEMPO electrodes showed a TEMPO response in cycle 1 only, suggesting possible p-TEMPO dissolution in the electrolyte. Overall, the results show that the use of a noncovalent immobilization method allows facile preparation of p-TEMPO functionalized electrodes and demonstrates the potential of p-TEMPO noncovalent bonding in organic LIB applications. Figure 1

Spin Catalysis in Photochemical Reactions and Its Applications to Quantum Information Nanotechnology

Chemistry as a science about spin and electric charge of micro particles which provide driving forces of atomic interactions and molecular structure transformations fits pretty well to the modern Quantum Information Science (QIS) requirements. Today’s computers operate only electric current signals in the semiconductor networks but the electron-spin properties are not exploited in a large extend. Spintronics provides spin-polarized currents and manipulates magnetic spin interactions; it uses mostly solid state chemistry of heavy elements. But a rich organic chemistry of solvents and fin films offers a great potential for molecular electronics and quantum computing. Photo-excited organic complexes of the “chromophore–radical” type provide good promise for many technological applications in molecular spintronics and electronics, including QIS technology. The doublet state photo excitation of stable organic radical being delocalized onto the linked anthracene molecule within picoseconds and subsequently evolved into a quartet state for big radicals (a pure high spin state) of the mixed radical-triplet character presents a sensible spin-optical interface for qubit in quantum computing. This high-spin state is coherently addressable with EPR microwaves even at room temperature, with the optical read-out induced by intersystem crossing (ISC) to emissive triplet state. Such integration of radical luminescence and high-spin states EPR provides the organic materials involvement into emerging QIS technologies

Highly bright stable organic radicals encapsulated by amphiphilic polypeptide for efficient near-infrared phototheranostics

Stable organic radical molecules have received extensive attention due to their unique electronic structure and photophysical properties, and the highly fluorescent quantum efficiency has great appeal to bioimaging. However, still scarce reports on the application of them on the therapy of tumors, especially theranostics. Here, 3,6-dibromocarbazole modified tris (2,4,6-trichlorophenyl) methane radical (TB) has been synthesized with high NIR fluorescence quantum efficiency, and free radical nanoparticles (NPs) have been prepared using the precursor of the radical doping strategy. The free radical molecule TB and its precursor molecule HTB were mixed in proportion and encapsulated with an amphiphilic polypeptide (PEG-PAsp) to obtain the NPs. The 4% NPs can achieve a high fluorescence quantum efficiency (18.68%) in the NIR region. In addition, the NPs also have a good ability to produce reactive oxygen species (ROS) under either normoxia or hypoxia conditions, which makes it possible for photodynamic therapy (PDT). Interestingly, the NPs also show preferable photothermal ability (PCE = 42.39%) for photothermal therapy (PTT). Both in vitro and in vivo studies reveal that the as-prepared radical NPS show a NIR fluorescence imaging-guided synergistic PTT and type I/II PDT to tumors. It provides new strategies and new clues for the application of free radical molecules in the theranostics of tumors.

Synthesis and Characterization of Face-to-Face Arylsulfanyl and Phenoxyl Radicals Embedded in Mesoporous Silicas

Recent applications of bi-, oligo-, or polyradicals to spin sciences have generated considerable interest in the design of new bi-/oligoradical organic molecules. Nevertheless, studies of physicochemical properties open shell systems are generally based on stable homonuclear organic radicals, which represent only a small portion of the existing radicals. In this context, diazene precursors of heteroatomic radicals were incorporated into the SBA-15 silica framework. Photolysis at 360 nm of the diazene moiety resulted in the formation of two face-to-face oxygen- and sulfur-centered radicals. These systems were characterized by X-, Q-, and W-band EPR spectroscopy by comparing them to silicas functionalized with either face-to-face sulfur-centered radicals or face-to-face oxygen-centered radicals. These EPR studies allowed measuring their half-life as well as their relaxation times (T1 and T2). The properties of silicas functionalized with sulfur- and oxygen-centered radicals fall between those measured for the two reference systems functionalized with only sulfur- or oxygen-centered radicals. These nanostructured silicas functionalized by two radicals of different nature are new potential candidates as a polarizing agent for DNP NMR.

Dual Charge Transfer Generated from Stable Mixed-Valence Radical Crystals for Boosting Solar-to-Thermal Conversion.

Realizing dual charge transfer (CT) based on stable organic radicals in one system is a long-sought goal, however, remains challenging. In this work, a stable mixed-valence radical crystal is designed via a surfactant-assisted method, namely TTF-(TTF+• )2 -RC (where TTF = tetrathiafulvalene), containing dual CT interactions. The solubilization of surfactants enables successful co-crystallization of mixed-valence TTF molecules with different polarity in aqueous solutions. Short intermolecular distances between adjacent TTF moieties within TTF-(TTF+• )2 -RC facilitate both inter-valence CT (IVCT) between neutral TTF and TTF+• , and inter-radical CT (IRCT) between two TTF+• in radical π-dimer, which are confirmed by single-crystal X-ray diffraction, solid-state absorption, electron spin resonance measurements, and DFT calculations. Moreover, TTF-(TTF+• )2 -RC reveals an open-shell singlet diradical ground state with the antiferromagnetic coupling of 2J = -657 cm-1 and an unprecedented temperature-dependent magnetic property, manifesting the main monoradical characters of IVCT at 113-203 K while the spin-spin interactions in radical dimers of IRCT are predominant at 263-353 K. Notably, dual CT characters endow TTF-(TTF+• )2 -RC with strong light absorption over the full solar spectrum and outstanding stability. As a result, TTF-(TTF+• )2 -RC exhibits significantly enhanced photothermal property, an increase of 46.6°C within 180 s upon one-sun illumination.