Single-Molecule Magnetoluminescence from a Spatially Confined Persistent Diradical Emitter.

Luminescent radicals are an emerging class of materials that exhibit unique photofunctions not found in closed-shell molecules due to their open-shell electronic structure. Particularly promising are photofunctions in which radical's spin and luminescence are correlated; for example, when a magnetic field can affect luminescence (i.e., magnetoluminescence, ML). These photofunctions could be useful in the new science of spin photonics. However, previous observations of ML in radicals have been limited to systems in which radicals are randomly doped in host crystals or polymerized through metal complexation. This study shows that a covalently linked luminescent radical dimer (diradical) can exhibit ML as a single-molecular property. This facilitates detailed elucidation of the requirements for and mechanisms of ML in radicals and can aid the rational design of ML-active radicals based on synthetic chemistry.

Triarylamine-Substituted Benzimidazoliums as Electron Donor-Acceptor Dyad-Type Photocatalysts for Reductive Organic Transformations.

Triarylamine-substituted benzimidazoliums (BI+-PhNAr2), new electron donor-acceptor dyad molecules, were synthesized. Their photocatalytic properties for reductive organic transformations were explored using absorption and fluorescence spectroscopy, redox potential determinations, density functional theory calculations, transient absorption spectroscopy, and reduction reactions of selected substrates. The results show that irradiation of BI+-PhNAr2 promotes photoinduced intramolecular electron transfer to form a long-lived (∼300 µs) charge shifted state (BI•-PhN•+Ar2). In the pathway for photocatalysis of reduction reactions of substrates, BI•-PhN•+Ar2 is subsequently transformed to the neutral benzimidazolyl radical (BI•-PhNAr2) by single-electron transfer from the donor 1,3-dimethyl-2-phenylbenzimidazoline (BIH-Ph) serving as a cooperative agent. Among the benzimidazoliums explored, the bromo-substituted analogue BI+-PhN(C6H4Br-p)2 in conjunction with BIH-Ph demonstrates the most consistent catalytic performance.

Rapid expansion of the invasive-like red macroalga, Chondria tumulosa (Rhodophyta), on the coral reefs of the Papahanaumokuakea Marine National Monument.

A cryptogenic, invasive-like red macroalga, Chondria tumulosa, was first observed in 2016 forming thick mats on the forereef of Manawai Atoll within Papahanaumokuakea Marine National Monument. Subsequent expeditions revealed an increased abundance of this alga. In 2021, unattached C. tumulosa was observed forming a network of dark, meandering accumulations throughout the atoll's inner lagoon. High-resolution satellite imagery revealed that these accumulations became visible in 2015 (length: ~0.74 km; area: ~0.88 km2 ) and increased 56-fold in length and 115-fold in area by 2021 (length: 41.32 km; area: 101.34 km2 ). An exponential expansion rate of ~16.02 km · y-1 (length), ~44.75 km2 · y-1 (area). This study presents the comprehensive temporal and spatial expansion of C. tumulosa accumulations for Manawai Atoll since its discovery, providing ecologist and resource managers with a proxy to gauge the overall abundance trend of this invasive-like alga.

Transient photocurrent and optical absorption of disordered thin-film semiconductors: In-depth injection and nonlinear response.

The time-of-flight method is a fundamental approach for characterizing the transport properties of semiconductors. Recently, the transient photocurrent and optical absorption kinetics have been simultaneously measured for thin films; pulsed-light excitation of thin films should give rise to non-negligible in-depth carrier injection. Yet, the effects of in-depth carrier injection on the transient currents and optical absorption have not yet been elucidated theoretically. Here, by considering the in-depth carrier injection in simulations, we found a 1/t1-α/2 initial time (t) dependence rather than the conventional 1/t1-α dependence under a weak external electric field, where α < 1 is the index of dispersive diffusion. The asymptotic transient currents are not influenced by the initial in-depth carrier injection and follow the conventional 1/t1+α time dependence. We also present the relation between the field-dependent mobility coefficient and the diffusion coefficient when the transport is dispersive. The field dependence of the transport coefficients influences the transit time in the photocurrent kinetics dividing two power-law decay regimes. The classical Scher-Montroll theory predicts that a1 + a2 = 2 when the initial photocurrent decay is given by 1/ta1 and the asymptotic photocurrent decay is given by 1/ta2 . The results shed light on the interpretation of the power-law exponent of 1/ta1 when a1 + a2 ≠ 2.

An Element-Substituted Cyclobutadiene Exhibiting High-Energy Blue Phosphorescence.

1,3,2,4-Diazadiboretidine, an isoelectronic heteroanalogue of cyclobutadiene, is an interesting chemical species in terms of comparison with the carbon system, whereas its properties have never been investigated experimentally. According to Baird's rule, Hückel antiaromatic cyclobutadiene acquires aromaticity in the lowest triplet state. Here we report experimental and theoretical studies on the ground- and excited-state antiaromaticity/aromaticity as well as the photophysical properties of an isolable 1,3,2,4-diazadiboretidine derivative. The crystal structure of the diazadiboretidine derivative revealed that the B2 N2 ring adopts a planar rhombic geometry in the ground state. Yet, theoretical calculations showed that the B2 N2 ring turns to a square geometry with a nonaromatic character in the lowest triplet state. Notably, the diazadiboretidine derivative has the lowest singlet and triplet states lying at close energy levels and displays blue phosphorescence.

Peak autumn leaf colouring along latitudinal and elevational gradients in Japan evaluated with online phenological data.

We evaluated the spatial characteristics of the first day of peak leaf colouring (PLCstart) and their relationships with air temperature along latitudinal and elevational gradients in Japan from 2015 to 2017. Leaf colouring information collected from more than 740 sites via citizen science was analysed, representing elevations from 0 to 2800 m and latitudes from 32°N to 44°N. We found that locations with earlier PLCstart dates (day of year 265-294) displayed steeper slopes in elevation per degree of latitude than locations with later PLCstart dates (day of year 295-314). This statistically significant result indicates that the influence of elevation on PLCstart (vertical gradient) weakened as the leaf colouring season progressed in Japan. In addition to these spatial characteristics, the PLCstart and the warmth index (based on monthly mean air temperature) showed significant linear correlations for latitudinal and elevational gradients. This result suggests that the sensitivity of PLCstart to air temperature, as manifested in both latitudinal and elevational gradients, is constant. This study suggests that online phenological data may provide more accurate results for a regional scale (100-1000 km) than the datasets used by previous studies.

Spin-dependent electron transfer dynamics in a platinum-complex-donor-acceptor triad studied by transient-absorption detected magnetic field effect.

For realization of efficient organic light-energy conversion systems, controlling the lifetime of photogenerated charge separated states in donor (D)-acceptor (A) molecules is of much importance; the spin dynamics is one of the important controlling factors. We previously reported that the covalently-linked 1,3-bis(2-pyridylimino)-isoindolate platinum (BPIPt)-dimethoxytriphenylamine (D)-naphthaldiimide (A) triad molecule (BPIPt-DA) exhibits a triplet-born long-lived charge separated state (BPIPt-D•+A•-), the lifetime of which is significantly increased from 4 µs to 10 µs by an applied magnetic field of 270 mT in room temperature tetrahydrofuran (THF). The purpose of the present study is to clarify detailed dynamics of spin-dependent generation and the decay of BPIPt-D+A-. For this purpose, we measured transient optical absorption (TA) and the TA-detected magnetic field effect (MFE) as functions of temperature and dispersion media. In THF at 183 K, MFE-detected transient spectra of the intermediate BPIPt•--D•+A state are observed. We have successfully quantified the recombination loss at this state by a kinetic simulation of MFE without using any reference molecules. The lifetime of the final BPIPt-D•+A•- state in a cellulose acetate polymer matrix at room temperature is significantly prolonged to 20 µs at 0 mT and 96 µs at 250 mT compared to those in THF. From the comparison of temperature dependences of the two media, effects of molecular motions on the electronic coupling and the spin relaxation are discussed.

Biological processes dominate seasonality of remotely sensed canopy greenness in an Amazon evergreen forest.

Satellite observations of Amazon forests show seasonal and interannual variations, but the underlying biological processes remain debated. Here we combined radiative transfer models (RTMs) with field observations of Amazon forest leaf and canopy characteristics to test three hypotheses for satellite-observed canopy reflectance seasonality: seasonal changes in leaf area index, in canopy-surface leafless crown fraction and/or in leaf demography. Canopy RTMs (PROSAIL and FLiES), driven by these three factors combined, simulated satellite-observed seasonal patterns well, explaining c. 70% of the variability in a key reflectance-based vegetation index (MAIAC EVI, which removes artifacts that would otherwise arise from clouds/aerosols and sun-sensor geometry). Leaf area index, leafless crown fraction and leaf demography independently accounted for 1, 33 and 66% of FLiES-simulated EVI seasonality, respectively. These factors also strongly influenced modeled near-infrared (NIR) reflectance, explaining why both modeled and observed EVI, which is especially sensitive to NIR, captures canopy seasonal dynamics well. Our improved analysis of canopy-scale biophysics rules out satellite artifacts as significant causes of satellite-observed seasonal patterns at this site, implying that aggregated phenology explains the larger scale remotely observed patterns. This work significantly reconciles current controversies about satellite-detected Amazon phenology, and improves our use of satellite observations to study climate-phenology relationships in the tropics.

Benzimidazolium Naphthoxide Betaine Is a Visible Light Promoted Organic Photoredox Catalyst.

Benzimidazolium naphthoxide (-ONap-BI+) was first synthesized and utilized as an unprecedented betaine photoredox catalyst. Photoexcited state of -ONap-BI+ generated by visible light irradiation catalyzes the reductive deiodination as well as desulfonylation reactions in which 1,3-dimethyl-2-phenylbenzimidazoline (Ph-BIH) cooperates with as an electron and hydrogen atom donor. Significant solvent effects on the reaction progress were discovered, and specific solvation toward imidazolium and naphthoxide moieties of -ONap-BI+ was proposed.

Visible Light and Hydroxynaphthylbenzimidazoline Promoted Transition-Metal-Catalyst-Free Desulfonylation of N-Sulfonylamides and N-Sulfonylamines.

A visible light promoted process for desulfonylation of N-sulfonylamides and -amines has been developed, in which 1,3-dimethyl-2-hydroxynaphthylbenzimidazoline (HONap-BIH) serves as a light absorbing, electron and hydrogen atom donor, and a household white light-emitting diode serves as a light source. The process transforms various N-sulfonylamide and -amine substrates to desulfonylated products in moderate to excellent yields. The observation that the fluorescence of 1-methyl-2-naphthoxy anion is efficiently quenched by the substrates suggests that the mechanism for the photoinduced desulfonylation reaction begins with photoexcitation of the naphthoxide chromophore in HONap-BIH, which generates an excited species via intramolecular proton transfer between the HONap and BIH moieties. This process triggers single electron transfer to the substrate, which promotes loss of the sulfonyl group to form the free amide or amine. The results of studies employing radical probe substrates as well as DFT calculations suggest that selective nitrogen-sulfur bond cleavage of the substrate radical anion generates either a pair of an amide or amine anion and a sulfonyl radical or that of an amidyl or aminyl radical and sulfinate anion, depending on the nature of the N-substituent on the substrate. An intermolecular version of this protocol, in which 1-methyl-2-naphthol and 1,3-dimethyl-2-phenylbenzimidazoline are used concomitantly, was also examined.

Effect of molecular diffusion on the spin dynamics of a micellized radical pair in low magnetic fields studied by Monte Carlo simulation.

Magnetic field effect is a powerful tool to study dynamics and kinetics of radical pairs (RPs), which are one of the most important intermediates for organic photon-energy conversion reactions. However, quantitative discussion regarding the relationship between the modulation of interelectron interactions and spin dynamics at low magnetic fields (<10 mT) is still an open question. We have studied the spin dynamics of a long-lived RP in a micelle by newly developed Monte Carlo simulation, in which fluctuations of the exchange and magnetic dipolar interactions by in-cage diffusion are directly introduced to the time-domain spin dynamics calculation. State-dependent relaxation/dephasing times of a few to a few tens of nanoseconds are obtained by simulations without hyperfine interactions (HFIs) as a function of the mutual diffusion constant (∼10(-6) cm(2)/s). Simulations with the HFIs exhibit incoherent singlet-triplet (S-T) mixings resulting from interplay between the HFIs and the fluctuating spin-spin interactions. The experimentally observed incoherent S-T mixing of ∼20 ns at 3 mT for a singlet-born RP in a sodium dodecyl sulfate micelle is reproduced by the simulation with reasonable diffusion coefficients. The computational method developed here contributes to quantitative detection of molecular motion that governs the recombination efficiency of RPs.

Electron spin polarization transfer from photogenerated spin-correlated radical pairs to a stable radical observer spin.

A series of donor-chromophore-acceptor-stable radical (D-C-A-R(•)) molecules having well-defined molecular structures were synthesized to study the factors affecting electron spin polarization transfer from the photogenerated D(+•)-C-A(-•) spin-correlated radical pair (RP) to the stable radical R(•). Theory suggests that the magnitude of this transfer depends on the spin-spin exchange interaction (2JDA) of D(+•)-C-A(-•). Yet, the generality of this prediction has never been demonstrated. In the D-C-A-R(•) molecules described herein, D is 4-methoxyaniline (MeOAn), 2,3-dihydro-1,4-benzodioxin-6-amine (DioxAn), or benzobisdioxole aniline (BDXAn), C is 4-aminonaphthalene-1,8-dicarboximide, and A is naphthalene-1,8:4,5-bis(dicarboximide) (1A,B-3A,B) or pyromellitimide (4A,B-6A,B). The terminal imide of the acceptors is functionalized with either a hydrocarbon (1A-6A) or a 2,2,6,6-tetramethyl-1-piperidinyloxyl radical (R(•)) (1B-6B). Photoexcitation of C with 416-nm laser pulses results in two-step charge separation to yield D(+•)-C-A(-•)-(R(•)). Time-resolved electron paramagnetic resonance (TREPR) spectroscopy using continuous-wave (CW) microwaves at both 295 and 85 K and pulsed microwaves at 85 K (electron spin-echo detection) was used to probe the initial formation of the spin-polarized RP and the subsequent polarization of the attached R(•) radical. The TREPR spectra show that |2JDA| for D(+•)-C-A(-•) decreases in the order MeOAn(+•) > DioxAn(+•) > BDXAn(+•) as a result of their spin density distributions, whereas the spin-spin dipolar interaction (dDA) remains nearly constant. Given this systematic variation in |2JDA|, electron spin-echo-detected EPR spectra of 1B-6B at 85 K show that the magnitude of the spin polarization transferred from the RP to R(•) depends on |2JDA|.

Manipulating photogenerated radical ion pair lifetimes in wirelike molecules using microwave pulses: molecular spintronic gates.

We have studied spin-dependent charge transfer dynamics in wirelike donor-bridge-acceptor (D-B-A) molecules comprising a phenothiazine (PTZ) donor, an oligo(2,7-fluorene) (FL(n)) bridge, and a perylene-3,4:9,10-bis(dicarboximide) (PDI) acceptor, PTZ-FL(3)-PDI (1) and PTZ-FL(4)-PDI (2), dissolved in the magnetic field-aligned nematic phase of 4-cyano-4'-n-pentylbiphenyl (5CB) at 295 K. Time-resolved EPR spectroscopy using both continuous wave and pulsed microwaves shows that the photogenerated radical pairs (RPs), PTZ(+•)-FL(3)-PDI(-•) and PTZ(+•)-FL(4)-PDI(-•), recombine much faster from the singlet RP manifold than the triplet RP manifold. When a strong resonant microwave π pulse is applied following RP photogeneration in 1 and 2, the RP lifetimes increase about 50-fold as indicated by electron spin-echo detection. This result shows that the RP lifetime can be greatly extended by rapidly switching off fast triplet RP recombination.

Magnetic field-induced switching of the radical-pair intersystem crossing mechanism in a donor-bridge-acceptor molecule for artificial photosynthesis.

A covalent, fixed-distance donor-bridge-acceptor (D-B-A) molecule was synthesized that upon photoexcitation undergoes ultrafast charge separation to yield a radical ion pair (RP) in which the spin-spin exchange interaction (2J) between the two radicals is sufficiently large to result in preferential RP intersystem crossing to the highest-energy RP eigenstate (T(+1)) at the 350 mT magnetic field characteristic of X-band (9.5 GHz) EPR spectroscopy. This behavior is unprecedented in covalent D-B-A molecules, and is evidenced by the time-resolved EPR (TREPR) spectrum at X-band of (3*)D-B-A derived from RP recombination, which shows all six canonical EPR transitions polarized in emission (e,e,e,e,e,e). In contrast, when the RP is photogenerated in a 3400 mT magnetic field, the TREPR triplet spectrum at W-band (94 GHz) of (3*)D-B-A displays the (a,e,e,a,a,e) polarization pattern characteristic of a weakly coupled RP precursor, similar to that observed in photosynthetic reaction center proteins, and indicates a switch to selective population of the lower-energy T(0) eigenstate.

Photogenerated Radical Pair between Flavin and a Tryptophan-Containing Transmembrane-Type Peptide in a Large Unilamellar Vesicle.

Electron-transfer (ET) reactions in biological systems, such as those with magnetic sensors based on flavoproteins and electron transport at biomembrane interfaces, are interesting and important issues that require understanding. As a model system of flavoproteins in biomimetic environments, we report the dynamics of the radical pair generated by photoinduced ET between riboflavin tetrabutylate (RFTB) and tryptophan (Trp) residues in a transmembrane-type polypeptide, both of which are distributed in a large unilamellar vesicle of 1,2-dimyristoyl-sn-glycero-3-phosphocholine. The Trp residues locate near the hydrophilic membrane interface, as confirmed by a dual-fluorescence quenching assay. The fluorescence and transient absorption upon photoexcitation of RFTB indicate that ET from both the singlet and triplet excited states occurs at the hydrophilic interface, whereas the RFTB in the hydrophobic region does not contribute to ET. The ET efficiency and the magnetic field effect (MFE) on the RFTB anion increase significantly above the gel-to-liquid crystal phase transition temperature due to a decrease in microviscosity. The MFE analysis indicates that the radical pair generated from the triplet ET channel exhibits a long lifetime as those in micellar systems due to the strong cage effect of the vesicle.

Novel azalides derived from 16-membered macrolides. III. Azalides modified at the C-15 and 4'' positions: Improved antibacterial activities.

The design and synthesis of 16-membered azalides modified at the C-15 and 4'' positions are described. The compounds we report here are characterized by an arylpropenyl group attached to the C-15 position of macrolactone and a carbamoyl group at the C-4'' position in a neutral sugar. Introduction of alkylcarbamoyl groups to the C-4'' position was regioselectively achieved by unique and convenient methods via acyl migration. As a result of optimization at the C-3 and 15 positions, several compounds were found to have potent activity against mef- and erm-resistant bacterial strains. These results suggest that 16-membered azalides could be promising compounds as clinical candidates.

Time-resolved EPR studies of charge recombination and triplet-state formation within donor-bridge-acceptor molecules having wire-like oligofluorene bridges.

Spin-selective charge recombination of photogenerated radical ion pairs within a series of donor-bridge-acceptor (D-B-A) molecules, where D = phenothiazine (PTZ), B = oligo(2,7-fluorenyl), and A = perylene-3,4:9,10-bis(dicarboximide) (PDI), PTZ-FL(n)-PDI, where n = 1-4 (compounds 1-4), is studied using time-resolved electron paramagnetic resonance (TREPR) spectroscopy in which the microwave source is either continuous-wave or pulsed. Radical ion pair TREPR spectra are observed for 3 and 4 at 90-294 K, while the neutral triplet state of PDI ((3)*PDI) is observed at 90-294 K for 2-4 and at 90 K for 1. (3)*PDI is produced by three mechanisms, as elucidated by its zero-field splitting parameters and spin polarization pattern. The mechanisms are spin-orbit-induced intersystem crossing (SO-ISC) in PDI aggregates, direct spin-orbit charge-transfer intersystem crossing (SOCT) from the singlet radical pair within 1, and radical pair intersystem crossing (RP-ISC) as a result of S-T(0) mixing of the radical ion pair states in 2-4. The temperature dependence of the spin-spin exchange interaction (2J) shows a dramatic decrease at low temperatures, indicating that the electronic coupling between the radical ions decreases due to an increase in the average fluorene-fluorene dihedral angle at low temperatures. The charge recombination rates for 3 and 4 decrease at low temperature, but that for 2 is almost temperature-independent. These results strongly suggest that the dominant mechanism of charge recombination for n >or= 3 is incoherent thermal hopping, which results in wire-like charge transfer.

Competitive electron transfer and enhanced intersystem crossing in photoexcited covalent TEMPO-perylene-3,4:9,10-bis(dicarboximide) dyads: unusual spin polarization resulting from the radical-triplet interaction.

A stable 2,2,6,6-tetramethyl-1-piperidinyloxyl (TEMPO) radical was covalently attached at its 4-position to the imide nitrogen atom of a perylene-3,4:9,10-bis(dicarboximide) (PDI) to produce TEMPO-PDI, 1, having a well-defined distance and orientation between TEMPO and PDI. Transient optical absorption experiments in toluene following selective photoexcitation of the PDI chromophore in TEMPO-PDI show that enhanced intersystem crossing occurs with tau = 45 +/- 1 ps, resulting in formation of TEMPO-(3*)PDI, while the same experiment in THF shows that the electron-transfer reaction TEMPO-(1*)PDI --> TEMPO(+*)-PDI(-*) occurs with tau = 1.2 +/- 0.2 ps and thus competes effectively with enhanced intersystem crossing. Time-resolved EPR (TREPR) spectroscopy on the photogenerated three-spin system TEMPO-(3*)PDI in toluene at 295 K initially shows a broad signal assigned to spin-polarized (3*)PDI, which thermalizes at longer times and is accompanied by formation of an emissively polarized TEMPO radical. No signals are observed in THF at 295 K. The TREPR spectrum of TEMPO-(3*)PDI at 85 K in toluene shows an emissive/absorptive signal due to TEMPO and a broad triplet signal due to (3*)PDI having a spin polarization pattern characteristic of overpopulation of its T(0) sublevel. This unusual spin polarization pattern does not result from radical pair intersystem crossing because electron transfer does not occur at 85 K. The observed spin polarization of (3*)PDI cannot be readily explained by mechanisms discussed previously, leading us to propose a new spin polarization mechanism, which requires that the radical and attached triplet are in the weak exchange regime.

Cultivation potential projections of breadfruit (Artocarpus altilis) under climate change scenarios using an empirically validated suitability model calibrated in Hawai'i.

Humanity faces significant challenges to agriculture and human nutrition, and changes in climate are predicted to make such challenges greater in the future. Neglected and underutilized crops may play a role in mitigating and addressing such challenges. Breadfruit is a long-lived tree crop that is a nutritious, carbohydrate-rich staple, which is a priority crop in this regard. A fuzzy-set modeling approach was applied, refined, and validated for breadfruit to determine its current and future potential productivity. Hawai'i was used as a model system, with over 1,200 naturalized trees utilized to calibrate a habitat suitability model and 56 producer sites used to validate the model. The parameters were then applied globally on 17 global climate models at the RCP 4.5 and RCP 8.5 global climate projections for 2070. Overall, breadfruit suitability increases in area and in quality, with larger increases occurring in the RCP 8.5 projection. Current producing regions largely remain unchanged in both projections, indicating relative stability of production potential in current growing regions. Breadfruit, and other tropical indigenous food crops present strong opportunities for cultivation and food security risk management strategies moving forward.