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In the last decades, socio-economical changes occurred in Italy have deeply affected woodland, particularly coppices. Although most of them, above all in public land, are being converted to high forests, in the last years coppices have been experiencing an increase in their use. The claimed need to reconcile silviculture and biodiversity conservation calls for a better understanding of the effects of coppice management practices on the different components of biodiversity. Using birds as environmental indicators, we studied differences in species composition and diversity of bird communities in coppices and “transitory stands” (ex-coppices recently converted in high stands) in the Alpe della Luna forest (Arezzo), in Tuscan Apennines. Relative frequency of each species and the mean abundance and richness at point level were compared among forest typologies. To test the effects of different management types on bird communities, descriptive models (GLM) have been applied using stand age and the amount of non-forest habitats as predictors. Our results show that 34.4% of the species (57.1% considering only forest species) are affected by the forest management type: 9 species (7 considering only forest species) were more common in transitory stands, while only two (of which one considered forest species) in coppices. Overall, richness is higher in transitory stands, where species of mature forests have been found; on the contrary, coppices did not host any open habitat species, as stated in other studies. Richness in forest species is positively related to stand age for both coppice and transitory stands; the amount of open habitats is positively correlated with number of open-habitat species, but it did not negatively affect richness in forest species that apparently did not suffer for any boundary effect.

Wind energy has experienced a very rapid growth in the last few years and the majority of predictions speculate a similar scenario also for the near future. Despite the fact that wind energy is carbon free, and thus does not contribute to global warming, wind farms are not free from impacting the environment in which they are built, particularly bird and bat populations – impacts that, at least in some cases, could be remarkable and thus need to be studied and monitored. In this paper, we present the results after the first year of monitoring, aiming to understand impacts of a wind farm on birds, particularly on raptors, both residents and migrators. The study area, located in central Tuscany, hosts a very rich raptor community with some species of conservation concern. Comparing data gathered before and after the wind farm construction, we note a dramatic decrease in the number of raptor observations, even though no species have definitely left the area. Significant differences arise also considering habitat use and bird behaviour, with raptors flying higher and away from turbines, stressing an avoidance effect. [ABSTRACT FROM PUBLISHER]

Carbene-metal-amides (CMAs) are emerging delayed fluorescence materials for organic light-emitting diode (OLED) applications. CMAs possess fast, efficient emission owing to rapid forward and reverse intersystem crossing (ISC) rates. The resulting dynamic equilibrium between singlet and triplet spin manifolds distinguishes CMAs from most purely organic thermally activated delayed fluorescence emitters. However, direct experimental triplet characterization in CMAs is underutilized, limiting our detailed understanding of the ISC mechanism. In this work, we combine time-resolved spectroscopy with tuning of state energies through environmental polarity and metal substitution, focusing on the interplay between charge-transfer ( 3 CT) and local exciton ( 3 LE) triplets. Unlike previous photophysical work, we investigate evaporated host : guest films of CMAs and small-molecule hosts for increased device relevance. Transient absorption reveals an evolution in the triplet excited-state absorption (ESA) consistent with a change in orbital character between hosts with differing dielectric constants. Using quantum chemical calculations, we simulate ESAs of the lowest triplet states, highlighting the contribution of only 3 CT and donor-moiety 3 LE states to spectral features, with no strong evidence for a low-lying acceptor-centered 3 LE. Thus, our work provides a blueprint for understanding the role of triplet excited states in CMAs which will enable further intelligent optimization of this promising class of materials., (© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

In plants, light-harvesting complexes serve as antennas to collect and transfer the absorbed energy to reaction centers, but also regulate energy transport by dissipating the excitation energy of chlorophylls. This process, known as nonphotochemical quenching, seems to be activated by conformational changes within the light-harvesting complex, but the quenching mechanisms remain elusive. Recent spectroscopic measurements suggest the carotenoid S* dark state as the quencher of chlorophylls' excitation. By investigating lutein embedded in different conformations of CP29 (a minor antenna in plants) via nonadiabatic excited state dynamics simulations, we reveal that different conformations of the complex differently stabilize the lutein s-trans conformer with respect to the dominant s-cis one. We show that the s-trans conformer presents the spectroscopic signatures of the S* state and rationalize its ability to accept energy from the closest excited chlorophylls, providing thus a relationship between the complex's conformation and the nonphotochemical quenching., (© 2024. The Author(s).)

The energetic landscape at the interface between electron donating and accepting molecular materials favors efficient conversion of intermolecular charge-transfer (CT) states into free charge carriers (FCC) in high-performance organic solar cells. Here, we elucidate how interfacial energetics, charge generation and radiative recombination are affected by molecular arrangement. We experimentally determine the CT dissociation properties of a series of model, small molecule donor-acceptor blends, where the used acceptors (B2PYMPM, B3PYMPM and B4PYMPM) differ only in the nitrogen position of their lateral pyridine rings. We find that the formation of an ordered, face-on molecular packing in B4PYMPM is beneficial to efficient, field-independent charge separation, leading to fill factors above 70% in photovoltaic devices. This is rationalized by a comprehensive computational protocol showing that, compared to the more amorphous and isotropically oriented B2PYMPM, the higher structural order of B4PYMPM molecules leads to more delocalized CT states. Furthermore, we find no correlation between the quantum efficiency of FCC radiative recombination and the bound or unbound nature of the CT states. This work highlights the importance of structural ordering at donor-acceptor interfaces for efficient FCC generation and shows that less bound CT states do not preclude efficient radiative recombination.

The development of luminescent organic radicals has resulted in materials with excellent optical properties for near-infrared emission. Applications of light generation in this range span from bioimaging to surveillance. Although the unpaired electron arrangements of radicals enable efficient radiative transitions within the doublet-spin manifold in organic light-emitting diodes, their performance is limited by non-radiative pathways introduced in electroluminescence. Here we present a host-guest design for organic light-emitting diodes that exploits energy transfer with up to 9.6% external quantum efficiency for 800 nm emission. The tris(2,4,6-trichlorophenyl)methyl-triphenyl-amine radical guest is energy-matched to the triplet state in a charge-transporting anthracene-derivative host. We show from optical spectroscopy and quantum-chemical modelling that reversible host-guest triplet-doublet energy transfer allows efficient harvesting of host triplet excitons., Competing Interests: Competing interestsThe authors declare no competing interests., (© The Author(s) 2024.)

Molecules present a versatile platform for quantum information science 1,2 and are candidates for sensing and computation applications 3,4 . Robust spin-optical interfaces are key to harnessing the quantum resources of materials 5 . To date, carbon-based candidates have been non-luminescent 6,7 , which prevents optical readout via emission. Here we report organic molecules showing both efficient luminescence and near-unity generation yield of excited states with spin multiplicity S > 1. This was achieved by designing an energy resonance between emissive doublet and triplet levels, here on covalently coupled tris(2,4,6-trichlorophenyl) methyl-carbazole radicals and anthracene. We observed that the doublet photoexcitation delocalized onto the linked acene within a few picoseconds and subsequently evolved to a pure high-spin state (quartet for monoradical, quintet for biradical) of mixed radical-triplet character near 1.8 eV. These high-spin states are coherently addressable with microwaves even at 295 K, with optical readout enabled by reverse intersystem crossing to emissive states. Furthermore, for the biradical, on return to the ground state the previously uncorrelated radical spins either side of the anthracene shows strong spin correlation. Our approach simultaneously supports a high efficiency of initialization, spin manipulations and light-based readout at room temperature. The integration of luminescence and high-spin states creates an organic materials platform for emerging quantum technologies., (© 2023. The Author(s).)

Habitat loss is a potential long-term effect of projected climate change for Mediterranean forest ecosystems. Here, we investigated the effectiveness of a close-to-nature silvicultural practice to conserve an old-growth white oak forest patch in Sicily (Italy) and promote regeneration dynamics. The study area, although small, is distinctive for its isolation, position and environmental characteristics. We conducted a Before-After Control-Impact (BACI) study to analyse the responses of different taxonomic groups (vascular plants and birds) to silvicultural treatments (selection thinning, no thinning), and to determine whether close-to-nature silviculture practices may cause significant shifts in the investigated communities. Specifically, we assessed the responses of (1) vascular plants by means of species diversity and taxonomic distinctness indices and (2) birds in terms of diversity, abundance and forest specialisation. Preliminary results suggest that cautious close-to-nature silviculture practice could-by mimicking natural gap dynamics-contribute to maintaining old-growth forest patches and promote oak seedling emergence without short-term detrimental impacts on biodiversity. Although the monitoring has to be repeated over the long-term, the multi-taxon approach and indices incorporating information on taxonomic relationships into diversity measures were demonstrated to be valuable tools for interpreting biotic community structure and dynamics.

Engineering a low singlet-triplet energy gap (ΔE ST ) is necessary for efficient reverse intersystem crossing (rISC) in delayed fluorescence (DF) organic semiconductors but results in a small radiative rate that limits performance in LEDs. Here, we study a model DF material, BF2, that exhibits a strong optical absorption (absorption coefficient = 3.8 × 10 5  cm -1 ) and a relatively large ΔE ST of 0.2 eV. In isolated BF2 molecules, intramolecular rISC is slow (delayed lifetime = 260 μs), but in aggregated films, BF2 generates intermolecular charge transfer (inter-CT) states on picosecond timescales. In contrast to the microsecond intramolecular rISC that is promoted by spin-orbit interactions in most isolated DF molecules, photoluminescence-detected magnetic resonance shows that these inter-CT states undergo rISC mediated by hyperfine interactions on a ~24 ns timescale and have an average electron-hole separation of ≥1.5 nm. Transfer back to the emissive singlet exciton then enables efficient DF and LED operation. Thus, access to these inter-CT states, which is possible even at low BF2 doping concentrations of 4 wt%, resolves the conflicting requirements of fast radiative emission and low ΔE ST in organic DF emitters., (© 2021. The Author(s).)

Organic solar cells are approaching power conversion efficiencies of other thin-film technologies. However, in order to become truly market competitive, the still substantial voltage losses need to be reduced. Here, the synthesis and characterization of four novel arylamine-based push-pull molecular donors was described, two of them exhibiting a methyl group at the para-position of the external phenyl ring of the arylamine block. Assessing the charge-transfer state properties and the effects of methylation on the open-circuit voltage of the device showed that devices based on methylated versions of the molecular donors exhibited reduced voltage losses due to decreased non-radiative recombination. Modelling suggested that methylation resulted in a tighter interaction between donor and acceptor molecules, turning into a larger oscillator strength to the charge-transfer states, thereby ensuing reduced non-radiative decay rates., (© 2021 The Authors. ChemSusChem published by Wiley-VCH GmbH.)

The use of non-fullerene acceptors (NFAs) in organic solar cells has led to power conversion efficiencies as high as 18% 1 . However, organic solar cells are still less efficient than inorganic solar cells, which typically have power conversion efficiencies of more than 20% 2 . A key reason for this difference is that organic solar cells have low open-circuit voltages relative to their optical bandgaps 3 , owing to non-radiative recombination 4 . For organic solar cells to compete with inorganic solar cells in terms of efficiency, non-radiative loss pathways must be identified and suppressed. Here we show that in most organic solar cells that use NFAs, the majority of charge recombination under open-circuit conditions proceeds via the formation of non-emissive NFA triplet excitons; in the benchmark PM6:Y6 blend 5 , this fraction reaches 90%, reducing the open-circuit voltage by 60 mV. We prevent recombination via this non-radiative channel by engineering substantial hybridization between the NFA triplet excitons and the spin-triplet charge-transfer excitons. Modelling suggests that the rate of back charge transfer from spin-triplet charge-transfer excitons to molecular triplet excitons may be reduced by an order of magnitude, enabling re-dissociation of the spin-triplet charge-transfer exciton. We demonstrate NFA systems in which the formation of triplet excitons is suppressed. This work thus provides a design pathway for organic solar cells with power conversion efficiencies of 20% or more., (© 2021. The Author(s), under exclusive licence to Springer Nature Limited.)

We report on computational studies of the potential of three borane Lewis acids (LAs) (B(C 6 F 5 ) 3 (BCF), BF 3 , and BBr 3 ) to form stable adducts and/or to generate positive polarons with three different semiconducting π-conjugated polymers (PFPT, PCPDTPT and PCPDTBT). Density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations based on range-separated hybrid (RSH) functionals provide insight into changes in the electronic structure and optical properties upon adduct formation between LAs and the two polymers containing pyridine moieties, PFPT and PCPDTPT, unravelling the complex interplay between partial hybridization, charge transfer and changes in the polymer backbone conformation. We then assess the potential of BCF to induce p-doping in PCPDTBT, which does not contain pyridine groups, by computing the energetics of various reaction mechanisms proposed in the literature. We find that reaction of BCF(OH 2 ) to form protonated PCPDTBT and [BCF(OH)] - , followed by electron transfer from a pristine to a protonated PCPDTBT chain is highly endergonic, and thus unlikely at low doping concentration. The theoretical and experimental data can, however, be reconciled if one considers the formation of [BCF(OH)BCF] - or [BCF(OH)(OH 2 )BCF] - counterions rather than [BCF(OH)] - and invokes subsequent reactions resulting in the elimination of H 2 ., Competing Interests: The authors declare no competing financial interest., (This journal is © The Royal Society of Chemistry.)

π-Conjugated push-pull molecules based on triphenylamine and 1,1,4,4-tetracyanobuta-1,3-diene (TCBD) have been functionalized with different terminal arene units. In solution, these highly TCBD-twisted systems showed a strong internal charge transfer band in the visible spectrum and no detectable photoluminescence (PL). Photophysical and theoretical investigations revealed very short singlet excited state deactivation time of ≈10 ps resulting from significant conformational changes of the TCBD-arene moiety upon photoexcitation, opening a pathway for non-radiative decay. The PL was recovered in vacuum-processed films or when the molecules were dispersed in a PMMA matrix leading to a significant increase of the excited state deactivation time. As shown by cyclic voltammetry, these molecules can act as electron donors compared to C 60 . Hence, vacuum-processed planar heterojunction organic solar cells were fabricated leading to a maximum power conversion efficiency of ca. 1.9 % which decreases with the increase of the arene size., (© 2020 Wiley-VCH GmbH.)

In an effort to gain a comprehensive picture of the interfacial states in bulk heterojunction solar cells, we provide a combined experimental-theoretical analysis of the energetics and dynamics of low-lying electronic charge-transfer (CT) states in donor:acceptor blends with a large frontier orbital energy offset. By varying the blend composition and temperature, we unravel the static and dynamic contributions to the disordered density of states (DOS) of the CT-state manifold and assess their recombination to the ground state. Namely, we find that static disorder (conformational and electrostatic) shapes the CT DOS and that fast nonradiative recombination crops the low-energy tail of the distribution probed by external quantum efficiency (EQE) measurements (thereby largely contributing to voltage losses). Our results then question the standard practice of extracting microscopic parameters such as exciton energy and energetic disorder from EQE.

Organic solar cells usually utilise a heterojunction between electron-donating (D) and electron-accepting (A) materials to split excitons into charges. However, the use of D-A blends intrinsically limits the photovoltage and introduces morphological instability. Here, we demonstrate that polycrystalline films of chemically identical molecules offer a promising alternative and show that photoexcitation of α-sexithiophene (α-6T) films results in efficient charge generation. This leads to α-6T based homojunction organic solar cells with an external quantum efficiency reaching up to 44% and an open-circuit voltage of 1.61 V. Morphological, photoemission, and modelling studies show that boundaries between α-6T crystalline domains with different orientations generate an electrostatic landscape with an interfacial energy offset of 0.4 eV, which promotes the formation of hybridised exciton/charge-transfer states at the interface, dissociating efficiently into free charges. Our findings open new avenues for organic solar cell design where material energetics are tuned through molecular electrostatic engineering and mesoscale structural control.

We compare two small π-conjugated donor-bridge-acceptor organic molecules differing mainly in the number of thiophene rings in their bridging motifs (1 ring in 1; 2 rings in 2) with the aim of rationalizing the origin of the enhancement in the singlet exciton diffusion coefficient and length of 1 with respect to 2. By combining force field molecular dynamics and micro electrostatic schemes with time-dependent density functional theory and kinetic Monte Carlo simulations, we dissect the nature of the lowest electronic excitations in amorphous thin films of these molecules and model the transport of singlet excitons across their broadly disordered energy landscapes. In addition to a longer excited-state lifetime associated with a more pronounced intramolecular charge-transfer character, our calculations reveal that singlet excitons in 1 are capable of funneling through long-distance hopping percolation pathways, presumably as a result of the less anisotropic shape of the molecule, which favours long-range 3D transport.

Thin films of an iron(ii) complex with a photochromic diarylethene-based ligand and featuring a spin-crossover behaviour have been grown by sublimation in ultra-high vacuum on highly oriented pyrolytic graphite and spectroscopically characterized through high-resolution X-ray and ultraviolet photoemission, as well as via X-ray absorption. Temperature-dependent studies demonstrated that the thermally induced spin-crossover is preserved at a sub-monolayer (0.7 ML) coverage. Although the photochromic ligand ad hoc integrated into the complex allows the photo-switching of the spin state of the complex at room temperature both in bulk and for a thick film on highly oriented pyrolytic graphite, this photomagnetic effect is not observed in sub-monolayer deposits. Ab initio calculations justify this behaviour as the result of specific adsorbate-substrate interactions leading to the stabilization of the photoinactive form of the diarylethene ligand over photoactive one on the surface.