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Objective and Approach Pupils ‘Educated in Other Than At School’ (EOTAS) are some of the most vulnerable learners, who, for reasons such as mental health or behavioural difficulties, do not attend a mainstream school. We linked population data from Education Wales (EDUW) between 2010-19 to primary and secondary healthcare records. Individuals included in the EOTAS dataset aged from 7 to 18 years were identified as cases. Controls were pseudo-randomly selected based on equivalent age distribution. We used regression approach to compare characteristics of EOTAS pupils with controls and evaluate their risks of self-harm and mental health conditions before and after being in EOTAS provision. Results Being male, high deprivation levels, and previous records childhood maltreatment, self-harm, and mental health conditions resulted in higher odds of being in EOTAS provision. Female in EOTAS provision entered at a later age, and with higher proportion of co-morbidities. Pupils in EOTAS provision had increased incidence of self-harm and mental health conditions from one year after entering EOTAS provision up to 24 years of age than controls with similar characteristics. Conclusions An important proportion of pupils in EOTAS provision are from the most deprived areas in Wales, with complex life trajectories, social, emotional, and mental health needs. Implications EOTAS provision is not sufficient to attend the social, emotional, and mental health needs of their pupils. Long-term support and a better integration with social care, primary and specialist mental health services is required.

Background People under the care of mental health services are at increased risk of suicide. Existing studies are small in scale and lack comparisons. Aims To identify opportunities for suicide prevention and underpinning data enhancement in people with recent contact with mental health services. Method This population-based study includes people who died by suicide in the year following a mental health services contact in Wales, 2001–2015 (cases), paired with similar patients who did not die by suicide (controls). We linked the National Confidential Inquiry into Suicide and Safety in Mental Health and the Suicide Information Database – Cymru with primary and secondary healthcare records. We present results of conditional logistic regression. Results We matched 1031 cases with 5155 controls. In the year before their death, 98.3% of cases were in contact with healthcare services, and 28.5% presented with self-harm. Cases had more emergency department contacts (odds ratio 2.4, 95% CI 2.1–2.7) and emergency hospital admissions (odds ratio 1.5, 95% CI 1.4–1.7), but fewer primary care contacts (odds ratio 0.7, 95% CI 0.6–0.9) and out-patient appointments (odds ratio 0.2, 95% CI 0.2–0.3) than controls. Odds ratios were larger in females than males for injury and poisoning (odds ratio: 3.3 (95% CI 2.5–4.5) v. 2.6 (95% CI 2.1–3.1)). Conclusions We may be missing existing opportunities to intervene, particularly in emergency departments and hospital admissions with self-harm presentations and with unattributed self-harm, especially in females. Prevention efforts should focus on strengthening routine care contacts, responding to emergency contacts and better self-harm care. There are benefits to enhancing clinical audit systems with routinely collected data.

Background: Concern that self-harm and mental health conditions are increasing in university students may reflect widening access to higher education, existing population trends and/or stressors associated with this setting. Aims: To compare population-level data on self-harm, neurodevelopmental and mental health conditions between university students and non-students with similar characteristics before and during enrolment. Method: This cohort study linked electronic records from the Higher Education Statistics Agency for 2012–2018 to primary and secondary healthcare records. Students were undergraduates aged 18 to 24 years at university entry. Non-students were pseudo-randomly selected based on an equivalent age distribution. Logistic regressions were used to calculate odds ratios. Poisson regressions were used to calculate incidence rate ratios (IRR). Results: The study included 96 760 students and 151 795 non-students. Being male, self-harm and mental health conditions recorded before university entry, and higher deprivation levels, resulted in lower odds of becoming a student and higher odds of drop-out from university. IRRs for self-harm, depression, anxiety, autism spectrum disorder (ASD), drug use and schizophrenia were lower for students. IRRs for self-harm, depression, attention-deficit hyperactivity disorder, ASD, alcohol use and schizophrenia increased more in students than in non-students over time. Older students experienced greater risk of self-harm and mental health conditions, whereas younger students were more at risk of alcohol use than non-student counterparts. Conclusions: Mental health conditions in students are common and diverse. While at university, students require person-centred stepped care, integrated with local third-sector and healthcare services to address specific conditions. [ABSTRACT FROM AUTHOR]

The overall aim of the present study was to understand how dancers' perception and parents' own perceptions of parents' responsiveness and competence support were associated with dancers' self-perceptions and thriving. In total, 64 dancers and 91 parents for a total of 52 matching dyads participated in the study. Dancers were aged 7-24 years, trained on average 4.17 times/weeks, and were involved in Irish dancing for an average of 9.71 years. Participants completed self-reported questionnaires assessing their perceived responsiveness, competence support, self-perceptions, and thriving. Main analyses consisted of mediations performed with structural equation modeling. Results demonstrate that dancers' perceptions of their parents' responsiveness and competence support are associated with their self-perceptions and thriving. Responsiveness and competence support of their second parent was more strongly associated with thriving than responsiveness and competence support of the main parent. Parents' own perceptions of competence support were positively associated with dancers' thriving.

In recent years, an increasing number of fully organic molecules capable of thermally activated delayed fluorescence (TADF) have been reported, often with very small or even inverted singlet-triplet (INVEST) energy gaps. These molecules typically exhibit complex photophysics due to the close energy levels of multiple singlet and triplet states, which create various transition pathways toward emission. A predictive model for the rates of these transitions is thus essential for assessing the suitability of new materials for light-emitting devices. Quantum Dynamics (QD) calculations are ideal for this purpose, as they include quantum effects, without the limitations of first-order perturbative approaches, also allowing taking into account more than two electronic states at once. However, the huge computational demands of QD methodologies, especially for large molecules, currently limit their use as a standard tool. To address this problem, we here employ a strategy that allows us to include almost the whole set of the vibrational coordinates by selecting the key elements of the Hilbert space that significantly impact dynamics, thereby hugely reducing the computational burden. Application of this protocol to two relatively large INVEST molecules reveals that internal conversion in these systems is very fast, making indirect emissive pathways a possible channel for the population of the S 1 state. More importantly, this study demonstrates that the dynamics can be accurately described even with a significantly reduced vibrational space, thus allowing quantum dynamics calculations that yield accurate transition rates in a few minutes of computational time.

The cage escape yield, i.e., the separation of the geminate radical pair formed immediately after bimolecular excited-state electron transfer, was studied in 11 solvents using six Fe(III), Ru(II), and Ir(III) photosensitizers and tri- p -tolylamine as the electron donor. Among all complexes, the largest cage escape yields (0.67-1) were recorded for the Ir(III) photosensitizer, showing the highest potential as a photocatalyst in photoredox catalysis. These yields dropped to values around 0.65 for both Ru(II) photosensitizers and to values around 0.38 for the Os(II) photosensitizer. Interestingly, for both open-shell Fe(III) complexes, the yields were small (<0.1) in solvents with dielectric constant greater than 20 but were shown to reach values up to 0.58 in solvents with low dielectric constants. The results presented herein on closed-shell photosensitizers suggest that the low rate of triplet-singlet intersystem crossing within the manifold of states of the geminate radical pair implies that charge recombination toward the ground state is a spin-forbidden process, favoring large cage escape yields that are not influenced by dielectric effects. Geminate charge recombination in open-shell metal complexes, such as the two Fe(III) photosensitizers studied herein, is no longer a spin-forbidden process and becomes highly sensitive to solvent effects. Altogether, this study provides general guidelines for factors influencing bimolecular excited-state reactivity using prototypical photosensitizers but also allows one to foresee a great development of Fe(III) photosensitizers with the 2 LMCT excited state in photoredox catalysis, providing that solvents with low dielectric constants are used.

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.)

An air-stable B 3 ,N 3 -containing dibenzobisanthene (8) was prepared in 29% yield by heating a 1,3,5-tri(azasilaanthryl)benzene (5) with BBr 3 (180 °C). Under these conditions, the reaction does not stop after threefold SiMe 2 /BBr exchange but proceeds further via two rearrangement and two intramolecular C-H borylation steps. Some mechanistic details were unveiled by using smaller model systems and applying lower reaction temperatures. According to X-ray crystallography, compound 8 has a helically distorted scaffold. Due to its multiple resonance structure, it shows a narrow-band blue-green emission ( λ em = 493 nm; Φ PL = 84%; FWHM = 0.20 eV; THF); samples measured in PMMA gave prompt and delayed fluorescence lifetimes of 10.7 ns and 136 μs, respectively. The optical properties of 8 and of structurally related species were also investigated by quantum-chemical means: most of these compounds exhibit a small energy gap Δ E ST between the lowest excited singlet (S 1 ) and triplet (T 1 ) states and a non-negligible spin-orbit coupling (SOC) between S 1 and T 1 /T 2 , demonstrating their potential as thermally activated delayed fluorescence (TADF) emitters.

Inverted singlet-triplet gap (INVEST) materials have promising photophysical properties for optoelectronic applications due to an inversion of their lowest singlet (S 1 ) and triplet (T 1 ) excited states. This results in an exothermic reverse intersystem crossing (rISC) process that potentially enhances triplet harvesting, compared to thermally activated delayed fluorescence (TADF) emitters with endothermic rISCs. However, the processes and phenomena that facilitate conversion between excited states for INVEST materials are underexplored. We investigate the complex potential energy surfaces (PESs) of the excited states of three heavily studied azaphenalene INVEST compounds, namely, cyclazine, pentazine, and heptazine using two state-of-the-art computational methodologies, namely, RMS-CASPT2 and SCS-ADC(2) methods. Our findings suggest that ISC and rISC processes take place directly between the S 1 and T 1 electronic states in all three compounds through a minimum-energy crossing point (MECP) with an activation energy barrier between 0.11 to 0.58 eV above the S 1 state for ISC and between 0.06 and 0.36 eV above the T 1 state for rISC. We predict that higher-lying triplet states are not populated, since the crossing point structures to these states are not energetically accessible. Furthermore, the conical intersection (CI) between the ground and S 1 states is high in energy for all compounds (between 0.4 to 2.0 eV) which makes nonradiative decay back to the ground state a relatively slow process. We demonstrate that the spin-orbit coupling (SOC) driving the S 1 -T 1 conversion is enhanced by vibronic coupling with higher-lying singlet and triplet states possessing vibrational modes of proper symmetry. We also rationalize that the experimentally observed anti-Kasha emission of cyclazine is due to the energetically inaccessible CI between the bright S 2 and the dark S 1 states, hindering internal conversion. Finally, we show that SCS-ADC(2) is able to qualitatively reproduce excited state features, but consistently overpredict relative energies of excited state structural minima compared to RMS-CASPT2. The identification of these excited state features elaborates design rules for new INVEST emitters with improved emission quantum yields.

Background : There is little information about characteristics and long-term outcomes of individuals who self-harm during a suicide cluster. Aims : To compare characteristics of individuals who self-harmed during a suicide cluster in South Wales (∼10 deaths between December 2007 and March 2008) with others who self-harmed prior to the cluster and to evaluate 10-year self-harm and mortality outcomes. Method : Using records from the hospital serving the catchment area of the suicide cluster, enhanced by national routinely collected linked data, we created the following two groups: individuals who self-harmed (a) during the suicide cluster and (b) 1 year before. We compared individuals' characteristics and performed logistic regression to compute odds ratios of 10-year self-harm and mortality outcomes. Results : Individuals who self-harmed during the cluster were less likely to be hospitalized or have a mental health history than those who self-harmed prior to the cluster. No significant group differences were found for 10-year self-harm outcomes, but all-cause mortality was higher for males. Limitations : Sample size was small, and data were lacking on psychological and social proximity to individuals who died during the suicide cluster. Conclusion : Our findings highlight the importance of long-term healthcare follow-up of those who self-harm during a suicide cluster, particularly males.

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.)