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We report the development of light-emitting dendrimers with heteroleptic or homoleptic iridium(III) complexes at the core, with one, two, or three first- or second-generation biphenyl-based dendrons attached to the 2-phenylpyridyl ligand that is involved in the emission of light. The 5-phenyl-1-methyl3-n-propyl-1H-1,2,4-triazole co-ligand was not dendronised and was not involved in the emission process. The dendrimers with two emissive ligands were found to have the highest solution photoluminescence quantum yields (PLQYs) which were greater than 90% independent of the dendrimer generation. The second-generation dendrimers were all found to have higher neat film PLQYs than their first-generation counterparts due to the increased shielding of the emissive core by the dendrons and surface groups. The maximum external quantum efficiencies of devices made from the neat film and a guest:host blend of the second-generation dendrimer with two emissive ligands were found to be the highest (7.5% and 15.8%, respectively), which was attributed to a balance between the interactions required for charge transport and minimising those that lead to non-radiative processes. Thus, we have demonstrated that combining dendrimer generation and number of emissive dendronised ligands is a viable strategy for optimising light-emitting dendrimer OLED performance. [ABSTRACT FROM AUTHOR]

Controlled functionalization of 2D black phosphorus (BP) nanosheets provides unique opportunities to tune their chemical, physical, and electronic properties. Herein, the preparation of single‐atom nickel‐doped BP (Ni–BP) sheets using a simple solution‐based strategy is reported. Using the Ni–BP sheets as a passivation layer on top of a perovskite film leads to standard perovskite solar cells (PSCs) with improved performance. The standard n–i–p PSCs with the Ni–BP interlayer achieve maximum power conversion efficiencies of over 22%, with negligible hysteresis and a modest improvement in stability when subjected to different testing conditions. The perovskite films prepared with Ni–BP sheets‐based passivation are found to have reduced defect densities as well as improved charge‐transfer properties and carrier lifetimes. Density‐functional theory calculations support the experimental results through showing that the atomic Ni‐doping increases the work function of the BP interlayer, enabling better hole extraction, as well as increasing the surface hydrophobicity of the BP layer, hence reducing water sorption into the perovskite film. [ABSTRACT FROM AUTHOR]

Singlet fission (SF) is a potential avenue for augmenting the performance of silicon photovoltaics, but the scarcity of SF materials energy‐matched to silicon represents a barrier to the commercial realization of this technology. In this work, a molecular engineering approach is described to increase the energy of the S1 and T1 energy levels of diketopyrrolopyrrole derivatives such that the energy‐level requirements for exothermic SF and energy‐transfer to silicon are met. Time‐resolved photoluminescence studies show that the silicon‐matched materials are SF active in the solid state, forming a correlated triplet pair 1(TT) – a crucial intermediate in the SF process – as observed through Herzberg‐Teller emission from 1(TT) at both 77 K and room temperature. Transient electron paramagnetic resonance studies show that the correlated triplet pair does not readily separate into the unbound triplets, which is a requirement for energy harvesting by silicon. The fact that the triplet pair do not separate into free triplets is attributed to the intermolecular crystal packing within the thin films. Nevertheless, these results demonstrate a promising route for energy‐tuning silicon‐matched SF materials. [ABSTRACT FROM AUTHOR]

In‐field rapid and reliable identification of nerve agents is critical for the protection of Defence and National Security personnel as well as communities. Fluorescence‐based detectors can be portable and provide rapid detection of chemical threats. However, most current approaches cannot differentiate between dilute vapors of nerve agent classes and are susceptible to false positives due to the presence of common acids. Here a fluorescence‐based method is shown for rapid differentiation between the V‐series and phosphonofluoridate G‐series nerve agents and avoids false positives due to common acids. Differentiation is achieved through harnessing two different mechanisms. Detection of the V‐series is achieved using photoinduced hole transfer whereby the fluorescence of the sensing material is quenched in the presence of the V‐series agent. The G‐series is detected using a turn‐on mechanism in which a silylated excited state intramolecular proton transfer sensing molecule is selectively deprotected by hydrogen fluoride, which is typically found as a contaminant and/or breakdown product in G‐series agents such as sarin. The strategy provided discrimination between classes, as the sensor for the G‐series agent class is insensitive to the V‐series agent, and vice versa, and neither responded to common acids. [ABSTRACT FROM AUTHOR]

Bulk heterojunction organic solar cells have undergone significant improvements in power conversion efficiency and stability over the past decade. However, translation from laboratory-scale devices to commercial panels is complicated by the sensitivity of the efficiency to morphological changes, which requires delicate control of the processing conditions. A homojunction architecture, with only a single chromophoric material in the light absorbing layer, could provide a pathway to overcoming problems associated with controlling complex blend morphologies. However, to achieve that goal the organic semiconductor would need to have a dielectric constant of ≈10 such that free charge carriers are formed directly upon photoexcitation. In this study we explore the effect of fluorination on the low and high frequency dielectric constants of two sets of materials with monomeric (A′–A–D) or dimeric (A′–A–D–D–A–A′) structures, where A′ is an aldehyde, A is a protonated or fluorinated benzothiadiazole, and D is a glycolated 4H-cyclopenta[2,1-b:3,4-b′]dithiophene (CPDT) donor unit. Fluorination was found to have only a small effect on the film absorption properties (small blue shift and decreased coefficient), but led to films with increased density relative to the protonated material (1.44 g cm−3versus 1.32 g cm−3), and dispersive unbalanced electron (≈10−6 cm2 V−1 s−1) and hole transport (≈10−5 cm2 V−1 s−1). Critically, while the low frequency dielectric constant of the fluorinated dimeric material was larger than that of the protonated (8.3 versus 7.3), the optical frequency dielectric constant that is thought to be critical for exciton dissociation was smaller (3.3 versus 3.6). [ABSTRACT FROM AUTHOR]