Extensive photochemical restructuring of molecule-metal surfaces under room light.

The molecule-metal interface is of paramount importance for many devices and processes, and directly involved in photocatalysis, molecular electronics, nanophotonics, and molecular (bio-)sensing. Here the photostability of this interface is shown to be sensitive even to room light levels for specific molecules and metals. Optical spectroscopy is used to track photoinduced migration of gold atoms when functionalised with different thiolated molecules that form uniform monolayers on Au. Nucleation and growth of characteristic surface metal nanostructures is observed from the light-driven adatoms. By watching the spectral shifts of optical modes from nanoparticles used to precoat these surfaces, we identify processes involved in the photo-migration mechanism and the chemical groups that facilitate it. This photosensitivity of the molecule-metal interface highlights the significance of optically induced surface reconstruction. In some catalytic contexts this can enhance activity, especially utilising atomically dispersed gold. Conversely, in electronic device applications such reconstructions introduce problematic aging effects.

Electrochemical deposition of a semiconducting gold dithiolene complex with NIR absorption.

Here, the synthesis of a new anionic gold dithiolene complex, NBu4·[1-i], and that of its corresponding neutral gold complex 2 is reported. Complex 2 shows strong absorption into the IR, semiconductivity (σRT = 3.06 × 10-7 S cm-1) with an activation energy of 0.25 eV, and weakly temperature dependent paramagnetic susceptibility, indicating strong intermolecular interactions in the solid state. As a consequence of their strong intermolecular interactions, neutral gold dithiolene complexes are often highly insoluble, limiting their utility and processability. Electrochemical deposition is used to deposit conductive films of complex 2, which retain the NIR properties present in the bulk material, indicting that the strong intermolecular interactions are retained in the film.

Probing the structural and electronic response of Magnus green salt compounds [Pt(NH2R)4][PtCl4] (R = H, CH3) to pressure.

Despite possessing the desirable crystal packing and short PtPt stacking distances required for a large piezoresistive response, the conductivity-pressure response of the Magnus green salt [Pt(NH3)4][PtCl4] is extremely sluggish. Through a combination of high-pressure X-ray diffraction and hybrid-DFT solid state calculations this study demonstrates that the poor conductivity-pressure response is due to a low volumetric compression anisotropy, a relatively large ambient pressure band gap and a lack of dispersion in the conduction band. Ligand modification (from NH3 to NH2CH3) does not enhance the piezoresistive response, causing even lower anisotropy of the volumetric compression and an unexpected phase transition at above 2 GPa. This study demonstrates that consideration of frontier band dispersion is a key design criterion, alongside crystal packing and PtPt stacking distances, for piezoresistive materials.

Pressure-induced non-innocence in bis(1,2-dionedioximato)Pt(ii) complexes: an experimental and theoretical study of their insulator-metal transitions.

Bis(1,2-dionedioximato) complexes of Pt(ii) are known for their propensity to form linear chains of metal complexes in the solid state, and under the application of pressure members of the family display interesting optical and conductive properties. Two examples, Pt(bqd)2 and Pt(dmg)2, are known to undergo insulator-to-metal-to-insulator transitions, with the metallic state reached at 0.8-1.4 GPa and 5 GPa, respectively. Previous interpretations of these materials' behaviour focused on the role of the filled dz2 and vacant p orbitals on platinum, with little consideration to the role of the ligand. Here, the pressure-structural behaviour of Pt(bqd)2 is investigated through single crystal X-ray diffraction, the first such study on this material. The difference in conductive behaviour under pressure between Pt(bqd)2 and Pt(dmg)2 is then interpreted through a combination of experimental and computational methods, including conductivity measurements under high pressure and electronic structure calculations. Our computational work reveals the significant contribution from ligand low-lying vacant π-orbitals to the frontier orbitals and bands in these complexes, and provides an explanation for the experimentally observed re-entrant insulator-to-metal-to-insulator transitions, and the differences in behaviour between the two compounds.

Unusual dual-emissive heteroleptic iridium complexes incorporating TADF cyclometalating ligands.

Five new neutral heteroleptic iridium(iii) complexes IrL2(pic) (2-6) based on the archetypical blue emitter FIrpic have been synthesised. The cyclometallating ligands L are derived from 2-(2,6-F2-3-pyridyl)-4-mesitylpyridine (7), 2-(3-cyano-2,6-F2-phenyl)-4-mesitylpyridine (8), 2-(2,6-F2-phenyl)-4-[2,7-(HexO)2-9H-carbazol-9-yl]pyridine (9), 2-(2,6-F2-3-pyridyl)-4-[2,7-(HexO)2-9H-carbazol-9-yl]pyridine (10) and 2-(3-cyano-2,6-F2-phenyl)-4-[2,7-(HexO)2-9H-carbazol-9-yl]pyridine (11) for complexes 2, 3, 4, 5 and 6, respectively. The carbazole-functionalised ligands 9-11 show weak thermally activated delayed fluorescence (TADF) in solution. Complexes 5 and 6 reveal dual emission in polar solvents. A broad charge transfer (CT) band appears and increases in intensity relative to the higher energy emission band as solvent polarity is increased. The dual emission occurs when the energy of the ligand 3CT state is comparable to that of the 3MLCT state of the complex, resulting in fast interconversion between the two. Assignment of the ligand TADF and dual emission properties is supported by hybrid density functional theory (DFT) and time dependent DFT (TD-DFT) calculations. Phosphorescent organic light emitting devices (PhOLEDs) have been fabricated using these complexes as sky-blue emitters, and their performance is compared to devices using FIrpic and the previously reported complex IrL2(pic) 1 (L from the 2-(2,6-F2-phenyl)-4-mesitylpyridine ligand). For identical device structures, the device containing the carbazole complex 4 performs best out of the seven complexes. The dual emission observed in solution for complexes 5 and 6 is not observed in their devices.

Pyridylpyrazole N

A series of blue iridium(iii) complexes (12-15) comprising sulfonyl-functionalised phenylpyridyl cyclometalating ligands and pyridylpyrazole N^N ligands are reported, with an X-ray crystal structure obtained for 12. The complexes are highly emissive with photoluminescence quantum yields of 0.52-0.70 in dichloromethane solutions: two of the complexes (12 and 14) show emissions at λ 457 nm which is considerably blue-shifted compared to the archetypal blue emitter FIrpic (λmax 468 nm). The short excited state lifetimes (1.8-3.3 µs) and spectral profiles are consistent with phosphorescence from a mixture of ligand-centred and MLCT excited states. Density functional (DFT) and time dependent DFT (TD-DFT) calculations are in agreement with the electrochemical properties and the blue phosphorescence of the complexes. The additional mesityl substituent on the pyridylpyrazole ligand of 12 and 13 enhances the solubility of the complexes facilitating thin film formation by solution processing. Phosphorescent organic light-emitting diodes (PhOLEDs) have been fabricated using 12 or 13 in a solution-processed single-emitting layer using either poly(vinylcarbazole) (PVK) or 1,3-bis(N-carbazolyl)benzene (mCP) as host. The most blue-shifted electroluminescence (λ 460 nm, CIEx,y 0.15, 0.21) is obtained for an OLED containing complex 12 and mCP, with a brightness of 5400 cd m-2 at 10 V which is high for PhOLEDs with similar blue CIE coordinates using a solution-processed emitter layer.

Teaching the stoma care routine to a patient with low vision.

Teaching the patient with a newly formed stoma but who also has low vision to manage his/her stoma independently can be a difficult task. This case study shows how a nurse taught a patient with low vision to become independent in relation to his newly formed stoma, with a view to being discharged home successfully. At the time the stoma care nurse used her past experience and common sense in achieving this aim. After the event the stoma care nurse researched the literature and discovered that there are accessories/devices available to assist patients with low vision to manage their stoma and help improve their vision. On reflection, the stoma care nurse felt she did not have sufficient time preoperatively with the patient, which prevented her from being able to change the course of action. She has now improved her knowledge, which will assist her in the future if she has to care for another patient with low vision who has had a newly formed stoma.