2-(Thienyl)quinoxaline derivatives and their application in Ir(III) complexes yielding tuneable deep red emitters.

The synthesis and characterisation of eleven different 2-(thienyl)quinoxaline species that incorporate different points of functionality, including at the thiophene or quinoxaline rings, are described. These species display variable fluorescence properties in the visible region (λem = 401-491 nm) depending upon the molecular structures and extent of conjugation. The series of 2-(thienyl)quinoxaline species were then investigated as cyclometalating agents for Ir(III) to yield [Ir(C^N)2(bipy)]PF6 (where C^N = the cyclometalated ligand; bipy = 2,2'-bipyridine). Eight complexes were successfully isolated and fully characterised by an array of spectroscopic and analytical techniques. Two Ir(III) examples were structurally characterised in the solid state using single crystal X-ray diffraction; both structures confirmed the proposed formulations and coordination spheres in each case showing that the thiophene coordinates via a Ir-C bond. The photophysical properties of the complexes revealed that each complex is luminescent under ambient conditions with a range of emission wavelengths observed (665-751 nm) indicating that electronic tuning can be achieved via both the thienyl and quinoxaline moieties.

Predictors and correlates of emotionalism across acquired and progressive neurological conditions: A systematic review.

Emotionalism can develop following a range of neurological disorders; however the aetiology of emotionalism is still unclear. To identify anatomical, neuropsychological and psychological predictors and correlates of emotionalism across neurological disorders: stroke, Parkinson's disease, multiple sclerosis, traumatic brain injury, Alzheimer's disease, vascular dementia and amyotrophic lateral sclerosis. To explore if these predictors and correlates of emotionalism differ across neurological disorders. A comprehensive systematic search was completed of four databases: MEDLINE, CINAHL Complete, PsycINFO and EMBASE. Methodological quality was assessed using the Quality Assessment Tool for Observational Cohort and Cross-Sectional Studies and each study was graded according to the level of evidence using the Scottish Intercollegiate Guidelines Network. Fifty papers (participants N = 1922) were included. 25 studies were rated as "Fair," 21 "Good" and 4 "Poor." The review identified predictors and correlates found in several neurological disorder such as bulbar networks, serotonergic pathways, genetics and female gender. Multiple studies across diseases (stroke, MS, ALS) indicate emotionalism is associated with cognitive impairment, especially frontal deficits. Due to the disproportionate number of studies identified across neurological disorders, it is difficult to draw definitive answers. Further research is required across neurological disorders to explore similarities and differences in anatomical, neuropsychological and psychological predictors and correlates.

Organometallic Platinum(II) Photosensitisers that Demonstrate Ligand-Modulated Triplet-Triplet Annihilation Energy Upconversion Efficiencies.

A series of 2-phenylquinoxaline ligands have been synthesised that introduce either CF3 or OCF3 electron-withdrawing groups at different positions of the phenyl ring. These ligands were investigated as cyclometalating reagents for platinum(II) to give neutral complexes of the form [Pt(C^N)(acac)] (in which C^N=cyclometalating ligand; acac=acetyl acetonate). X-ray crystallographic studies on three examples showed that the complexes adopt an approximate square planar geometry. All examples revealed strong Pt-Pt linear contacts of 3.2041(6), 3.2199(3) and 3.2586(2) Å. The highly coloured complexes display efficient visible absorption at 400-500 nm (ϵ ≈5000 M-1  cm-1 ) and orange red photoluminescent characteristics (λem =603-620 nm; Φem ≤37 %), which were subtly tuned by the ligand. Triplet emitting character was confirmed by microsecond luminescence lifetimes and the photogeneration of singlet oxygen with quantum efficiencies up to 57 %. Each complex was investigated as a photosensitiser for triplet-triplet annihilation energy upconversion using 9,10-diphenylanthracene as the annihilator species: a range of good upconversion efficiencies (ΦUC 5.9-14.1 %) were observed and shown to be strongly influenced by the ligand structure in each case.

Post-stroke emotionalism (PSE): a qualitative longitudinal study exploring individuals' experience with PSE.

PURPOSE: Post-stroke emotionalism (PSE) is a common consequence of stroke characterised by episodes of crying or laughing. There is only one published qualitative study exploring the experience of emotionalism to date. This study aimed to explore individual's experience of PSE and develop a theoretical client-derived framework to shape future psychological interventions. MATERIALS AND METHODS: A primary analysis of the qualitative pseudonymised pre-collected semi-structured interview data of the TEARS study was completed. Participants were recruited from nine acute stroke units in Scotland with participants commencing the study at baseline (two-weeks) and they either continued or dropped out. Interviews were completed at two-weeks, six-months and 12-months post-stroke. RESULTS: Data was analysed from 52 participants at two-weeks, 25 participants at six-months and 23 participants at 12-months. Three major themes were identified: "In the moment," describing characteristics and triggers, "Ways of coping," highlighted a variation of coping strategies including avoidance or acceptance and "Impact," outlining the longer-term effects of PSE such as individuals' beliefs. CONCLUSION: The results indicate specific psychological aspects of PSE which could be viable targets in psychological interventions such as increasing adaptive coping strategies and challenging negatively held beliefs.IMPLICATIONS FOR REHABILITATIONEmotionalism can cause emotional consequences such as distress, embarrassment and fear.Helping individuals to develop insight into triggers for emotionalism could be beneficial to help gain understanding and awareness whereby post-stroke emotionalism (PSE) has the potential to be anticipated and adapted to psychologically.Potential adaptive responses such as acceptance or control and better anticipation of episodes of emotionalism could help to reduce the emotional consequences of PSE.

Polysubstituted Ligand Framework for Color Tuning Phosphorescent Iridium(III) Complexes.

A series of ligands have been synthesized based upon a polysubstituted 2-phenylquinoxaline core structure. These ligands introduce different combinations of fluorine and methyl substituents on both the phenyl and quinoxaline constituent rings. The resultant investigation of these species as cyclometalating agents for Ir(III) gave cationic complexes of the form [Ir(C^N)2(bipy)]PF6 (where C^N = cyclometalating ligand; bipy = 2,2'-bipyridine). X-ray crystallographic studies were conducted on four complexes and each revealed the expected distorted octahedral geometry based upon a cis-C,C and trans-N,N ligand arrangement at Ir(III). Supporting computational studies predict that each of the complexes share the same general descriptions for the frontier orbitals. TD-DFT calculations suggest MLCT contributions to the lowest energy absorption and a likely MLCT/ILCT/LLCT nature to the emitting state. Experimentally, the complexes display tunable luminescence across the yellow-orange-red part of the visible spectrum (λem = 579-655 nm).