The syntheses and the electrochemical spectroscopic properties of a suite of asymmetrical bistridentate cyclometalated Ru(II) complexes bearing terminal triphenylamine (TPA) substituents are reported. These complexes, which contain structural design elements common to both inorganic and organic dyes that exhibit superior power conversion efficiencies in the dye-sensitized solar cell (DSSC), are broadly formulated as [Ru(II)(L-2,5'-thiophene-TPA-R(1))(L-R(2))](+) [L = tridentate chelating ligand (e.g., 2,2':6',2''-terpyridine (tpy); deprotonated forms of 1,3-di(pyridin-2-yl)benzene (Hdpb) or 6-phenyl-2,2'-bipyridine (Hpbpy)); R(1) = -H, -Me, -OMe; R(2) = -H, -CO(2)Me, -CO(2)H]. The following structural attributes were systematically modified for the series: (i) electron-donating character of the terminal substituents (e.g., R(1) = -H, -Me, -OMe) placed para to the amine of the "L-2,5'-thiophene-TPA-R(1)" ligand framework; (ii) electron-withdrawing character of the tridentate chelate distal to the TPA-substituted ligand (e.g., R(2) = -H, -CO(2)Me, -CO(2)H); and (iii) position of the organometallic bond about the Ru(II) center. UV-vis spectra reveal intense and broad absorption bands arising from a collection of metal-to-ligand charge-transfer (MLCT) and TPA-based intraligand charge-transfer (ILCT) transitions that, in certain cases, extend beyond 800 nm. Electrochemical data indicate that the oxidative behavior of the TPA and metal chelate units can be independently modulated except in cases where the anionic phenyl ring is in direct conjugation with the TPA unit. In most cases, the anionic character of the cyclometalating ligands renders a metal-based oxidation event prior to the oxidation of the TPA unit. This situation can, however, be reversed with an appropriately positioned Ru-C bond and electron-rich R(1) group. This finding is important in that this arrangement confines the highest occupied molecular orbital (HOMO) to the TPA unit rather than the metal, which is optimal for sensitizing TiO(2); indeed, a remarkably high power conversion efficiency (η) in the DSSC (i.e., 8.02%) is measured for the TPA-substituted pbpy(-) chelate where R(1) = -OMe. These results provide a comprehensive strategy for improving the performance of bistridentate Ru sensitizers devoid of NCS(-) groups for the DSSC.

Light-driven decomposition of Ir(acac)3 spin-cast on a conducting glass substrate produces a thin conformal film of amorphous iridium oxide, a-IrO x . The decomposition process, which was carried out under an ambient atmosphere at room temperature and tracked by Fourier transform infrared (FTIR) spectroscopy, appears to proceed by way of a ligand-to-metal charge transfer (LMCT) process. The amorphous nature of the films is based on the lack of any observable Bragg reflections by powder X-ray diffraction techniques; the elemental composition was corroborated by X-ray photoelectron spectroscopy (XPS) measurements. The films are found to be excellent electrocatalysts for mediating the oxygen evolution reaction (OER) in acidic media, as evidenced by the onset of catalysis at 130 mV and a Tafel slope of 34 mV dec–1. These parameters enable current densities of 1 and 10 mA cm–2 to be reached at 190 and 220 mV, respectively. Exposing the films to higher temperatures (500 °C) renders a film of crystalline iridium oxide, c-IrO x , which displays a Tafel slope of 60 mV dec–1, thus requiring an additional 50 mV to reach a current density of 1 mA cm–2. The film of a-IrO x reported here is among the best OER electrocatalysts reported to date.

Key Points Question Are mental health disorders associated with health care utilization and costs among people with chronic diseases? Findings In this population-based cohort study of 991 445 Canadian adults, including 156 296 with a mental health disorder, 3-year adjusted mean costs were $38 250 for those with a mental health disorder and $22 280 for those without a mental health disorder. Presence of a mental health disorder was associated with higher rates of hospitalization and emergency department visits, including when considering only visits associated with chronic disease and ambulatory care–sensitive conditions. Meaning In this study, mental health disorders were associated with substantially higher resource utilization and health care costs in patients with chronic diseases.

The syntheses and physicochemical properties of nine bis-tridentate ruthenium(II) complexes containing one cyclometalating ligand furnished with terminal triphenylamine (TPA) substituents are reported. The structure of each complex conforms to a molecular scaffold formulated as [Ru(II)(TPA-2,5-thiophene-pbpy)(Me(3)tctpy)] (pbpy = 6-phenyl-2,2'-bipyridine; Me(3)tctpy = trimethyl-4,4',4''-tricarboxylate-2,2':6',2''-terpyridine), where various electron-donating groups (EDGs) and electron-withdrawing groups (EWGs) are installed about the TPA unit and the anionic ring of the pbpy ligand. It is found that the redox chemistry of the Ru center and the TPA unit can be independently modulated by (i) placing EWGs (e.g., -CF(3)) or EDGs (e.g., -OMe) on the anionic ring of the pbpy ligand (substituted sites denoted as R(2) or R(3)) and/or (ii) installing electron-donating substituents (e.g., -H, -Me, -OMe) para to the amine of the TPA group (i.e., R(1)). The first oxidation potential is localized to the TPA unit when, for example, EDGs are placed at R(1) with EWGs at R(2) (e.g., the TPA(•+)/TPA(0) and Ru(III)/Ru(II) redox couples appear at +0.98 and +1.27 V vs NHE, respectively, when R(1) = -OMe and R(2) = -CF(3)). This situation is reversed when R(3) = EDG and R(1) = -H: TPA-based and metal-centered oxidation waves occur at +1.20 and +1.11 V vs NHE, respectively. The UV-vis spectrum for each complex is broad (e.g., absorption bands are extended from the UV region to beyond 800 nm in all cases) and intense (e.g., ε ∼ 10(4) M(-1)·cm(-1)) because of the overlapping intraligand charge-transfer and metal-to-ligand charge-transfer transitions. The information derived from this study offers guiding principles for modulating the physicochemical properties of bichromic cyclometalated ruthenium(II) complexes.

BackgroundAnti-glomerular basement membrane (anti-GBM) disease is characterized by circulating IgG glomerular basement membrane antibodies and is clinically expressed as a rapidly progressive crescentic glomerulonephritis (GN), with 30–60% of patients also developing pulmonary hemorrhage. Classically, the renal biopsy shows glomerular crescent formation, bright linear staining of glomerular basement membranes (GBM) for IgG on direct immunofluorescence (IF), and the serologic presence of circulating anti-GBM antibodies. Recently, patients with linear IgG IF staining, undetectable circulating anti-GBM antibodies and glomerular changes atypical for anti-GBM disease have been described as “atypical anti-GBM disease”, with a distinctly more benign clinical course than typical anti-GBM disease. We present a case report of a patient with negative anti-GBM serology but positive linear IgG staining by IF, severe diffuse crescentic and endocapillary proliferative glomerulonephritis, and renal failure, complicated by severe pulmonary hemorrhage after immunosuppression, likely due to cytomegalovirus (CMV) pneumonitis.Case presentationA 24-year-old man was admitted to hospital with hemoptysis and renal failure. Investigations for anti-GBM serology by addressable laser bead immunoassay (ALBIA) was negative for anti-GBM antibodies. Renal biopsy showed diffuse endocapillary proliferative glomerulonephritis with membranoproliferative features and diffuse circumferential crescents. Direct IF showed strong linear staining for IgG along GBMs. The patient’s hemoptysis improved with immunosuppression, but 1 month later he was readmitted with gross hemoptysis, which was refractory to further cyclophosphamide, plasma exchange and rituximab. Bronchoalveolar lavage (BAL) and blood work confirmed CMV pneumonitis, and the patient’s hemoptysis resolved with ganciclovir, though he became dialysis dependent.ConclusionsThis case demonstrates an atypical presentation of anti-GBM disease with both crescents and endocapillary hypercellularity and negative serology. The patient is dialysis dependent, unlike most previously described patients with atypical anti-GBM disease. The course was complicated by CMV pneumonitis, which contributed to the severity of the pulmonary manifestations and added diagnostic difficulty.