Rational design and syntheses of four iridium complexes (1-4) bearing two substituted quinoxalines and an additional 5-(2-pyridyl) pyrazolate or triazolate as the third coordinating ligand are reported. Single-crystal X-ray diffraction studies of 1 reveal a distorted octahedral geometry, in which two dpqx ligands adopt an eclipse configuration, for which the quinoxaline N atoms and the C atoms of orthometalated phenyl groups are located at the mutual trans- and cis-positions, respectively. The lowest absorption band for all complexes consists of a mixture of heavy-atom Ir(III)-enhanced 3MLCT and 3pipi* transitions, and the phosphorescent peak wavelength can be fine-tuned to cover the spectral range of 622-649 nm with high quantum efficiencies. The cyclic voltammetry was measured, showing a reversible, metal-centered oxidation with potentials at 0.76-1.03 V, as well as two reversible reduction waves with potentials ranging from -1.61 to -2.06 V, attributed to the sequential addition of two electrons to the more electron-accepting heterocyclic portion of two distinctive cyclometalated C/N ligands. Complex 1 was used as the representative example to fabricate the red-emitting PLEDs by blending it into a PVK-PBD polymer mixture. The devices exhibited the characteristic emission profile of 1 with peak maxima located at 640 nm. The maximum external quantum efficiency was 3.15% ph/el with a brightness of 1751 cd/m2 at a current density of 67.4 mA/cm2, and the maximum brightness of 7750 cd/m2 was achieved at the applied voltage of 21 V and with CIE coordinates of (0.64, 0.31).

No abstract

ObjectivesChanges in impedance between 24 hours and one month after cochlear implantation have never been explored due to the inability to switch on within one day. This study examined the effect of early activation (within 24 hours) on the evolution of electrode impedance with the aim of providing information on the tissue-to-electrode interface when electrical stimulation was commenced one day post implantation.MethodsWe performed a retrospective review at a single institution. Patients who received a Nucleus 24RECA implant system (Cochlear, Sydney, Australia) and underwent initial switch-on within 24 hours postoperatively were included. Impedance measurements were obtained intraoperatively and postoperatively at 1 day, 1 week, 4 weeks, and 8 weeks.ResultsA significant drop in impedance was noted 1 day after an initial activation within 24 hours followed by a significant rise in impedance in all channels until 1 week, after which the impedance behaved differently in different segments. Basal and mid-portion electrodes revealed a slight increase while apical electrodes showed a slight decrease in impedance from 1 week to 8 weeks postoperatively. Impedance was relatively stable 4 weeks after surgery.ConclusionsThis is the first study to report the evolution of impedance in all channels between initial mapping 1 day and 1 month after cochlear implantation. The underlying mechanism for the differences in behavior between different segments of the electrode may be associated with the combined effect of dynamics among the interplay of cell cover formation, electrical stimulation, and fibrotic reaction.

A new series of new iridium (III) complexes (1–5) bearing ligands derived from benzoquinoxaline were designed and synthesized. X-ray structural analyses of 1 reveal a distorted octahedral geometry around the Ir atom in which the pyrazolate chelate is located opposite to the cis-oriented carbon donor atoms of benzoquinoxaline, while the benzoquinoxaline ligands adopt an eclipse configuration and their coordinated nitrogen atoms and carbon adopt trans- and cis-orientation, respectively. Complexes 1–5 exhibit moderate NIR phosphorescence with peak maxima located at around 910–930 nm. As supported by the TDDFT approach, the transition mainly involves benzoquinoxaline 3π–π* intraligand charge transfer (ILCT) and metal (Ir) to benzoquinoxaline charge transfer (MLCT) of which the spectroscopy and dynamics of relaxation have been thoroughly investigated. The relatively weak NIR emission can be tentatively rationalized by the low energy gap of which the radiationless deactivation may be governed by nearly temperature-independent, weak-bonding motions in combination with a minor channel incorporating small torsional motions associated with phenyl ring in the benzoquinoxaline sites.Key words: phosphorescence, NIR, iridium, benzoquinoxaline, isoquinoline, bipyridine, pyrazolate, acetylacetonate.