New Approaches to Stretched Film Sample Alignment and Data Collection for Vibrational Linear Dichroism.

Rapid measurements of vibrational linear dichroism (VLD) infrared spectra are shown to be possible by using stretched polymer films and an extension of existing instrumentation designed for vibrational circular dichroism spectroscopy. Earlier techniques can be extended using additional inexpensive polymer substrates to record good-quality VLD spectra of a significantly wider range of compounds with comparatively short sample-preparation times. The polymer substrates used, polyethylene and polytetrafluoroethylene, are commonly available and inexpensive, and samples are more easily prepared than that for many earlier stretched-film and crystal studies. Data are presented for neutral hydrophobic organic molecules on hydrophobic films including acridine, anthracene, fluorene, and recently synthesized S-(4-((4-cyanophenyl)ethynyl)phenyl)ethanethioate. We extend the approach to polar or ionic species, including 2,2'-bipyridine, 1,10-phenanthroline, and sodium dodecyl sulfate, by oxidizing polyethylene films to change their wetting properties. The combination of new instrumentation and modified sample preparation methods is useful in basic spectroscopy for untangling and assigning complicated infrared spectra. Nevertheless, it is not a panacea as surface-adsorbed molecules are often not monodispersed, and higher analyte concentrations can lead to aggregation and resonance phenomena that have previously been observed for infrared spectra on surfaces. These effects can be assessed by varying the sample concentration. The focus of this paper is experimental, and detailed analysis of most of the spectra lies outside its scope, including some well-studied compounds such as acridine and anthracene that allow comparisons with earlier research.

Tunable Light-Emission Properties of Solution-Processable N-Heterocyclic Carbene Cyclometalated Gold(III) Complexes for Organic Light-Emitting Diodes.

N-Heterocyclic carbene (NHC) cyclometalated gold(III) complexes remain very scarce and therefore their photophysical properties remain currently underexplored. Moreover, gold(III) complexes emitting in the blue region of the electromagnetic spectrum are rare. In this work, a series of four phosphorescent gold(III) complexes was investigated bearing four different NHC monocyclometalated (C^C*)-type ligands and a dianionic (N^N)-type ancillary ligand ((N^N)=5,5'-(propane-2,2-diyl)bis(3-(trifluoromethyl)-1 H-pyrazole) (mepzH2 )). The complexes exhibit strong phosphorescence when doped in poly(methyl methacrylate) (PMMA) at room temperature, which were systematically tuned from sky-blue [λPL =456 nm, CIE coordinates: (0.20, 034)] to green [λPL =516 nm, CIE coordinates: (0.31, 0.54)] by varying the monocyclometalated (C^C*) ligand framework. The complexes revealed high quantum efficiencies (ϕPL ) of up to 43 % and excited-state lifetimes (τ0 ) between 15-266 µs. The radiative rate constant values found for these complexes (kr =103 -104  s-1 ) are the highest found in comparison to previously known best-performing monocyclometalated gold(III) complexes. Density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations of these complexes further lend support to the excited-state nature of these complexes. The calculations showed a significant contribution of the gold(III) metal center in the lowest unoccupied molecular orbitals (LUMOs) of up to 18 %, which was found to be unique for this class of cyclometalated gold(III) complexes. Additionally, organic light-emitting diodes (OLEDs) were fabricated by using a solution process to provide the first insight into the electroluminescent (EL) properties of this new class of gold(III) complexes.