Molecular Design and Synthetic Approaches for the Realization of Multichannel Radiative Decay Pathways in Gold(III) Complexes and Their Applications in Organic Light-Emitting Devices.

A unique class of tridentate diaryltriazine ligand-containing gold(III) complexes with thermally activated delayed fluorescence (TADF) and/or thermally stimulated delayed phosphorescence (TSDP) properties has been designed and synthesized. With a simple structural modification on the coordination of carbazole moiety in the monodentate ligand, a large spectral shift of ∼160 nm (ca. 4900 cm) spanning from sky blue to red emissions has been demonstrated in solid-state thin films.

Achieving efficient and stable blue thermally activated delayed fluorescence organic light-emitting diodes based on four-coordinate fluoroboron emitters by simple substitution molecular engineering.

Achieving both high efficiency and high stability in blue thermally activated delayed fluorescence organic light-emitting diodes (TADF-OLEDs) is challenging for practical displays and lighting. Here, we have successfully developed a series of sky-blue to pure-blue emitting donor-acceptor (D-A) type TADF materials featuring a four-coordinated boron with 2,2'-(pyridine-2,6-diyl)diphenolate (dppy) ligands, 1-8. Synergistic engineering of substituents on the phenyl bridge as well as the electronic properties and the attached positions of heteroatom N-donors not only enables fine-tuning of the emission colors, but also modulates the nature and energies of their triplet excited states that are important for the reverse intersystem crossing (RISC).

Quinoline, Indole, and Isogranatanine Alkaloids from Malayan .

Nine new alkaloids, eugeniinalines A-H (-) and (+)-eburnamenine -oxide (), comprising one quinoline, six indole, and two isogranatanine alkaloids, were isolated from the stem-bark extract of the Malayan . The structures and absolute configurations of these alkaloids were established based on the analysis of the spectroscopic data, GIAO NMR calculations, DP4+ probability analysis, TDDFT-ECD method, and X-ray diffraction analysis. Eugeniinaline A () represents a new pentacyclic quinoline alkaloid with a 6/6/5/6/7 ring system.

Enhancing operational stability of OLEDs based on subatomic modified thermally activated delayed fluorescence compounds.

The realization of operationally stable blue organic light-emitting diodes is a challenging issue across the field. While device optimization has been a focus to effectively prolong device lifetime, strategies based on molecular engineering of chemical structures, particularly at the subatomic level, remains little. Herein, we explore the effect of targeted deuteration on donor and/or acceptor units of thermally activated delayed fluorescence emitters and investigate the structure-property relationship between intrinsic molecular stability, based on isotopic effect, and device operational stability.

Tetradentate CCNN Ligand-Containing Gold(III) Complexes with Orange to Deep-Red Thermally Activated Delayed Fluorescence (TADF) and Their Application in Organic Light-Emitting Devices.

A new class of thermally activated delayed fluorescence (TADF) tetradentate CCNN ligand-containing gold(III) complexes containing acridinyl moieties has been designed and synthesized. These complexes exhibit orange-red to deep-red emission with photoluminescence quantum yields (PLQYs) of up to 0.76 in solid-state thin films.

Surface or Internal Hydration - Does It Really Matter?

The precise location of an ion or electron, whether it is internally solvated or residing on the surface of a water cluster, remains an intriguing question. Subtle differences in the hydrogen bonding network may lead to a preference for one or the other. Here we discuss spectroscopic probes of the structure of gas-phase hydrated ions in combination with quantum chemistry, as well as H/D exchange as a means of structure elucidation.

Thermally Activated vs. Photochemical Hydrogen Evolution Reactions-A Tale of Three Metals.

Molecular processes behind hydrogen evolution reactions can be quite complex. In macroscopic electrochemical cells, it is extremely difficult to elucidate and understand their mechanism. Gas phase models, consisting of a metal ion and a small number of water molecules, provide unique opportunities to understand the reaction pathways in great detail.

Stimuli-Induced Reversible Transformation between Decanuclear and Pentanuclear Gold(I) Sulfido Complexes.

Decanuclear and pentanuclear gold(I) sulfido complexes of phenanthrene- and dibenzothiophene-based diphosphine ligands were synthesized and characterized. Unprecedented stimuli-induced reversible transformation between decanuclear and pentanuclear gold(I) sulfido complexes was observed, which could be readily monitored by NMR and UV-vis absorption spectroscopy in solution. Remarkably, the decanuclear gold(I) sulfido complex () was found to show a highly reversible transformation process, which is stable for over 10 successive cycles in solution.

Carbazolylgold(iii) complexes with thermally activated delayed fluorescence switched on by ligand manipulation as high efficiency organic light-emitting devices with small efficiency roll-offs.

A series of carbazolyl ligands has been designed and synthesized through the integration of various electron-donating and electron-accepting motifs, including electron-donating 4-(diphenylamino)aryl and electron-accepting cyano and diphenylphosphine oxide moieties, for the development of a new class of gold(iii) complexes, where the energies of their triplet intraligand and ligand-to-ligand charge transfer excited states can be manipulated for the activation of thermally activated delayed fluorescence (TADF). Upon excitation, these complexes show high photoluminescence quantum yields of up to 80% in solid-state thin films, with short excited state lifetimes down to 1 μs. Vacuum-deposited and solution-processed organic light-emitting devices based on these complexes demonstrate promising electroluminescence (EL) performance with maximum external quantum efficiencies of 15.

Synthesis, Electrochemistry, Photophysics, and Photochemistry of a Discrete Tetranuclear Copper(I) Sulfido Cluster.

A tetranuclear copper(I) complex, [Cu{μ-(PhP)NH}(μ-S)](PF) (), was synthesized. It was found to display intense and long-lived phosphorescence in the solid and solution states. The lowest-energy excited state was assigned as ligand-to-metal charge transfer (LMCT) [S → Cu] mixed with some metal-centered (ds/dp) character.

Molecular Alignment of Alkynylplatinum(II) 2,6-Bis(benzimidazol-2-yl)pyridine Double Complex Salts and the Formation of Well-Ordered Nanostructures Directed by Pt···Pt and Donor-Acceptor Interactions.

A new class of alkynylplatinum(II) bzimpy (bzimpy = bis(benzimidazol-2-yl)pyridine) double complex salts (DCSs) containing dialkoxynaphthalene or pyromellitic diimide moieties on the alkynyl ligand has been reported to display distinct morphological properties compared to their precursor alkynylplatinum(II) complexes, with the capability of being aligned by the directional Pt···Pt and/or π-π stacking interactions. The incorporation of donor and acceptor units on the alkynyl ligands has been found to significantly perturb the alignment of the oppositely charged complex ions in the DCSs to stack in a twisted head-to-head manner, attributed to the additional driving forces of electrostatic and donor-acceptor interactions. The modulation of the Pt···Pt distances and the extent of aggregate formation have been demonstrated by altering the charge matching between the platinum(II) bzimpy moieties and the donor or acceptor moieties on the alkynyl ligand.

Photochromic dithienylethene-containing four-coordinate boron(III) compounds with a spirocyclic scaffold.

A new series of four-coordinate boron compounds bearing a photochromic dithienylethene-containing C^C ligand and an ancillary N^C ligand have been successfully designed and synthesised. These compounds exhibit reversible photochromism upon photoexcitation with percentage conversions of 71-96% and readily tuneable photocycloreversion quantum yields by convenient modification of the ancillary ligand to turn on the thermally activated upconversion from the lower-lying unreactive excited state to the higher-lying photoreactive excited state.

Decomposition of nitrous oxide in hydrated cobalt(I) clusters: a theoretical insight into the mechanistic roles of ligand-binding modes.

Hydrated cobalt(i) cluster ions, [Co(H2O)n]+, can decompose the inert nitrous oxide molecule, N2O. Density functional theory suggests that N2O can anchor to Co+ of [Co(N2O)(H2O)n]+ through either O end-on (η1-OL) or N end-on (η1-NL) coordinate mode. The latter is thermodynamically more favorable resulting from a subtle π backdonation from Co+ to N2O.

Getting Ready for the Hydrogen Evolution Reaction: The Infrared Spectrum of Hydrated Aluminum Hydride-Hydroxide HAlOH (H O) , n=9-14.

Hydrated singly charged aluminum ions eliminate molecular hydrogen in a size regime from 11 to 24 water molecules. Here we probe the structure of HAlOH (H O) , n=9-14, by infrared multiple photon spectroscopy in the region of 1400-2250 cm . Based on quantum chemical calculations, we assign the features at 1940 cm and 1850 cm to the Al-H stretch in five- and six-coordinate aluminum(III) complexes, respectively.

Formation of n → π interaction facilitating dissociative electron transfer in isolated tyrosine-containing molecular peptide radical cations.

Long-range electron transfer in proteins can be rationalized as a sequential short-distance electron-hopping processes via amino acid residues having low ionization energy as relay stations. Tyrosine residues can serve as such redox-active intermediates through one-electron oxidation to form a π-radical cation at its phenol side chain. An electron transfer from a vicinal functional group to this π-electron hole completes an elementary step of charge migration.

Evidence for the Prerequisite Formation of Phenoxyl Radicals in Radical-Mediated Peptide Tyrosine Nitration In Vacuo.

The elementary mechanism of radical-mediated peptide tyrosine nitration, which is a hallmark of post-translational modification of proteins under nitrative stress in vivo, has been elucidated in detail by using an integrated approach that combines the gas-phase synthesis of prototypical molecular tyrosine-containing peptide radical cations, ion-molecule reactions, and isotopic labeling experiments with DFT calculations. This reaction first involves the radical recombination of NO towards the prerequisite phenoxyl radical tautomer of a tyrosine residue, followed by proton rearrangements, finally yielding the stable and regioselective 3-nitrotyrosyl residue product. In contrast, nitration with the π-phenolic radical cation tautomer is inefficient.

Infrared Spectroscopy of Size-Selected Hydrated Carbon Dioxide Radical Anions CO (H O) (n=2-61) in the C-O Stretch Region.

Understanding the intrinsic properties of the hydrated carbon dioxide radical anions CO (H O) is relevant for electrochemical carbon dioxide functionalization. CO (H O) (n=2-61) is investigated by using infrared action spectroscopy in the 1150-2220 cm region in an ICR (ion cyclotron resonance) cell cooled to T=80 K. The spectra show an absorption band around 1280 cm , which is assigned to the symmetric C-O stretching vibration ν .

The experience of mindful yoga for older adults with depression.

WHAT IS KNOWN ON THE SUBJECT?: Mindful yoga combines yoga techniques with the mindfulness-based stress reduction approach. Previous studies on mindful yoga have reported improvements in depression for working-age adults, but no studies have been conducted with older people. WHAT THE PAPER ADDS TO EXISTING KNOWLEDGE?: Mindful yoga may be a safe and acceptable intervention to improve the mental and physical health of older adults with depression.

Kinetics of the reaction of CO˙(HO), n = 0, 1, 2, with nitric acid, a key reaction in tropospheric negative ion chemistry.

A significant fraction of nitrate in the troposphere is formed in the reactions of HNO3 with the carbonate radical anion CO3˙- and the mono- and dihydrated species CO3˙-(H2O)1,2. A reaction mechanism was proposed in earlier flow reactor studies, which is investigated here in more detail by quantum chemical calculations and experimental reactivity studies of mass selected ions under ultra-high vacuum conditions. Bare CO3˙- forms NO3-(OH˙) as well as NO3-, with a total rate coefficient of 1.

Self-Assembled Binuclear Cu(II)-Histidine Complex for Absolute Configuration and Enantiomeric Excess Determination of Naproxen by Tandem Mass Spectrometry.

Naproxen is one of the most consumed nonsteroidal anti-inflammatory drugs and marketed as S-naproxen since R-naproxen is hepatotoxic. In this study, chiral recognition of naproxen has been investigated by tandem mass spectrometry (MS/MS). Among all diastereomeric complexes formed between naproxen and the examined chiral selectors, including cyclodextrins (α/β/γ-CD), modified phenylalanines ( N-acetyl-phenylalanine, N-t-butoxycarbonyl-phenylalanine, N-9-fluorenylmethyloxycarbonyl-phenylalanine), amino acids (Trp, Phe, Tyr, His), glucose, tartaric acid, and vancomycin, a novel binuclear metal bound diastereomeric complexes [(M(II))( S/ R-naproxen)(l-His)-3H] (M = Cu, Ni, or Co with Cu being the best) could allow effective identification of the absolute configuration of naproxen and determination of its enantiomeric excess ( ee) through MS/MS analysis.

Hydration Leads to Efficient Reactions of the Carbonate Radical Anion with Hydrogen Chloride in the Gas Phase.

The carbonate radical anion CO is a key intermediate in tropospheric anion chemistry. Despite its radical character, only a small number of reactions have been reported in the literature. Here we investigate the gas-phase reactions of CO and CO(HO) with HCl under ultrahigh vacuum conditions.

Charge transfer reactions between gas-phase hydrated electrons, molecular oxygen and carbon dioxide at temperatures of 80-300 K.

The recombination reactions of gas-phase hydrated electrons (H2O)n˙(-) with CO2 and O2, as well as the charge exchange reaction of CO2˙(-)(H2O)n with O2, were studied by Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry in the temperature range T = 80-300 K. Comparison of the rate constants with collision models shows that CO2 reacts with 50% collision efficiency, while O2 reacts considerably slower. Nanocalorimetry yields internally consistent results for the three reactions.