Azide telechelics chain extended by click reaction: Synthesis,characterization, and cross‐linking

Azide telechelics of poly(dimethylsiloxane) (PDMS), polypropylene oxide (PPO), and polyethylene oxide (PEO) were synthesized from the corresponding epoxy telechelics and characterized. These oligomeric azides were chain extended by reaction with bispropargyl ether of bisphenol A (BPEBA) through a copper‐catalyzed azide‐alkyne cycloaddition (CuAAC) reaction. PDMS manifested a faster reaction in contrast to PPO or PEO. The chain‐extended polymers underwent cross‐linking above 170°C through thermal cleavage of residual (terminal) azide groups. This was manifested in their rheograms and was further substantiated by FTIR and NMR spectroscopic analyses. Dynamic mechanical analyses of the cross‐linked polymers exhibited characteristic transitions of hard and soft segments, implying microphase separation in the system. Microscopic evaluation of the thermally cross‐linked sample revealed a porous morphology with microsized to nanosized pores.     

Molecular Design Strategy for Orange Red Thermally Activated Delayed Fluorescence Emitters in Organic Light-Emitting Diodes (OLEDs)

Pure organic molecules based thermally activated delayed fluorescence (TADF) emitters have been successfully developed in recent years for their propitious application in highly efficient organic light emitting diodes (OLEDs). In the case of orange red emitters, the non-radiative process is known to be a serious issue due to its lower lying singlet energy level. However, recent studies indicate that there are tremendous efforts put to develop efficient orange red TADF emitters. In addition, the external quantum efficiency (EQE) of heteroaromatic based orange red TADF OLEDs surpassed 30 %. Such heteroaromatic type emitters showed wide emission spectra; therefore, more attention is being paid to develop highly efficient orange red TADF emitters along with good color purity. Herein, the recent progress of orange red TADF emitters based on molecular structures, such as cyanobenzene, heteroaromatic, naphthalimide, and boron-based acceptors, are reviewed. Further, our insight on these acceptors has been provided by their photophysical studies and device performances. Future perspectives of orange red TADF emitters for real practical applications are discussed.     

An unusual [4 + 4] cycloadduct from an o-quinodimethane: Characterisation and computational studies

Trapping of a pyrimidinone-derived o-quinodimethane with tetraphenylcyclopentadienone gives a mixture of the [4 + 2] and formal [4 + 4] adducts. Computational studies show that the latter arises by a sequence of [4 + 2] cycloaddition, homolysis, radical recombination to a spiro-tetrahydrofuran and Claisen rearrangement under the thermolytic conditions.     

Performance of cryogenic probes as a function of ionic strength and sample tube geometry

The pursuit for more sensitive NMR probes culminated with development of the cryogenic cooled NMR probe. A key factor for the sensitivity is the overall resistance of RF circuitry and sample. Lowering the coil temperature to approximately 25 K and the use of superconducting coil material has greatly reduced the resistance contribution of the hardware. However, the resistance of a salty sample remains the same and evolves as the major factor determining the signal-to-noise ratio. Several approaches have been proposed to reduce the resistance contribution of the sample. These range from encapsulating proteins in a water cavity formed by reverse micelles in low viscosity fluids to the optimal selection of low mobility, low conductivity buffer ions. Here we demonstrate that changing the sample diameter has a pronounced effect on the sample resistance and this results in dramatic improvements of the signal-to-noise ratio and shorter pi/2 pulses. We determined these parameters for common 5 mm NMR tubes under different experimental conditions and compared them to the 2, 3 and 4 mm tubes, in addition, 5mm Shigemi tubes were included since these are widely used. We demonstrate benefits and applicability of studying NMR samples with up to 4M salt concentrations in cryogenic probes. Under high salt conditions, best results in terms of short pi/2 pulses and high signal-to-noise ratios are obtained using 2 or 3mm NMR tubes, especially when limited sample is available. The 4 mm tube is preferred when sample amounts are abundant at intermediate salt conditions.     

Charge transfer excited-state dynamics in DNA duplexes substituted with an ethynylpyrenyldeoxyuridine electron source and a fluorodeoxyuridine electron trap

Studies of six 5-(pyren-1-yl-ethynyl)-2'-deoxyuridine (U(PY))-substituted DNA duplexes in this work test and support the conclusions reported by Gaballah et al. (J. Phys. Chem. B 2005, 109, 5927-5934) based on investigations of 5-(2-pyren-1-yl-ethylenyl)-2'-deoxyuridine (U(PE))-substituted DNA hairpins. As expected because of the rigid ethynyl linker in U(PY) (compared to the flexible ethylenyl linker in U(PE)), U(PY)-substituted duplexes do not show enhanced charge transfer (CT) emission quantum yields for duplexes with 5-fluorodeoxyuridine (U(F)) electron traps near U(PY) compared to duplexes without traps. Furthermore, the average CT lifetime and emission quantum yield of U(PY)-substituted duplexes is independent of the U(F) trap location. These new results strongly suggest that the excess electron in the PY*+/dU*- CT state of U(PY) is restrained from hopping to nearby U(F) traps due to attraction to PY*+.     

The absorption and excitation spectroscopy of matrix-isolated atomic manganese: sites of isolation in the solid rare gases

This study collects information from absorption and luminescence excitation spectra recorded for Mn atoms isolated in the solid rare gases Ar, Kr, and Xe and presents an analysis of the site occupancy, based on the polarizabilities of the rare gases and the observed spectral shifts. Two thermally stable sites of isolation exist for atomic Mn in solid Ar and Kr, while a single thermally stable site is present in Mn/Xe. Site occupancy assignments are based on the application of a polarizability model to the z (6)P(5/2)<--a (6)S(5/2); z (8)P(5/2)<--a (6)S(5/2), and y (6)P(5/2)<--a (6)S(5/2) electronic transitions of atomic Mn. From an analysis of the observed RG matrix-to-gas phase energy shifts for P<--S type transitions, this model allows the association of certain site types occupied by metal atoms in the rare gas solids. The required condition being a linear dependence of the matrix shifts with rare gas polarizability for those metal atoms "trapped" in a particular site type. Application of the polarizability model in conjunction with trends observed in site dominance, established a connection between the blue sites in Ar and Kr and the single site in Xe. Use of the known MgRG ground state bond lengths facilitated an identification of the sites of Mn atom isolation assuming the transference of the known MgRG bond lengths to the MnRG systems. Substitutional site occupancy of atomic Mn is assigned to the blue sites in Ar and Kr and the single site in Xe, while tetra-vacancy site occupancy is assigned to the red sites in Ar and Kr. Consistent with these assignments, Mn atoms in solid Ar show a preference for trapping in tetra-vacancy sites whereas in solid Kr, single substitutional sites are preferred and in Xe, this is the only site observed.