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1. Targeting Oxide Concentration in Tantalum Oxide-Fluoride Anions

   https://doi.org/10.1016/j.solidstatesciences.2023.107369  

   Kamp, Kendall R; Wang, Yiran; Poeppelmeier, Kenneth R (December 2023, Solid State Sciences)

   The design of both molecular and non-molecular solid materials with specific properties fundamentally relies on the controlled synthesis of crystals with desired functional groups, bonding motifs, polarity, chirality, and more. To this end, fluoride and oxide-fluoride anions have been utilized as basic building units (BBUs) in the synthesis of noncentrosymmetric racemic materials for their ability to create polar axes that facilitate the breaking of an inversion center as demonstrated in a series of compounds with [MF6]2- anions (M = Ti, Zr, Hf). Targeting an analog with a [TaOF5]2- anion, the phase space of (CuO, Ta2O5)/bpy/HF(aq)/H2O (bpy = 2,2′- bipyridine) was investigated and three new compounds with Cu-bpy cations and Ta-fluoride or Ta-oxyfluoride anions were synthesized: [Cu(bpy)2][TaF6], [Cu (bpy)2][Ta2OF10], and [Cu(bpy)F(H2O)2]2[TaF7]•H2O with the anions [TaF6]-, [Ta2OF10]2-, and [TaF7]2-, respectively. The formation of these anions was found to be a product of both the concentration of hydrofluoric acid in solution and the ratio of metal-oxide starting materials to ligand. This work contributes to the understanding of mixed anion formation in the solid state. 

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2. Multi-stimuli responsive luminescent azepane-substituted β-diketones and difluoroboron complexes

   https://doi.org/10.1039/c7qm00137a  

   Wang, Fang; DeRosa, Christopher A.; Daly, Margaret L.; Song, Daniel; Sabat, Michal; Fraser, Cassandra L. (January 2017, Materials Chemistry Frontiers)

   Difluoroboron β-diketonate (BF 2 bdk) compounds show environment-sensitive optical properties in solution, aggregation-induced emission (AIE) and multi-stimuli responsive fluorescence switching in the solid state. Here, a series of 4-azepane-substituted β-diketone (bdk) ligands ( L-H , L-OMe , L-Br ) and their corresponding difluoroboron dyes ( D-H , D-OMe , D-Br ) were synthesized, and various responsive fluorescence properties of the compounds were studied, including solvatochromism, viscochromism, AIE, mechanochromic luminescence (ML) and halochromism. Compared to the β-diketones, the boron complexes exhibited higher extinction coefficients but lower quantum yields, and red-shifted absorption and emission in CH 2 Cl 2 . Computational studies showed that intramolecular charge transfer (ICT) dominated rather than π–π* transitions in all the compounds regardless of boron coordination. In solution, all the bdk ligands and boron dyes showed red-shifted emission in more polar solvents and increased fluorescence intensity in more viscous media. Upon aggregation, the emission of the β-diketones was quenched, however, the boronated dyes showed increased emission, indicative of AIE. Solid-state emission properties, ML and halochromism, were investigated on spin cast films. For ML, smearing caused a bathochromic emission shift for L-Br , and powder X-ray diffraction (XRD) patterns showed that the “as spun” and thermally annealed states were more crystalline and the smeared state was amorphous. No obvious ML emission shift was observed for L-H or L-OMe , and the boronated dyes were not mechano-active. Trifluoroacetic acid (TFA) and triethylamine (TEA) vapors were used to study halochromism. Large hypsochromic emission shifts were observed for all the compounds after exposure to TFA vapor, and reversible fluorescence switching was achieved using the acid/base pair. 

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3. Pyrene-Benzimidazole Derivatives as Novel Blue Emitters for OLEDs

   https://doi.org/10.3390/molecules26216523  

   De Silva, Thenahandi Prasanthi; Youm, Sang Gil; Fronczek, Frank R.; Sahasrabudhe, Girija; Nesterov, Evgueni E.; Warner, Isiah M. (November 2021, Molecules)

   Three novel small organic heterocyclic compounds: 2-(1,2-diphenyl)-1H-benzimidazole-7-tert-butylpyrene (compound A), 1,3-di(1,2-diphenyl)-1H-benzimidazole-7-tert-butylpyrene (compound B), and 1,3,6,8-tetra(1,2-diphenyl)-1H-benzimidazolepyrene (compound C) were synthesized and characterized for possible applications as blue OLED emitters. The specific molecular design targeted decreasing intermolecular aggregation and disrupting crystallinity in the solid-state, in order to reduce dye aggregation, and thus obtain efficient pure blue photo- and electroluminescence. Accordingly, the new compounds displayed reasonably high spectral purity in both solution- and solid-states with average CIE coordinates of (0.160 ± 0.005, 0.029 ± 0.009) in solution and (0.152 ± 0.007, 0.126 ± 0.005) in solid-state. These compounds showed a systematic decrease in degree of crystallinity and intermolecular aggregation due to increasing steric hindrance, as revealed using powder X-ray diffraction analysis and spectroscopic studies. An organic light-emitting diode (OLED) prototype fabricated using compound B as the non-doped emissive layer displayed an external quantum efficiency (EQE) of 0.35 (±0.04)% and luminance 100 (±6) cd m−2 at 5.5 V with an essentially pure blue electroluminescence corresponding to CIE coordinates of (0.1482, 0.1300). The highest EQE observed from this OLED prototype was 4.3 (±0.3)% at 3.5 V, and the highest luminance of 290 (±10) cd m−2 at 7.5 V. These values were found comparable to characteristics of the best pure blue OLED devices based on simple fluorescent small-molecule organic chromophores. 

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4. How Radical Are "Radical" Photocatalysts? A Closed-Shell Meisenheimer Complex Is Identified as a Super-Reducing Photoreagent

   https://doi.org/10.1021/jacs.1c06844  

   Rieth, Adam J.; Gonzalez, Miguel; Kudisch, Bryan; Nava, Matthew; Nocera, Daniel G. (September 2021, Journal of the American Chemical Society)

   Super-reducing excited states have the potential to activate strong bonds, leading to unprecedented photoreactivity. Excited states of radical anions, accessed via reduction of a precatalyst followed by light absorption, have been proposed to drive photoredox transformations under super-reducing conditions. Here, we investigate the radical anion of naphthalene monoimide as a photoreductant and find that the radical doublet excited state has a lifetime of 24 ps, which is too short to facilitate photoredox activity. To account for the apparent photoreactivity of the radical anion, we identify an emissive two-electron reduced Meisenheimer complex of naphthalene monoimide, [NMI(H)](-). The singlet excited state of [NMI(H)](-) is a potent reductant (-3.08 V vs Fc/Fc(+)), is long-lived (20 ns), and its emission can be dynamically quenched by chloroarenes to drive a radical photochemistry, establishing that it is this emissive excited state that is competent for reported C-C and C-P coupling reactivity. These results provide a mechanistic basis for photoreactivity at highly reducing potentials via singlet excited state manifolds and lays out a clear path for the development of exceptionally reducing photoreagents derived from electron-rich closed-shell anions. 

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5. Shortwave infrared luminescent Pt-nanowires: a mechanistic study of emission in solution and in the solid state

   https://doi.org/10.1039/c7dt02317k  

   Cheadle, Carl; Ratcliff, Jessica; Berezin, Mikhail; Pal'shin, Vadim; Nemykin, Victor N.; Gerasimchuk, Nikolay N. (January 2017, Dalton Trans.)

   Several complexes of “PtL 2 ” composition containing two cyanoxime anions – 2-oximino-2-cyano- N -piperidineacetamide (PiPCO − ) and 2-oximino-2-cyano- N -morpholylacetamide (MCO − ) – have been obtained and characterized both in solution and in the solid state. Complexes exist as two distinct polymorphs: monomeric yellow complexes and dark-green [PtL 2 ] n 1D polymers, while for the MCO − anion a red, solvent containing dimeric [Pt(MCO) 2 ·DMSO] 2 complex has also been isolated. The interconversion of polymorphs was investigated. The monomeric PtL 2 units are arranged into anisotropic extended solid [PtL 2 ] n polymers with the help of Pt⋯Pt metallophilic interactions. Crystal structures of monomeric PtL 2 (L = PiPCO − , MCO − ) and red dimeric [Pt(MCO) 2 ·DMSO] 2 complexes were determined and revealed the cis -arrangement of cyanoxime anions. The Pt–Pt distance in the “head-to-tail” red dimer was found to be 3.133 Å. The structure of the polymeric [Pt(PiPCO) 2 ] n compound was elucidated using the EXAFS method and evidenced the formation of Pt-wires with ∼3.15 Å intermetallic separation. The EPR spectra of both 1D polymers at variable temperatures indicate the absence of Pt( iii ) species. Both pure dark-green [PtL 2 ] n polymers showed a considerable room temperature electrical conductivity of 20–30 S cm −1 , which evidences the formation of a mixed valence Pt( ii )/Pt( iv ) system. We discovered that these 1D polymeric [PtL 2 ] n complexes show an intense NIR fluorescence beyond 1000 nm, while yellow monomeric PtL 2 complexes are not emissive at all. The room temperature excitation spectra of 1D polymeric [PtL 2 ] n complexes demonstrated their strong emission beyond 1000 nm regardless of the used excitation wavelength between 350 and 800 nm, which is typical of systems with delocalized charge carriers. For the first time the formation of mixed valence “metal wires” held together by metallophilic interactions is directly linked both with an intense fluorescence in the NIR region of the spectrum and with the electrical conductivity. The effect of the concentration of [PtL 2 ] n complexes dispersed in the dielectric salt matrix on the photoluminescence wavelength and intensity was investigated. Both polymers show a quantum yield that is remarkably high for this region of the spectrum, reaching ∼2%. Variable temperature emission of polymeric [PtL 2 ] n in the −190–+60 °C range was studied as well. 

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