Diboraanthracene-Doped Polymer Systems for Colour-Tuneable Room-Temperature Organic Afterglow.

Organic ultralong room temperature phosphorescence (RTP), or organic afterglow, is a unique phenomenon, gaining widespread attention due to its far-reaching application potential and fundamental interest. Here, two laterally expanded 9,10-dimesityl-dihydro-9,10-diboraanthracene (DBA) derivatives are demonstrated as excellent afterglow materials for red and blue-green light emission, which is traced back to persistent thermally activated delayed fluorescence and RTP. The lateral substitution of polycyclic DBA scaffold, together with weak transversal electron-donating mesityl groups, ensures the optimal molecular properties for (reverse) intersystem crossing and long-lived triplet states in a rigid poly(methyl methacrylate) matrix. The achieved afterglow emission quantum yields of up to 3 % and 15 %, afterglow lifetimes up to 0.8 s and 3.2 s and afterglow durations up to 5 s and 25 s (for red and blue-green emitters, respectively) are attributed to the properties of single molecules.

Developing organoboranes as phase transfer catalysts for nucleophilic fluorination using CsF.

Despite the general high fluorophilicity of boron, organoboranes such as BEt3 and 3,5-(CF3)2C6H3-BPin are shown herein for the first time, to our knowledge, to be effective (solid to solution) phase-transfer catalysts for the fluorination of certain organohalides with CsF. Significant (up to 30% e.e.) chiral induction during nucleophilic fluorination to form ß-fluoroamines using oxazaborolidine (pre)catalysts and CsF also can be achieved. Screening different boranes revealed a correlation between calculated fluoride affinity of the borane and nucleophilic fluorination reactivity, with sufficient fluoride affinity required for boranes to react with CsF and form Cs[fluoroborate] salts, but too high a fluoride affinity leading to fluoroborates that are poor at transferring fluoride to an electrophile. Fluoride affinity is only one component controlling reactivity in this context; effective fluorination also is dependent on the ligation of Cs+ which effects both the phase transfer of CsF and the magnitude of the [Cs⋯F-BR3] interaction and thus the B-F bond strength. Effective ligation of Cs+ (e.g. by [2.2.2]-cryptand) facilitates phase transfer of CsF by the borane but also weakens the Cs⋯F-B interaction which in turn strengthens the B-F bond - thus disfavouring fluoride transfer to an electrophile. Combined, these findings indicate that optimal borane mediated fluorination occurs using robust (to the fluorination conditions) boranes with fluoride affinity of ca. 105 kJ mol-1 (relative to Me3Si+) under conditions where a signficant Cs⋯F-B interaction persists.

Enhanced N-directed electrophilic C-H borylation generates BN-[5]- and [6]helicenes with improved photophysical properties.

Helicenes are chiral polycyclic aromatic hydrocarbons (PAHs) of significant interest, e.g. in supramolecular chemistry, materials science and asymmetric catalysis. Herein an enhanced N-directed electrophilic C-H borylation methodology has been developed that provides access to azaborine containing helicenes (BN-helicenes). This borylation process proceeds via protonation of an aminoborane with bistriflimidic acid. DFT calculations reveal the borenium cation formed by protonation to be more electrophilic than the product derived from aminoborane activation with BBr3. The synthesised helicenes include BN-analogues of archetypal all carbon [5]- and [6]helicenes. The replacement of a CC with a BN unit (that has a longer bond) on the outer helix increases the strain in the BN congeners and the racemization half-life for a BN-[5]helicene relative to the all carbon [5]helicene. BN incorporation also increases the fluorescence efficiency of the helicenes, a direct effect of BN incorporation altering the distribution of the key frontier orbitals across the helical backbone relative to carbo-helicenes.

Haloboration: scope, mechanism and utility.

Haloboration, the addition of B-X (X = Cl, Br, I) across an unsaturated moiety e.g., C[double bond, length as m-dash]Y or C[triple bond, length as m-dash]Y (Y = C, N, etc.), is dramatically less utilised than the ubiquitous hydroboration reaction. However, haloboration of alkynes in particular is a useful tool to access ambiphilic 1,2-disubstituted alkenes. The stereochemical outcome of the reaction is easily controlled and the resulting products have proven to be valuable building blocks in organic synthesis and materials chemistry. This review aims at providing the reader with a brief summary of the historic development and of the current mechanistic understanding of this transformation. Recent developments are discussed and select examples demonstrating the use of haloboration products are given with a focus on the major areas, specifically, natural product synthesis and the development of boron-doped polycyclic aromatic hydrocarbons (B-PAHs).

Aryl-aryl coupling in a polycyclic aromatic hydrocarbon with embedded tetracoordinate boron centre.

The addition of 2 eq. of MesLi to the biphenylene-containing 9,10-dihydro-9,10-diboraanthracene (DBA) 2 results in the formation of the corresponding oxaboraphenanthrene 3 after column chromatography under ambient conditions. In the initial step, the anionic B-Mes monoadduct of 2 is generated, which eliminates a formal [Mes2B:]- ion with concomitant C-C-bond formation (room temperature, 18 h). The resulting biphenylene-containing borafluorene 4 is still sufficiently Lewis acidic to add the second equivalent of MesLi ([4Mes]-). Using pristine 9-mesityl-9-borafluorene as a model system, we confirmed that both 4 and [4Mes]- should be capable of inserting an oxygen atom to furnish the observed oxaboraphenanthrene scaffold. The biphenylene-containing oxaboraphenanthrene 3 is a yellow compound with an absorption maximum at λmax = 450 nm. Similar to its DBA analogue 2, 3 shows no photoluminescence.

Changes of lung parenchyma density following high dose radiation therapy for thoracic carcinomas - an automated analysis of follow up CT scans.

BACKGROUND: An objective way to qualify the effect of radiotherapy (RT) on lung tissue is the analysis of CT scans after RT. In this analysis we focused on the changes in Hounsfield units (ΔHU) and the correlation with the corresponding radiation dose after RT. METHODS: Pre- and post-RT CT scans were matched and ΔHU was calculated using customized research software. ΔHU was calculated in 5-Gy-intervals and the correlation between ΔHU and the corresponding dose was calculated as well as the regression coefficients. Additionally the mean ΔHU and ΔHU in 5-Gy-intervals were calculated for each tumor entity. RESULTS: The mean density changes at 12 weeks and 6 months post RT were 28,16 HU and 32,83 HU. The correlation coefficient between radiation dose and ΔHU at 12 weeks and 6 months were 0,166 (p = 0,000) and 0,158 (p = 0,000). The resulting regression coefficient were 1439 HU/Gy (p = 0,000) and 1612 HU/Gy (p = 0,000). The individual regression coefficients for each patient range from - 2,23 HU/Gy to 7,46 HU/Gy at 12 weeks and - 0,45 HU/Gy to 10,51 HU/Gy at 6 months. When looking at the three tumor entities individually the highest ΔHU at 12 weeks was seen in patients with SCLC (38,13 HU) and at 6 month in those with esophageal carcinomas (40,98 HU). CONCLUSION: For most dose intervals there was an increase of ΔHU with an increased radiation dose. This is reflected by a statistically significant, although low correlation coefficient. The regression coefficients of all patients show large interindividual differences.

Simultaneous expansion of 9,10 boron-doped anthracene in longitudinal and lateral directions.

Doubly boron-doped anthracenes and pentacenes have been longitudinally and laterally expanded through annulation of thiophene or benzene rings. The obtained series of closely related compounds allowed an assessment of key structure-property relationships with a focus on optoelectronic characteristics. Most of the products are benchtop-stable blue emitters and capable of accepting two electrons in a reversible manner. The syntheses involved late-stage modifications through photocyclization or stepwise oxidative C-C coupling (DDQ/BF3·Et2O) as well as cyclocondensation of ortho-disilylated or -diborylated aryl building blocks.

How Boron Doping Shapes the Optoelectronic Properties of Canonical and Phenylene-Containing Oligoacenes: A Combined Experimental and Theoretical Investigation.

Optimized syntheses of 6,13-dimesityl-6,13-dihydro-6,13-diborapentacene (DBP) and a related compound (DBI) featuring two biphenylene-2,3-diyl units in place of naphthalene-2,3-diyl moieties are reported. Striking differences between the optoelectronic properties of DBP and DBI have been experimentally observed, and explained by quantum chemical calculations. DBP is a member of the oligoacene family, DBI is a linear [N]phenylene derivative. The yellow DBP shows blue photoluminescence, the deep red DBI is nonfluorescent. Both compounds give rise to two reversible redox transitions at E1/2 =-2.03 V, -2.75 V (DBP) and -1.52 V, -2.30 V (DBI; THF, vs. FcH/FcH+ ). The higher electron affinity of DBI agrees with a lower calculated LUMO energy level [-0.57 eV for DBI with respect to DBP @HF//SCS-MP2/def2-TZVP] and a higher Lewis acidity of its boron centers, which is reflected in the trend of adduct formation with small Lewis bases (MeCN, F- ). The thermochemistry underlying this trend, as well as the mechanism of fluorescence quenching in DBI, are revealed by state-of-the-art quantum chemical calculations. It is suggested that the nonradiative deactivation occurs via a low-lying, doubly excited state.