A Low Reabsorbing Luminescent Solar Concentrator Employing π-Conjugated Polymers

A highly efficient thin-film luminescent solar concentrator (LSC) utilizing two π-conjugated polymers as antennae for small amounts of the valued perylene bisimide Lumogen F Red 305 is presented. The LSC exhibits high photoluminescence quantum yield, low reabsorption, and relatively low refractive indices for waveguide matching. A Monte Carlo simulation predicts the LSC to possess exceptionally high optical efficiencies on large scales.National Science Foundation (U.S.) (Graduate Research Fellowship Program (Grant No. 1122374))Eni S.p.A. (Firm) (Eni-MIT Solar Frontiers Alliance

Understanding Uncertainty

A way to assess the information decrease uncertainty and project risk was described. Incorporating the method into real-time evaluation programs allowed continual updating of prognoses, such as the distance to a drilling target. Three case studies showed uncertainty analysis for geosteering into a thin pay section, a shaly-sand petrophysical analysis and a walkaway vertical seismic profile (VSP)

Red Phosphorescence from Benzo[2,1,3]thiadiazoles at Room Temperature

We describe the red phosphorescence exhibited by a class of structurally simple benzo[2,1,3]thiadiazoles at room temperature. The photophysical properties of these molecules in deoxygenated cyclohexane, including their absorption spectra, steady-state photoluminescence and excitation spectra, and phosphorescence lifetimes, are presented. Time-dependent density functional theory calculations were carried out to better understand the electronic excited states of these benzo[2,1,3]thiadiazoles and why they are capable of phosphorescence.National Science Foundation (U.S.) (1122374)United States. Dept. of Energy. Office of Basic Energy Sciences (DE-FG02-07ER46474

One-Pot Regiodirected Annulations for the Rapid Synthesis of Ï-Extended Oligomers

We demonstrate the broad applicability of the annulation protocol combining, in one pot, a direct arylation and cross aldol condensation for the straightforward synthesis at gram-scale of Ï-extended thiophene-based scaffolds. The regiospecific direct arylation drives the subsequent cross-aldol condensation proceed under the same basic conditions, and the overall protocol has broad applicability in the synthesis of extended aromatics wherein the thiophene ring is annulated with furans, pyridines, indoles, benzothiophenes, and benzofurans. These scaffolds can be further elaborated into Ï-extended, highly fluorescent oligomers with a central deficient benzothiadiazole unit with up to nine aromatic rings through coupling reactions

Nucleophilic Functionalization of the Calix[6]arene Para- and Meta-Position via p‑Bromodienone Route

It is here demonstrated that the p-bromodienone route, previously reported for calix[4]arenes, is also effective for the functionalization of the calix[6]arene macrocycle. Thus, alcoholic O-nucleophiles can be introduced at the calix[6]arene exo rim. In addition, the reaction of a calix[6]arene p-bromodienone derivative with an actived aromatic substrate, such as resorcinol, led to the first example of a meta-functionalized, inherently chiral calix[6]arene derivativ

Fluorofluorophores: Fluorescent Fluorous Chemical Tools Spanning the Visible Spectrum

“Fluoro” refers to both fluorescent and fluorinated compounds. Despite the shared prefix, there are very few fluorescent molecules that are soluble in perfluorinated solvents. This paucity is surprising, given that optical microscopy is a ubiquitous technique throughout the physical sciences and the orthogonality of fluorous materials is a commonly exploited strategy in synthetic chemistry, materials science, and chemical biology. We have addressed this shortage by synthesizing a panel of “fluorofluorophores,” fluorescent molecules containing high weight percent fluorine with optical properties spanning the visible spectrum. We demonstrate the utility of these fluorofluorophores by preparing fluorescent perfluorocarbon nanoemulsions.National Science Foundation (U.S.) (ECCS-0939514

Functionalized Poly(3-hexylthiophene)s via Lithium–Bromine Exchange

Poly(3-hexylthiophene) (P3HT) is one of the most extensively investigated conjugated polymers and has been employed as the active material in many devices including field-effect transistors, organic photovoltaics and sensors. As a result, methods to further tune the properties of P3HT are desirable for specific applications. Herein, we report a facile postpolymerization modification strategy to functionalize the 4-position of commercially available P3HT in two simple steps–bromination of the 4-position of P3HT (Br–P3HT) followed by lithium−bromine exchange and quenching with an electrophile. We achieved near quantitative lithium–bromine exchange with Br–P3HT, which requires over 100 thienyl lithiates to be present on a single polymer chain. The lithiated-P3HT is readily combined with functional electrophiles, resulting in P3HT derivatives with ketones, secondary alcohols, trimethylsilyl (TMS) group, fluorine, or an azide at the 4-position. We demonstrated that the azide-modified P3HT could undergo Cu-catalyzed or Cu-free click chemistry, significantly expanding the complexity of the structures that can be appended to P3HT using this method.National Science Foundation (U.S.) (ECCS-0939514