Understanding Hole Extraction of Inverted Perovskite Solar Cells.

This paper describes a correlation between charge extraction and energy-level alignment at the interface of polymeric hole transport layers and perovskite active layers. By tailoring the composition of the conjugated backbone of the hole transport material, energy levels between perovskites and hole transport layers are varied. Matching the band alignment at perovskite/hole transport interfaces dramatically improved charge extraction and thus device performance.

Transforming Ionene Polymers into Efficient Cathode Interlayers with Pendent Fullerenes.

A new and highly efficient cathode interlayer material for organic photovoltaics (OPVs) was produced by integrating C fullerene monomers into ionene polymers. The power of these novel "C -ionenes" for interface modification enables the use of numerous high work-function metals (e.g.

Combining Fullerenes and Zwitterions in Non-Conjugated Polymer Interlayers to Raise Solar Cell Efficiency.

Polymer zwitterions were synthesized by nucleophilic ring-opening of 3,3'-(but-2-ene-1,4-diyl)bis(1,2-oxathiolane 2,2-dioxide) (a bis-sultone) with functional perylene diimide (PDI) or fullerene monomers. Integration of these polymers into solar cell devices as cathode interlayers boosted efficiencies of fullerene-based organic photovoltaics (OPVs) from 2.75 % to 10.

Fluoride-Catalyzed Deblocking: A Route to Polymeric Urethanes.

We report a fluoride-catalyzed deblocking of urethanes as "blocked" isocyanates. Organic and inorganic sources of fluoride ion proved effective for deblocking urethanes and for converting polyurethanes to small molecules. Distinct from conventional deblocking chemistry involving organometallic compounds and high temperatures, the method we describe is metal-free and operates at or slightly above room temperature.

An approach to estimate spatial distribution of analyte within cells using spectrally-resolved fluorescence microscopy.

While fluorescence microscopy has become an essential tool amongst chemists and biologists for the detection of various analyte within cellular environments, non-uniform spatial distribution of sensors within cells often restricts extraction of reliable information on relative abundance of analytes in different subcellular regions. As an alternative to existing sensing methodologies such as ratiometric or FRET imaging, where relative proportion of analyte with respect to the sensor can be obtained within cells, we propose a methodology using spectrally-resolved fluorescence microscopy, via which both the relative abundance of sensor as well as their relative proportion with respect to the analyte can be simultaneously extracted for local subcellular regions. This method is exemplified using a BODIPY sensor, capable of detecting mercury ions within cellular environments, characterized by spectral blue-shift and concurrent enhancement of emission intensity.

Infinite Polyiodide Chains in the Pyrroloperylene-Iodine Complex: Insights into the Starch-Iodine and Perylene-Iodine Complexes.

We report the preparation and X-ray crystallographic characterization of the first crystalline homoatomic polymer chain, which is part of a semiconducting pyrroloperylene-iodine complex. The crystal structure contains infinite polyiodide I∞ (δ-) . Interestingly, the structure of iodine within the insoluble, blue starch-iodine complex has long remained elusive, but has been speculated as having infinite chains of iodine.

Boron-dipyrromethene based reversible and reusable selective chemosensor for fluoride detection.

We synthesized benzimidazole substituted boron-dipyrromethene 1 (BODIPY 1) by treating 3,5-diformyl BODIPY 2 with o-phenylenediamine under mild acid catalyzed conditions and characterized by using various spectroscopic techniques. The X-ray structure analysis revealed that the benzimidazole NH group is involved in intramolecular hydrogen bonding with fluoride atoms which resulted in a coplanar geometry between BODIPY and benzimidazole moiety. The presence of benzimidazole moiety at 3-position of BODIPY siginificantly altered the electronic properties, which is clearly evident in bathochromic shifts of absorption and fluorescence bands, improved quantum yields, increased lifetimes compared to BODIPY 2.

Stable core-modified calixsmaragdyrins: synthesis, structure and specific sensing of the hydrogen sulfate ion.

Stable calixoxa- and calixthiasmaragdyrins containing three methine bridges and two direct bonds connecting the five pyrrole/heterocycle rings were synthesized by [3 + 2] condensation of dipyrromethane with 16-oxatripyrrane and 16-thiatripyrrane respectively under mild acid-catalyzed conditions. The compounds were characterized by HR-MS, 1D & 2D NMR, absorption and electrochemical techniques and the structure of calixoxasmaragdyrin was solved by X-ray crystallography. The crystal structure analysis indicated that the calixoxasmaragdyrin macrocycle was highly distorted due to the flexibility introduced by one sp(3)meso-carbon.

Sensing Hg(II) in vitro and in vivo using a benzimidazole substituted BODIPY.

A multisignaling Hg(II) sensor based on a benzimidazole substituted BODIPY framework was designed, which displays excellent selectively toward Hg(II) in vitro and in vivo. Optical and fluorogenic measurements in solution reveal that the sensor can detect mercury ions at submicromolar concentrations, with high specificity. The detection of Hg(II) is associated with a blue-shift in optical spectra and a simultaneous increase in the fluorescence quantum yield of the sensor, which is attributed to a decrease in charge delocalization and inhibition of photoinduced electron transfer upon binding to Hg(II).

Synthesis of 3,5-bis(acrylaldehyde) boron-dipyrromethene and application in detection of cysteine and homocysteine in living cells.

Synthesis, characterization, and spectral and electrochemical properties of 3,5-bis(acrylaldehyde) BODIPY are described. The compound exhibited higher selectivity toward cysteine/homocysteine than toward other amino acids and thiol-containing compounds as shown by absorption and emission titration experiments and by experiments in living cells.

3,5-Diformyl-borondipyrromethene for selective detection of cyanide anion.

Cyanide is one of the most toxic inorganic anions, it is very harmful to human health but extremely useful in industrial activities. Herein, we used our recently reported boradiazaindacene (BODIPY) dye, 3,5-diformyl-borondipyrromethene (BODIPY 1) as an exclusive chemodosimetric and colorimetric sensor for CN(-) ion. Cyanide ion attacks the carbonyl groups of 1 via a nucleophilic addition reaction and converts to cyanohydrin which is reflected in the clear colour change as well as by the absorption, emission and electrochemical properties.

Synthesis, spectral, electrochemical, and anion binding properties of 3,5-bis(dipyrromethanyl) boron-dipyrromethenes.

Four new boron-dipyrromethenes (BODIPYs) containing dipyrromethanyl substituents at 3,5-positions, bis(3,5-dipyrromethanyl) BODIPYs 5-8, were synthesized by treating their corresponding 3,5-diformyl BODIPYs 1-4 with excess pyrrole under mild acid catalyzed reaction conditions. The compounds 5-8 are stable and freely soluble in common organic solvents. One-dimensional, two-dimensional NMR, high resolution mass spectrometry (HRMS), absorption, fluorescence, and electrochemical techniques were used to characterize the compounds.

Fabrication of unipolar graphene field-effect transistors by modifying source and drain electrode interfaces with zinc porphyrin.

We report a unipolar operation in reduced graphene oxide (RGO) field-effect transistors (FETs) via modification of the source/drain (S/D) electrode interfaces with self-assembled monolayers (SAMs) of 5-(4-hydroxyphenyl)-10,15,20-tri-(p-tolyl) zinc(II) porphyrin (Zn(II)TTPOH) molecules. The dipolar Zn(II)TTPOH molecules at the RGO/platinum (Pt) S/D interface results in an increase of the electron injection barrier and a reduction of the hole-injection barrier. Using dipole measurements from Kelvin probe force microscopy and highest occupied molecular orbital-lowest unoccupied molecular orbital (HOMO-LUMO) calculations from cyclic voltammetry, the electron and hole injection barriers were calculated to be 2.

3,5-Diformylboron dipyrromethenes as fluorescent pH sensors.

A series of boron dipyrromethene (BODIPY) dyes containing two aldehyde functional groups at the 3 and 5 positions have been synthesized in low-to-decent yields in two steps. In the first step, the meso-aryl dipyrromethanes were treated with POCl(3) in N,N-dimethylformamide to afford 1,9-diformylated dipyrromethanes. In the second step, the diformylated dipyrromethanes were first in situ oxidized with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone and then reacted with BF(3)·OEt(2) to afford 3,5-diformylboron dipyrromethenes.