Search

The first example of cobalt-catalyzed selective hydrogenation of nitriles to secondary imines is reported. The results demonstrate the significantly different selectivity compared with the previously reported cobalt catalytic system during the nitrile hydrogenation. A variety of aromatic and aliphatic nitriles are hydrogenated to the corresponding secondary imines.

The straightforward synthesis of 3,5-di(triphenylethylenyl) BODIPYs 1-3 from the condensation of 2-(triphenylethylenyl) pyrrole with aryl aldehydes are surprisingly found to produce side products that are hydrogenated at one of the two triphenylethylene substituents. It was also observed that the subsequent Scholl type reaction of 1 resulted in a "1,2-migratory shift" of one triphenylethylene substituent in addition to a ring closing reaction. Preliminary investigations, including DFT calculations and isolation of intermediates, were conducted to study these unusual observations on BODIPY chemistry.

A facile N-heterocyclic carbene catalytic enantioselective aza-Diels-Alder reaction of oxodiazenes with α-chloroaldehydes as dienophile precursors is reported, with excellent enantioselectivity (ee > 99%) and excellent yield (up to 93%). DFT study showed that cis-TSa, formed from a top face approach of oxodiazene to cis-IIa, is the most favorable transition state and is consistent with the experimental observations.

Several diazatetracene diimides with high electron affinity (up to 4.66 eV!) were prepared and well characterized. The LUMO energy level of these electron-deficient molecules was found to be closely related to their material stability. Compound 7 with ultrahigh electron affinity suffered from reduction and hydrolysis in the presence of silica gel or water. The stable compounds 3 and 6 showed n-channel FET behavior with an average electron mobility of 0.002 and 0.005 cm(2) V(-1) s(-1), respectively, using a solution processing method.

An anthracene unit was successfully fused to the zigzag edge of a boron dipyrromethene (BODIPY) core by an FeCl(3)-mediated oxidative cyclodehydrogenation reaction. Meanwhile, a dimer was also formed by both intramolecular cyclization and intermolecular coupling. The anthracene-fused BODIPY monomer 7a and dimer 7b showed small energy gaps (∼1.4 eV) and near-infrared absorption/emission. Moreover, they exhibited high photostability.

The first tetracene diimide derivative fused with four thiophene rings, TT-TDI, was synthesized by an FeCl(3) mediated oxidative cyclodehydrogenation reaction. TT-TDI exhibited a low band gap of 1.52 eV and amphoteric redox behavior. TT-TDI also showed a liquid crystalline property and ambipolar charge transport in thin film field-effect transistors.

Two perylene anhydride fused porphyrins 1 and 2 have been synthesized and employed successfully in dye-sensitized solar cells (DSCs). Both compounds showed broad incident monochromatic photon-to-current conversion efficiency spectra covering the entire visible spectral region and even extending into the near-infrared (NIR) region up to 1000 nm, which is impressive for ruthenium-free dyes in DSCs.

A novel ion pair catalyst containing a chiral counteranion can be readily derived by simply mixing cinchona alkaloid-derived diamine with chiral camphorsulfonic acid (CSA). A mixture of 9-amino(9-deoxy)epi-quinine 8 and (-)-CSA was found to be the best catalyst with matching chirality, enabling the direct amination of α-branched aldehydes to proceed in quantitative yields and with nearly perfect enantioselectivities. A 0.5 mol % catalyst loading was sufficient to catalyze the reaction, and a gram scale enantioselective synthesis of biologically important α-methyl phenylglycine has been successfully demonstrated.

H-shaped bridged oligothiophenes HT-1 and HT-2 were synthesized by two different approaches. Different from normal oligothiophenes, HT-1 and HT-2 showed low band gaps and amphoteric redox behaviors due to intramolecular charge transfer, which is further supported by time-dependent DFT calculations.

N-Annulated perylene fused porphyrins 1 and 2 were synthesized by oxidative dehydrogenation using a Sc(OTf)(3)/DDQ system. These newly synthesized hybrid molecules are highly soluble in organic solvents and exhibit remarkably intense near-IR absorption, as well as detectable photoluminescence quantum yields, all of which are comparable to or even exceed those of either meso-β doubly linked porphyrin dimer/trimer or bis/tri-N-annulated rylenes.

A new ladder-type bis-N-annulated quaterrylenebis(dicarboximide) (1) was synthesized, and it exhibits excellent solubility in common organic solvents, high molar absorptivity, and good stability. Moreover, it absorbs and emits light in the near-IR spectral region with a high fluorescence quantum yield. All these properties qualify it as a promising NIR dye for many applications.

A facile one-pot synthesis of N-(α-peroxy)indole and N-(α-peroxy)carbazole has been developed using metal-free, organo-acid-catalyzed three-component condensation reactions of indole/carbazole, aldehyde, and peroxide. Based on the reaction discovered, a new synthetic proposal for Fumitremorgin A and Verruculogen is introduced. Such a protocol could be easily handled and scaled up in an open atmosphere with a wide substrate scope, enabling the construction of a new molecule library.

Alkoxy-wrapped N-annulated perylene (NP) was synthesized and used as a rigid and coplanar π-linker for three push–pull type metal-free sensitizers QB1–QB3. Their optical and electrochemical properties were tuned by varying the structure of acceptor. These new dyes were applied in Co(II)/(III) based dye-sensitized solar cells, and power conversion efficiency up to 6.95% was achieved, indicating that NP could be used as a new building block for the design of high-performance sensitizers in the future.

Two 7,14-disubstituted-5,12-dithiapentacenes (1 and 2) with quinoidal conjugation were synthesized. Their ground-state quinoidal structures were proven by X-ray crystallographic analysis. They showed very different electronic and optical properties from those of the corresponding pentacene derivatives with diene conjugation, and their stability was significantly improved. Organic field effect transistors based on solution processed thin films of 1 and 2 exhibited a hole mobility of up to 0.032 cm(-2) V(-1) s(-1).

Stepwise cyanation of tetrabromonaphthalenediimide (NDI) 1 gave a series of cyanated NDIs 2-5 with the monocyanated NDI 2 and dicyanated NDI 3 isolated. The tri- and tetracyano- NDIs 4 and 5 show intrinsic instability toward moisture because of their extremely low-lying LUMO energy levels. The partially cyanated intermediates can be utilized as air-stable n-type semiconductors with OFET electron mobility up to 0.05 cm(2) V(-1) s(-1).

Incorporation of electron-deficient tetracyanoquinodimethane (TCNQ) into electron-rich thiophene-fused heptacene was successfully achieved for the purpose of stabilizing longer acenes and generating new n-type organic semiconductors. The heptacene-TCNQ derivative 1 was found to have good stability and an expected electron transporting property. Electron mobility up to 0.01 cm(2) V(-1) s(-1) has been obtained for this novel material in solution processed organic field effect transistors.

A series of novel bifunctional phosphine−sulfonamide organic catalysts were designed and readily prepared from natural amino acids, and they were utilized to promote enantioselective aza-Morita−Baylis−Hillman (MBH) reactions. l-Threonine-derived phosphine−sulfonamide 9b was found to be the most efficient catalyst, affording the desired aza-MBH adducts in high yields and with excellent enantioselectivities.

A N-annulated perylene unit was successfully fused to the meso- and β-positions of a boron dipyrromethene (BODIPY) core. The newly synthesized BODIPY dye 1b exhibits intensified near-infrared (NIR) absorption and the longest emission maximum ever observed for all BODIPY derivatives. In addition, this dye possesses excellent solubility and photostability, beneficial to practical applications.

Soluble and stable zethrenebis(dicarboximide) (1) was synthesized by an in situ Stille cross coupling/transannular cyclization reaction. 1 showed largely improved photostability and solubility compared with the very unstable zethrene and it also exhibited far-red absorption and emission with high photoluminescence quantum yield. Bromination of 1 with NBS/DMF gave its quinone form 2 via an unusual pathway.

A soluble and stable quinoidal bisanthene (3) was synthesized, and it exhibited high molar absorptivity in the near-IR spectral region. In addition, compound 3 also showed good electrochemical amphotericity with four reversible one-electron transfer steps. Compound 3 represents a rare example of soluble and stable pi-conjugated polycyclic hydrocarbons with quinoidal character.