Phospholes are known to exhibit characteristic optical and electrochemical properties derived from the phosphorus-bridged 1,3-dienic π system. Particular interest has recently been paid their π-conjugated derivatives, such as non-fused phospholes, dibenzo[b,d]phospholes, benzo[b]phospholes, benzo[c]phospholes related compounds. This perspective focuses on recent advances in synthesis of these phosphole-based systems with representative examples that would give valuable guidelines for...

Novel perylene imide derivatives with both electron-donating and bulky substituents have been synthesized for dye-sensitized solar cells. The power conversion efficiency reached 2.6%, which is the highest value among perylene-sensitized TiO2

A novel naphthyl-fused zinc porphyrin carboxylic acid has been synthesized and employed successfully in a dye-sensitized TiO2 solar cell, with power conversion efficiency of 4.1%, which is improved by 50% relative to the unfused reference cell.

A novel strategy for constructing a vertical arrangement of bicontinuous donor-acceptor arrays on semiconducting electrode has been developed. The relationship between the film structure and photoelectrochemical properties elucidated as function number donor layers first time. maximum incident photon-to-current efficiency value (21%) is comparable to highest (20%) reported arrangements electrodes.

5,10,15,20-Tetrakis(2,4,6-trimethylphenyl)-6'-carboxyquinoxalino[2,3-β]porphyrinatozinc (II) (ZnQMA) and 5,10,15,20-tetrakis(2,4,6-trimethylphenyl)-6',7'-dicarboxyquinoxalino[2,3-β]porphyrinatozinc (ZnQDA) have been synthesized to evaluate the effects of β,β'-carboxyquinoxalino moieties on structure optical, electrochemical, photovoltaic properties porphyrins. Both ZnQMA ZnQDA exhibited broadened red-shifted light absorption in UV−visible spectra compared with...

Novel unsymmetrically π-elongated porphyrins, in which the naphthyl moiety is fused to porphyrin core at bridge with a carboxyl group (fused-Zn-1) or opposite side of phenyl (fused-Zn-2), have been synthesized improve light-harvesting abilities porphyrin-sensitized solar cells. As results π-elongation low symmetry, Soret and Q bands fused-Zn-1 fused-Zn-2 were red-shifted broadened, intensity Q-band relative that band was enhanced. The fused-Zn-2-sensitized TiO2 cells showed power conversion...

We have prepared meso-bis(diarylamino)-substituted porphyrins (cis-ZnP and trans-ZnP), meso-diarylamino-substituted porphyrin (mono-ZnP), reference without the meso-diarylamino group (ZnP) to evaluate effects of substituent number position diarylamino groups on optical, electrochemical, photovoltaic properties for first time. With increasing groups, light-harvesting were improved in visible region. The optical electrochemical HOMO−LUMO gaps parallel those estimated by DFT calculations....

A series of meso-tetraphenylzincporphyrins have been prepared to examine the effects porphyrin substituents and adsorption conditions on photovoltaic properties porphyrin-sensitized TiO2 cells. The cell performance strongly depended linking bridge between core surface, bulkiness around core, immersing solvents times for adsorption. In particular, high cells was achieved when protic solvent (i.e., methanol) short time (0.5−1 h) were used dye TiO2, which is in sharp contrast with Ru...

Liquid crystalline donor (i.e., phthalocyanine) was covalently linked to acceptor (i.e, fullerene) achieve efficient charge-transport properties in a liquid phase. The columnar structure exhibited highly ambipolar character, demonstrating the potential utility of strategy organic electronics.

A profusion of phospholes: Diacenaphtho[1,2-b:1',2'-d]phospholes, a new class arene-fused phosphole π-systems, were synthesized and their structural electrochemical properties studied. The P-sulfide derivative has high electron-transporting ability (μ(E) =2.4×10(-3) cm(2) V(-1) s(-1)) in vacuum-deposited film.

This review presents a systematic and comprehensive survey of various applications bismuth compounds to organic transformations. The is organized on the basis type compounds, within each reactions are transformations involved. Emphasis placed recent literature, those which authors feel have synthetic potential. Less common aspects organobismuth also included briefly.

Novel 5-(5-carboxy-2-thienyl)-10,15,20-tris(2,4,6-trimethylphenyl)-porphyrinatozinc(II) (Zn5S), 5-(5-carboxy-2-furyl)-10,15,20-tris(2,4,6-trimethylphenyl)porphyrinatozinc(II) (Zn5O), and 5-(4-carboxy-2-thienyl)-10,15,20-tris(2,4,6-trimethylphenyl)porphyrinatozinc(II) (Zn4S) were synthesized to evaluate the spacer effects on structures of porphyrin films photovoltaic properties porphyrin-sensitized TiO2 solar cells. Each porphyrins showed different adsorption behavior saturated coverage...

Porphyrins are large heterocyclic macrocycles that bind metals to form complexes such as heme and chlorophyll. Porphyrinogens related in which the meso-carbons, carbon atoms connecting pyrroles or five-atom heterocycles, all partially reduced methylene, disrupting pi-electron conjugation. Both porphyrins porphyrinogens important components of natural synthetic systems, they have completely different coordination behavior. Consequently, chemistry entire porphyrin family, including regular...

Conjugated polymers with alternating main chain structures of zinc porphyrin−furan (PZnPF) and porphyrin−thiophene (PZnPT) have been synthesized by palladium(0)-catalyzed Stille coupling reaction. The optical, electrochemical, photophysical, photovoltaic properties PZnPF PZnPT were investigated to elucidate the effects heterole bridges (i.e., furan vs. thiophene) in porphyrin polymers. optical bandgap (1.75 eV) is smaller than that (1.90 eV), implying high delocalization π-electrons along...

Electrode structures and photovoltaic properties of porphyrin-sensitized solar cells with TiO2 Nb-, Ge-, Zr-added composite electrodes were examined to disclose the effects partial substitution Ti atom by other metals in electrodes. The prepared sol-gel process using laurylamine hydrochloride as a template for formation micellar precursors yielding well-defined mesoporous nanocrystalline structures, cases silica titania tubules nanoparticles templating mechanism. characterized transmission...

Phthalocyanines with high peripheral substitutions and free from potential contamination by regioisomers have been synthesized evaluated as photosensitizers for dye-sensitized solar cell applications. Each of the sterically hindered precursor compounds was accomplished Suzuki-Miyaura cross-coupling reactions arylchloride corresponding boronic acids. Metal phthalocyanine-sensitized cells showed no photocurrent generation due to its low excited singlet state (LUMO) compared conduction band...

Novel benzo[f]quinoxalino[2,3-β]porphyrin carboxylic acid (ZnBQA) and cyanoquinoxalino[6,7-β]porphyrin (ZnQCA) have been synthesized to evaluate the effects of π-elongation fused position quinoxaline-fused porphyrins on optical, electrochemical, photovoltaic properties. ZnBQA showed a split, red-shifted Soret band relative that quinoxalino[2,3-β]porphyrin (ZnQMA), while Q bands are rather blue-shifted. On other hand, both Q-bands ZnQCA compared those ZnQMA. The optical HOMO−LUMO gaps...

We have prepared a novel push–pull porphyrin with an electron-donating diarylamino group at the meso-position and electron-withdrawing 4-carboxy-2,3,5,6-tetrafluorophenylethynyl anchoring opposite to address substitution effects of fluorine atoms on photovoltaic properties for first time. The fluoro-substituted showed slightly improved light-harvesting when compared reference in solution, due enhancement charge-transfer character. porphyrin-sensitized TiO2 cell exhibited moderate power...

Abstract The first examples of air‐stable 20π‐electron 5,10,15,20‐tetraaryl‐5,15‐diaza‐5,15‐dihydroporphyrins, their 18π‐electron dications, and the 19π‐electron radical cation were prepared through metal‐templated annulation nickel(II) bis(5‐arylamino‐3‐chloro‐8‐mesityldipyrrin) complexes followed by oxidation. neutral derivatives are antiaromatic cationic aromatic in terms magnetic criterion aromaticity. meso N atoms these diazaporphyrinoids give rise to characteristic redox optical...

The syntheses, structures, and coordination chemistry of phosphole-containing hybrid calixphyrins (P,N2,X-hybrid calixphyrins) the catalytic activities their transition-metal complexes are reported. 5,10-porphodimethene type 14pi-P,(NH)2,X- 16pi-P,N2,X-hybrid (X = O, S, NH) prepared via acid-promoted dehydrative condensation between a sigma4-phosphatripyrrane corresponding 2,5-bis[hydroxy(phenyl)methyl]heteroles followed by DDQ oxidation. Both spectroscopic crystallographic data have...

Three types of bithiophene-fused benzo[c]phospholes were successfully prepared by Ti(II)-mediated cyclization the corresponding dialkynylated bithiophene derivatives as a key step. Each sigma(3)-phosphorus center benzo[c]phosphole subunits was readily transformed into sigma(4)-phosphorus Au coordination or oxygenation. In addition, subunit functionalized at alpha,alpha'-carbon atoms Pd-catalyzed cross-coupling reactions with heteroarylmetals and an S(N)Ar reaction hexafluorobenzene. The...

The synthesis, structures, optical and electrochemical properties, aromaticity of a series 5,15-diaza-10,20-dimesitylporphyrins (M-DAP; M = Pb, H(2), Ni, Pd, Pt, Zn; mesityl 2,4,6-trimethylphenyl) are reported. Treatment mesityl-substituted bis(5,5'-dibromodipyrrin) with sodium azide in the presence lead(II) acetylacetonate afforded Pb-DAP, which was quantitatively converted to H(2)-DAP by acidolysis. free base reacted palladium(II), platinum(II), zinc(II) salts give Pd-DAP, Pt-DAP, Zn-DAP,...

Abstract The present paper reports the first comprehensive study on synthesis, structures, optical and electrochemical properties, peripheral functionalizations of nickel(II) copper(II) complexes β‐unsubstituted 5,15‐diazaporphyrins (M‐DAP; M=Ni, Cu) pyridazine‐fused diazacorrinoids (Ni‐DACX; X=N, O). These two classes compounds were constructed starting from mesityldipyrromethane by a metal–template method. Ni‐DAP Cu‐DAP prepared in high yields reaction respective metal–bis(dibromodipyrrin)...