Chemical fixation of carbon dioxide (CO2), which is an inexpensive and renewable source, becoming more important. The development both new reactions catalysts needed to overcome the kinetic thermodynamic stability CO2. Organic metal with unique excellent activity selectivity have been developed for various chemical conversions In this perspective, we provide overview recent progress in field, classifying it into several categories, where each research concisely summarized one by using a...

We prepared bifunctional Mg(II) porphyrin catalysts 1 for the solvent-free synthesis of cyclic carbonates from epoxides and CO2. The activities 1d, 1h, 1i, which have Br(-), Cl(-), I(-) counteranions, respectively, increased in order 1i < 1h 1d. Catalysts 1d 1j-m, bear four tetraalkylammonium bromide groups with different alkyl chain lengths, showed comparable but slightly activities. Based on excellent catalyst we synthesized 1o eight groups, even higher catalytic activity (turnover number,...

Abstract Highly active bifunctional diporphyrin and triporphyrin catalysts were synthesized through Stille coupling reactions. As compared with a porphyrin monomer, both exhibited improved catalytic activities for the reaction of CO 2 epoxides to form cyclic carbonates, because multiple sites which cooperatively activate epoxide. Catalytic carefully investigated by controlling temperature, time, catalyst loading, very high turnover number frequency obtained: 220 000 46 h −1 , respectively,...

Abstract Bifunctional metalloporphyrins with quaternary ammonium bromides (nucleophiles) at the meta , para or ortho positions of meso ‐phenyl groups were synthesized as catalysts for formation cyclic carbonates from epoxides and carbon dioxide under solvent‐free conditions. The ‐substituted exhibited high catalytic performance, whereas ‐ showed moderate low activity, respectively. DFT calculations revealed origin advantage catalyst, which could use flexible cation position to stabilize...

Helical carbazole-based BODIPY analogues were readily synthesized via aza[7]helicenes. The structures of azahelicene-incorporated BF2 dyes elucidated by x-ray diffraction analysis. DFT calculations revealed that the π-conjugated system expanded from helicene moiety to framework. azahelicene-fused boron complexes showed Cotton effects and circularly polarized luminescence (CPL) in visible region. Furthermore, an axially chiral binaphthyl group was attached helically dyes, which enhanced...

Bifunctional Al porphyrins worked as excellent catalysts for the copolymerization of cyclohexene oxide (CHO) and CO₂.

Going around in circles: The copper(I)-mediated annulation of a doubly 1,3-butadiyne-bridged carbazole dimer with amines or Na2S provides isophlorins containing thiophene-carbazole moieties, respectively (see scheme). Oxidization the thiophene-containing isophlorin MnO2 gives corresponding porphyrin, which displays distinct aromaticity and remarkably intensified red-shifted absorption bands near IR region. Detailed facts importance to specialist readers are published as "Supporting...

Intramolecular aromatic oxidative coupling of 3,6‐bis(m‐terphenyl‐2’‐yl)carbazole provided a bis(m‐terphenyl)‐fused carbazole, while that 3,6‐bis(m‐terphenyl‐2’‐yl)‐1,8‐diphenylcarbazole afforded bis(quaterphenyl)‐fused carbazole. Borylation the latter furnished B,N‐embedded helical nanographene binding fluoride anion via structural change from three‐coordinate boron to four‐coordinate boron. The anionic charge derived is stabilized over expanded p‐framework, which leads high constant (Ka) 1...

The Scholl reaction has been used to synthesize a variety of polycyclic aromatic hydrocarbons, where 1,2‐aryl shifts have sometimes occurred yield unique rearrangement products. However, such are often uncontrollable, and the selective divergent synthesis with or without is desired. Here, we achieved control in carbazoles by N‐substituents. 3,6‐bis{2‐(2‐naphthyl)phenyl}carbazoles 3,6‐bis{2‐(9‐phenanthrenyl)phenyl}carbazoles an N‐benzyl group gave multiple azahelicenes via double...

Abstract Bifunctional Zn II porphyrin catalysts bearing tributylammonium bromide groups at the meta positions of meso ‐phenyl showed high catalytic activity for synthesis cyclic carbonates from epoxides and CO 2 . Herein, several substituents with different electronic properties were introduced para positions. Introduction electron‐donating decreased activity, whereas introduction electron‐withdrawing increased activity. The modulated Lewis acidity zinc center, which was confirmed by binding...

Carbazole-based BODIPYs were synthesized in three steps using an organometallic approach consisting of sequential Ir-catalyzed borylation, Suzuki–Miyaura coupling, and boron complexation. Various substituents introduced into the carbazole moiety, large substituent effects confirmed by means absorption spectroscopy, cyclic voltammetry, DFT calculations. Dibenzocarbazoles also converted corresponding BODIPYs.

Doubly (R)-binaphthyl-strapped porphyrins with methylene chains were synthesized. The CD spectra showed the positive Cotton effect around Soret bands, and several CPL. In addition, we found that chiral applicable to kinetic resolution of epoxide CO2.

Several carbazole-based boron dipyrromethene (BODIPY) dyes were synthesized by organometallic approaches. Thiazole, benzothiazole, imidazole, benzimidazole, triazole, and indolone substituents introduced at the 1-position of carbazole moiety, complexation each dipyrrin generated corresponding compounds 1, 2 a, 3-6. The properties these products investigated UV/Vis fluorescence spectroscopy, cyclic voltammetry, X-ray crystallography, DFT calculations. These exhibited large Stokes shifts, 3-5...

Chiral carbazole-based BODIPYs with a binaphthyl unit were synthesized via an Al-mediated reaction. Et2AlCl was found to be convenient reagent for the reaction give chiral in high yields. It has been shown first time that these show circularly polarized luminescence (CPL) both solution and solid state.

Hexameric and tetrameric porphyrin nanorings, Z6·T6 Z4·T4, were synthesized in 53% 14% yields, respectively, by the Sonogashira-type self-oligomerization of monomer 1 using hexadentate template T6 tetrapyridylporphyrin T4. Template-free nanorings Z6 Z4 also prepared. The femtosecond transient absorption measurements revealed fast excitation energy hopping (EEH) along these with rates 2–5 ps. Treatment chiral CT6 gave Z6·CT6 showing circular dichroism (CD) circularly polarized luminescence...

Abstract Helical carbazole‐based BODIPY analogues were readily synthesized via aza[7]helicenes. The structures of azahelicene‐incorporated BF 2 dyes elucidated by x‐ray diffraction analysis. DFT calculations revealed that the π‐conjugated system expanded from helicene moiety to framework. azahelicene‐fused boron complexes showed Cotton effects and circularly polarized luminescence (CPL) in visible region. Furthermore, an axially chiral binaphthyl group was attached helically dyes, which...

Cu(I)-catalyzed 1,3-dipolar cycloaddition of meso-ethynyl Zn(II) porphyrin with benzyl azide efficiently provides meso-1-benzyl-1H-1,2,3-triazolyl porphyrin, which assembles to form a slipped cofacial dimer by the complementary coordination triazole nitrogen atom at 3-position zinc center second moiety both in solid and solution states. Removal protection introduction 2-ethoxycarbonylphenyl greatly stabilize dimeric assembly through an additional hydrogen bonding interaction between NH...

Abstract Highly active bifunctional diporphyrin and triporphyrin catalysts were synthesized through Stille coupling reactions. As compared with a porphyrin monomer, both exhibited improved catalytic activities for the reaction of CO 2 epoxides to form cyclic carbonates, because multiple sites which cooperatively activate epoxide. Catalytic carefully investigated by controlling temperature, time, catalyst loading, very high turnover number frequency obtained: 220 000 46 h −1 , respectively,...

<italic>meso</italic>-Octamethylcalix[4]pyrrole worked as an organocatalyst for the conversion of epoxides and CO₂ into cyclic carbonates under solvent-free conditions.

Abstract Carbazole‐based aza[7]helicenes and hetero[9]helicenes were successfully obtained via the intramolecular Scholl reaction of 3,6‐bis(biphenyl‐2‐yl)carbazole congeners, while 3,6‐bis(naphthylphenyl)‐appended carbazole gave a triple helicene an unexpected simultaneous double aryl rearrangement. DFT calculations suggested that rearrangement proceeded arenium cation intermediate. In addition, methoxy‐appended substrate azahepta[8]circulene concurrent C−C bond formation. These helical...

Bifunctional aluminum porphyrins catalyzed the conversion of oxetane and CO2 into trimethylene carbonate (TMC) poly(trimethylene carbonate) (PTMC). The catalytic activity bifunctional catalysts is driven mainly by central Al3+ ion while TMC/PTMC selectivity controlled counteranions. A variety TMCs including bis(TMC) were prepared from oxetanes with different substituents. terpolymerization oxetane, CO2, or copolymerization TMC produced cross-linked PTMCs, one which was successfully used for...

Brain aging causes a wide variety of changes at the molecular and cellular levels, leading to decline cognitive functions increased vulnerability neurodegenerative disorders. The research aimed understanding brain has made much progress in recent decades. Technological innovations such as single-cell RNA-sequencing (scRNA-seq), proteomic analyses, spatial transcriptomic analyses have facilitated on dynamic occurring within neurons, glia, other cells along with their impacts intercellular...

Abstract meso ‐Triazolyl‐appended Zn II –porphyrins were readily prepared by Cu I ‐catalyzed 1,3‐dipolar cycloaddition of benzyl azide to ‐ethynylated –porphyrin (click chemistry). In noncoordinating CHCl 3 solvent, spontaneous assembly occurred form tetrameric array ( ) 2 from – ‐linked diporphyrins , and dodecameric porphyrin squares 4 5 the L ‐shaped triporphyrins . The structures these assemblies examined 1 H NMR spectra, absorption their gel permeation chromatography (GPC) retention...