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Complexation of 1,3,6,8-tetra(2-hydroxyphenyl)-2,7-diazapyrene with boron precursors provided the tetracoordinate diazapyrene boron complexes as separable anti- and syn-isomers. The structural difference of these isomers induces unique properties such as self-association behaviour of the syn-isomer and isomerisation of the anti-isomer in the solution and solid states. [ABSTRACT FROM AUTHOR]

In this Feature Article, we summarize the synthetic progress of hetero[8]circulenes, focusing on their structures and intrinsic properties. Various hetero[8]circulenes have been synthesized to date, of which structural features are categorized on the basis of the numbers of annulated pentagons. From the viewpoint of key steps, the synthetic routes are classified into two methodologies, the annulative construction of the central eight-membered ring and the ring fusion of eight-membered ring precursors. Electronic and photophysical properties based on the structural features and the introduced heteroatoms of hetero[8]circulenes are also described. [ABSTRACT FROM AUTHOR]

The neighboring effect of two adjacent heteroatoms influences the structures and properties of heterocyclic compounds. Herein, we demonstrated that the introduction of two adjacent sp2 nitrogen atoms into a porphyrinic skeleton significantly enhanced its Brønsted basicity due to the repulsive interaction between two lone pairs on the nitrogen atoms. Palladium‐ and copper‐templated ring closure of dichlorobis(dipyrrin) with hydrazine hydrate provided meso‐diazacorrphycene palladium and copper complexes in good yields. The structural, magnetic, and electrochemical properties of the diazacorrphycene complexes were investigated experimentally and theoretically to elucidate the effect of the meso‐nitrogen atoms. [ABSTRACT FROM AUTHOR]

The development of porphyrin synthesis by means of transition metal-catalyzed reactions is explored in this feature article. Porphyrins have been receiving much attention in a wide area of chemistry as functional dyes, non-linear optical materials, ligands for a variety of metals, structural motifs in supramolecules, and so forth. However, they have been merely recognized as a reaction substrate in transition metal-catalyzed transformations. Recently, application of such new methodologies to porphyrin synthesis has proven to be very powerful to create new types of porphyrinic compounds, which have their own intriguing structures and properties. New transformations on porphyrins via transition metal catalysis offer us prospects of new designs of architectures, thus facilitating further development of this important class of functional molecules. [ABSTRACT FROM AUTHOR]

Treatment of dodec-6-yne with triallylmanganate in the presence of 1,3,5-trimethylbenzene provides (Z)-dodec-6-ene. An addition of D2O before quenching the reaction affords the corresponding dideuterated alkene. The result suggests the existence of the manganese–alkyne complex as an intermediate. Treatment of methyl propargyl ethers as alkynes with tributylmanganate generates propargylmanganese species. The reaction of non-2-ynyl tetrahydropyran-2-yl ether with tributylmanganate provides tetradec-7-yn-1,5-diol and 6-hexylocta-6,7-dien-1,5-diol. [Copyright &y& Elsevier]

A highly regioselective radical addition of N,N-dichlorobenzenesulfonamide (dichloramine-B) to 1-alkenes is achieved at -78 °C by the use of triethylborane as a radical initiator. The reaction of 1,3-dienes with N,N-dichlorosulfonamide in the presence of Et[sub 3]B regioselectively provides N-chloroN-allylamide derivatives. N-Chloro-N-allylamides thus obtained react with a variety of alkenes to furnish pyrrolidine derivatives in good yields. A radical annulation reaction among N,Ndichlorosulfonamide, 1,3-dienes, and alkenes has been developed. [ABSTRACT FROM AUTHOR]

Reports on the bromine atom-transfer radical addition of alpha-bromoacetate with 1-alkene in water. Reaction in water at ambient temperature in the presence of triethylborane to yield 4-bromoalkanoate; Solvent effect by performing the reaction in various solvents; Origin of the solvent effect on bromine atom-transfer addition.

Alkyne cycloisomerization of 2,7,10,15-tetra(ortho-alkynylphenyl)benzo[g,p]chrysene containing bulky 4-alkoxy-2,6-dimethylphenyl groups at the alkyne terminals selectively proceeded at the sterically crowded bay-region. The obtained double helicene adopts a distorted structure with a high racemization barrier due to the intramolecular steric repulsion. [ABSTRACT FROM AUTHOR]

Recently, π–π stacked antiaromatic π‐systems have received considerable attention because they can exhibit stacked‐ring aromaticity due to substantial intermolecular orbital interactions. Here, we report three antiaromatic norcorrole dimers that self‐assemble to form supramolecular architectures through chiral self‐sorting. A 2,2’‐linked norcorrole dimer with 3,5‐di‐tert‐butylphenyl groups forms a π‐stacked dimer both in solid and solution states via homochiral self‐sorting. Its association constant in solution is (3.6±1.7)×105 M−1 at 20 °C. In the solid state, 3,3’‐linked norcorrole dimers with 3,5‐di‐tert‐butylphenyl and phenyl groups afford macrocyclic and helical supramolecular assemblies via heterochiral and homochiral self‐sorting, respectively. Notably, the subtle modification in the substituent resulted in a complete change in the structure of the aggregates and the chiral self‐sorting mode. The present findings demonstrate that structural manipulation in antiaromatic monomer units leads to the formation of various supramolecular assemblies on the basis of the attractive interactions between antiaromatic π‐systems. [ABSTRACT FROM AUTHOR]

DMF-appened cyclometalated platinum(II) and -(IV) porphyrins were synthesized via the double cleavage of sp² CH and sp³ CH bonds on one platinum center. [ABSTRACT FROM AUTHOR]

Abstract: Direct functionalization of aromatic substituents on [28]hexaphyrin was achieved by Ir-catalyzed borylation with the Smith–Miyaura–Hartwig protocol. High para selectivity was observed in the reaction on 2,6-dichlorophenyl and 2,6-dimethoxyphenyl substituents of [28]hexaphyrin. The reaction with [26]hexaphyrin resulted only in reduction of the substrate to provide [28]hexaphyrin without borylation, thus highlighting the importance of the oxidation state of substrates in this catalytic transformation. The borylated hexaphyrin can be used for Suzuki–Miyaura cross-coupling reaction. [Copyright &y& Elsevier]

Cover Feature: meso-Diazacorrphycenes: Neighboring Effect of Two Nitrogen Atoms (Chem. Eur. J. 37/2020) Keywords: aromaticity; basicity; neighboring effect; nitrogen; porphyrinoid EN aromaticity basicity neighboring effect nitrogen porphyrinoid 8173 8173 1 07/04/20 20200702 NES 200702 B Molecules with two adjacent heteroatoms b show attractive properties owing to the neighboring effect. Nitrogen was chosen and embedded as a N=N unit into the skeleton of corrphycene, which is a porphyrin isomer. [Extracted from the article]

We report the synthesis and properties of indeno[1,2,3,4‐pqra]perylene, which was prepared by the fusion of one anthracene unit with one naphthalene unit via three carbon‐carbon bonds. The synthetic route through two‐fold C−H arylation enabled not only the synthesis of unsubstituted indenoperylene, but also rapid access to its arylated derivatives on the gram scale. Indenoperylene is a medium‐sized aromatic hydrocarbon with the composition C24H12 that is isomeric to coronene. Nevertheless, its absorption covers the entire visible region owing to its small HOMO‐LUMO gap. Furthermore, indenoperylene exhibits high stability despite the absence of peripheral substituents. We propose that the unique electronic structure of indenoperylene originates from the coexistence of an electron‐withdrawing subunit (benzoaceanthrylene) and an electron‐donating subunit (perylene). The electronic properties of indenoperylene were modulated via post‐functionalization through regioselective bromination. The current research demonstrates that indenoperylene is a promising candidate as a main skeleton for near‐infrared‐responsive and redox‐active materials. [ABSTRACT FROM AUTHOR]

Norcorrole Ni(II) complexes have recently received considerable attention because they are readily accessible antiaromatic molecules. Their high stability under ambient conditions and ease of synthesis have enabled the exploration of the intrinsic properties of antiaromatic molecules. Here, we report the synthesis and properties of meso–meso singly linked porphyrin‐norcorrole hybrids and a triply linked porphyrin‐norcorrole hybrid. The singly linked and triply linked porphyrin‐norcorrole hybrids were fully characterized, including an X‐ray structural analysis. Due to their orthogonal conformation, the singly linked hybrids maintain the individual electronic properties of their porphyrin and norcorrole subunits, while the triply linked hybrid shows a significantly smaller electrochemical HOMO–LUMO gap (0.45 eV) than that of Ni(II) dimesitylnorcorrole (1.08 eV). Furthermore, the triply linked hybrid exhibits singlet diradical characteristics, as confirmed by VT NMR, ESR, and SQUID experiments. [ABSTRACT FROM AUTHOR]

Norcorrole Ni(II) complexes have recently received considerable attention because they are readily accessible antiaromatic molecules. Their high stability under ambient conditions and ease of synthesis have enabled the exploration of the intrinsic properties of antiaromatic molecules. Here, we report the synthesis and properties of meso–meso singly linked porphyrin‐norcorrole hybrids and a triply linked porphyrin‐norcorrole hybrid. The singly linked and triply linked porphyrin‐norcorrole hybrids were fully characterized, including an X‐ray structural analysis. Due to their orthogonal conformation, the singly linked hybrids maintain the individual electronic properties of their porphyrin and norcorrole subunits, while the triply linked hybrid shows a significantly smaller electrochemical HOMO–LUMO gap (0.45 eV) than that of Ni(II) dimesitylnorcorrole (1.08 eV). Furthermore, the triply linked hybrid exhibits singlet diradical characteristics, as confirmed by VT NMR, ESR, and SQUID experiments. [ABSTRACT FROM AUTHOR]

Highlights a study which examined the 1-iodocyclohexanecarbaldehyde's reaction to the acetaldehyde, with various Lewis acids. Identification of the acids; Details on the aldol-type reaction; Reference to the enolates, ketones and esters; Methodology used to conduct the study; Results of the study.

Presents a study on the reaction on a-iodo mixed acetals with allylsilanes in the presence of various Lewis acids. Description of reaction; How mixed iodo acetals can be easily prepared stereoselectivity; Information on the chemoselectivities in the reaction of a-iodo mixed acetals.

Quadruply BN‐fused tetrathia[8]circulenes were synthesized through four‐fold electrophilic borylation. The single‐crystal X‐ray diffraction analysis revealed that the BN‐fused tetrathia[8]circulene with peripheral phenyl groups exhibits crystal polymorphism, in which the circulene core adopts both planar and saddle conformations in the solid state. The experimental and theoretical studies revealed that the weaker aromaticity of azaborine compared with benzene renders the flexibility of the BN‐fused tetrathia[8]circulenes. [ABSTRACT FROM AUTHOR]

Iron hexamesityl-5,15-diazaporphyrin was synthesized through the cross-coupling reaction of tetrabromodiazaporphyrin. The use of chloroiron(III) hexamesityl-5,15-diazaporphyrin as a catalyst for oxidation of cyclooctane showed high performance with a total TON up to 731. The introduction of bulky mesityl groups at β-positions prevented the catalyst deactivation via formation of a μ-oxo dimer. [ABSTRACT FROM AUTHOR]

Self‐assembly of π‐conjugated molecules in solution generally occurs owing to either an enthalpic or an entropic gain; however, designing π‐conjugated systems that simultaneously exhibit enthalpically and entropically favorable self‐assembly behavior is challenging. Herein, the self‐assembly behavior of tetraazatetrathia[8]circulenes is disclosed, which is driven by both enthalpy and entropy. Single‐crystal X‐ray diffraction analysis demonstrated that molecules of these tetraazatetrathia[8]circulenes form face‐to‐face stacked dimers with a 1D columnar structure owing to the circularly arranged dipole moments. Importantly, concentration‐ and temperature‐dependent 1H NMR spectra revealed that the formation of self‐assemblies of tetraazatetrathia[8]circulenes in chloroform and methanol is favored by both enthalpic and entropic factors. The unique association behavior is due to the presence of sp2‐hybridized nitrogen atoms, which weakly coordinate to the hydrogen atoms of these solvents and reduce the π‐electron density of the circulene cores. [ABSTRACT FROM AUTHOR]

We have developed site-selective bromination on the mesityl substituents of 10,20-dimesityl-5,15-diazaporphyrins. Treatment of 10,20-dimesityl-5,15-diazaporphyrin and its nickel(II) complex with a combination of AuBr3/AgOTf induced selective bromination on the mesityl groups. These brominated products can be employed for late-stage modification of the aryl substituents. [ABSTRACT FROM AUTHOR]

Highly stable η²-porphyrin Ru(II) π complexes have been synthesized. The formation of the η² π bond has been facilitated through π-π stacking interactions between the porphyrin and the planar ligand on Ru. π coordination of ruthenium to porphyrin results in dramatic changes in the aromaticity and electronic properties. These properties are controllable via fine-tuning of the ligand on ruthenium. [ABSTRACT FROM AUTHOR]

The article describes Sc(OTf)3-catalyzed reaction of C6F5CHO and pyrrole in an aqueous micellar system. The reaction provided expanded porphyrins with direct bipyrrole linkages of which two novel heptaphyrins have been structurally characterized, thus demonstrating that the aqueous phase offers a new route to novel porphyrins.

The article reports that directly linked multiporphyrinic molecules have received much attention because of their unique properties. An efficient route is developed to meso-meso-linked porphyrins via Ag(I)- mediated coupling of meso-unsubstituted porphyrins. The cross- coupling reaction between bromo- and borylporphyrins is also a powerful tool. Consequently, borylated porphyrins that can be available via borylation of meso-bromoporphyrins are highly useful building blocks. Organoboron chemistry has been booming in fruitful combination with transition metal catalysis.

Examines a rhodium-catalyzed [2 + 2 + 2] cyclotrimerization of alkynes as a test case for an aqueous-organic biphasic system. Diels-Alder type mechanism involving the intermediacy of metallacyclopentadiene complexes; Preparation of a water-soluble rhodium catalyst; Reaction conditions.

Investigates oxidative heck-type reaction involving cleavage of a carbon-phosphorus bond of arylphosphonic acids. Reaction of arylphosphonic acids with a variety of alkenes; Influence of the presence of a palladium catalyst; Formation of phosphoric acid.

Examines the palladium-catalyzed reaction of alkynes with trifurgylgermane and carbon monoxide. Use of internal alkynes; Proposal of a plausible reaction mechanism; Reaction of acylgermanes with secondary amines.

Review: recent progress on borylation of large π-conjugated systems such as porphyrins, perylene bisimides, hexabenzocoronenes and dipyrrins; 98 refs. [ABSTRACT FROM AUTHOR]

NiII-Metallation of dicyanovinylene-bis(meso-aryl)dipyrrin 1 under refluxed toulene conditions resulted in the formation of a bicyclic pyrrolizine ring to afford two isomeric bisNiII expanded porphyrinoid complexes 2a and 2b. Furthermore, acyclic NiII dipyrrin complex 3 was also isolated. The respective structures for 2a, 2b, and 3 were elucidated by X-ray diffraction analysis. Macrocycles 2a and 2b exhibited typical features of aromatic porphyrinoids showing their longest wavelength absorption bands in the near infrared region ranging from 1100 to 1600 nm. [ABSTRACT FROM AUTHOR]

π-Extended dihydrophenazines were successfully prepared by oxidation of 2-( N-arylamino)anthracenes. Their roof-type conformations were revealed by X-ray diffraction analysis, and the analysis of the optical properties indicated the presence of intramolecular charge-transfer processes. Upon chemical oxidation, the electronic absorption dramatically changed in a two-step fashion. The electron spin resonance (ESR) analysis revealed that, depending on the amount of oxidant added, either a paramagnetic radical cation or a diamagnetic dication was generated. The NMR analysis revealed a conformational change upon oxidation, which was supported by theoretical calculations. A three-state electrochromic behavior was observed during the electrochemical oxidation and reduction cycles, showing sequential switching between visible and near-infrared (NIR) absorption properties upon application of electrochemical stimuli. [ABSTRACT FROM AUTHOR]

Examines the reaction of N,N-diethyldicholoacetamide with tributylmanganate (n-Bu3MnLi) to explore employment of trialkylmangate for a consecutive carbon-carbon bond formation. Use of N,N-diethyl-2-chlorohexanamide in 34% yield after the reaction mixture was quenched with 1 M HCI. Information on the reaction process.

Reports on the reaction of vicinal alkoxyiodoalkanes with butyllithium that proceeds in syn fashion to afford alkenes stereospecifically. Interconversion of olefinic geometrical isomers by an anti addition of an iodine-alkoxy moiety to an alkene and subsequent elimination of these groups.

Presents information on the stereoselective synthesis of allyl vinyl ethers from silyl enol ethers through mixed iodo acetals. Outline of experimental methods; Results of experiments conducted; Role of diastereoselectivity in stereoselective synthesis of the enol ether moiety; What led to the formation of (E)-alkenyl ether; Preparation of allyl vinyl etheres by mercury-or acid-catalyzed vinyl ether.

The relationship between the overall electronic structure of π‐conjugated molecules and the arrangement of their constituent elements is of fundamental importance. Establishing rational design guidelines for conjugated hydrocarbons with narrow HOMO‐LUMO gaps is useful to develop near‐infrared (NIR) responsive dyes and redox‐active materials. This study describes the synthesis and properties of three conjugated hydrocarbons, i. e. an indenonaphthoperylene, an indenoterrylene, and a diindenoterrylene. These molecules exhibit NIR absorption despite the absence of significant antiaromaticity and diradical character. Notably, the indenonaphthoperylene exhibits red‐to‐NIR emission in the 620–850 nm region. The indenoterrylene and the diindenoterrylene exhibit NIR absorption tailing to 870 and 940 nm, respectively. Moreover, the effect of the π‐extension of indenoperylene is disclosed in order to propose guidelines for achieving a narrow HOMO‐LUMO gap with negligible antiaromaticity and diradical character. [ABSTRACT FROM AUTHOR]

NiII 3,7,13,17‐tetrapyridyl‐5,15‐diazaporphyrin serves as a double tridentate ligand to PdII ions to provide a pincer‐type bispalladium complex. Electrochemical analysis revealed that the bispalladium complex shows excellent ability to accept electrons and reversible redox properties due to the coordination of the two cationic PdII centers to the meso‐nitrogen atoms. We isolated and characterized one‐ and two‐electron reduction species of the bispalladium complex. The 20π antiaromatic nature of the two‐electron reduction species was confirmed by 1H NMR spectroscopy, UV/Vis‐near‐IR (NIR) absorption spectra, and density functional theory (DFT) calculations. X‐ray diffraction revealed highly twisted structures for the bispalladium complexes regardless of the oxidation state. [ABSTRACT FROM AUTHOR]

NiII 3,7,13,17‐tetrapyridyl‐5,15‐diazaporphyrin serves as a double tridentate ligand to PdII ions to provide a pincer‐type bispalladium complex. Electrochemical analysis revealed that the bispalladium complex shows excellent ability to accept electrons and reversible redox properties due to the coordination of the two cationic PdII centers to the meso‐nitrogen atoms. We isolated and characterized one‐ and two‐electron reduction species of the bispalladium complex. The 20π antiaromatic nature of the two‐electron reduction species was confirmed by 1H NMR spectroscopy, UV/Vis‐near‐IR (NIR) absorption spectra, and density functional theory (DFT) calculations. X‐ray diffraction revealed highly twisted structures for the bispalladium complexes regardless of the oxidation state. [ABSTRACT FROM AUTHOR]

10-Silacorroles were obtained from the Pd-catalyzed silylative cyclization of a bis(α,α′-dibromodipyrrin) NiII precursor with dihydrosilanes. These 10-silacorroles show substantially red-shifted absorption bands relative to those of normal porphyrins and isocorroles. Notably, the corresponding free base and ZnII 10-silacorroles exhibit emissions in the NIR region. Theoretical calculations on these 10-silacorroles revealed the presence of σ*-π* conjugation between the silyl group and the tetrapyrrole π system, which significantly lowers their LUMO energy levels. [ABSTRACT FROM AUTHOR]

This review focuses on the postfunctionalization of porphyrins and related compounds through catalytic and stoichiometric organometallic methodologies. The employment of organometallic reactions has become common in porphyrin synthesis. Palladium-catalyzed cross-coupling reactions are now standard techniques for constructing carbon-carbon bonds in porphyrin synthesis. In addition, iridium- or palladium-catalyzed direct C-H functionalization of porphyrins is emerging as an efficient way to install various substituents onto porphyrins. Furthermore, the copper-mediated Huisgen cycloaddition reaction has become a frequent strategy to incorporate porphyrin units into functional molecules. The use of these organometallic techniques, along with the traditional porphyrin synthesis, now allows chemists to construct a wide range of highly elaborated and complex porphyrin architectures. [ABSTRACT FROM AUTHOR]

Preparation of organic semiconductors by solution processes is desirable to create flexible electronic devices. The use of soluble precursors, which exhibit high solubility in common organic solvents and afford the corresponding semiconducting molecules upon appropriate external stimuli such as heat and light, is a promising approach to realize this goal. Our group recently reported new soluble precursors, namely dinaphtho[1,8‐bc:1′,8′‐ef]thiepine bisimide (DNTBI) and its sulfoxide, which afforded perylene bisimide, a representative n‐type organic semiconductor, upon heating or light‐irradiation. In this work, we report the second‐generation synthetic route to DNTBI, which enabled gram‐scale and diversity‐oriented preparation of various N‐substituted DNTBIs. We also disclosed the suitable combination of leaving group (S or SO), external stimulus (heat or light), and N‐substituent to realize efficient charge transport. [ABSTRACT FROM AUTHOR]

We have synthesized NiII and AlIII 10-azacorroles through coordination-induced cyclisation of nitrogen-bridged bisdipyrrins. AlIII 10-azacorrole displayed contrasting optoelectronic behaviours from NiII 10-azacorrole, underlining the different electronic effects of the azacorrole ligand from the porphyrin. [ABSTRACT FROM AUTHOR]

Visible light-mediated α-arylation of α,β-unsaturated imides is achieved via aminium radicals generated from diarylalkylamines using a photoredox catalyst. On the basis of emission quenching experiments, a plausible pathway of the reaction is discussed. [ABSTRACT FROM AUTHOR]

Post‐functionalization of porphyrinoid catalysts provides a powerful tool for fine‐tuning their electronic structure. We have succeeded in the stepwise methylation of the peripheral nitrogen atoms in ruthenium and cobalt 5,15‐diazaporphyrins. The axial coordination of an anion to the metal center accelerates the second methylation through charge neutralization. N‐Methylation of the diazaporphyrin complexes effectively controls their electron deficiency, Lewis acidity, and catalytic activity. [ABSTRACT FROM AUTHOR]

The switching of cyclic π‐conjugation pathways using external stimuli is an attractive research topic in the field of organic chemistry. Here, we synthesized C4h‐symmetric octaaza[8]circulenes with four peripherally arranged amidine moieties that exhibit enhanced antiaromaticity upon protonation. Titration experiments with methanesulfonic acid revealed the formation of the tetraprotonated forms of the octaaza[8]circulenes in solution. Single‐crystal X‐ray diffraction analyses and theoretical calculations indicated that the contribution of the 8π antiaromatic character of the octaaza[8]circulenes is enhanced by the delocalization of charge through the protonation of the pyridine rings. [ABSTRACT FROM AUTHOR]

We synthesised thionium-ion embedded aromatic porphyrinoids: a free-base 5-thiaporphyrinium cation and its zinc complex. The sulphur atom effectively participates in the macrocyclic π-conjugation. Fluorescence quantum yields of thiaporphyrinium cations were lower than 1% unlike oxaporphyrinium cations. Detailed photophysical analysis and DFT calculations clarified the vibrational mode regarding the out-of-plane motion of the sulphur atom induced ultrafast quenching of the excited state in comparison to the corresponding oxaporphyrinium cations. [ABSTRACT FROM AUTHOR]

Using artificial hemes for the reconstruction of natural heme proteins represents a fascinating approach to enhance the bioactivity of the latter. We report the synthesis of various metal 5‐oxaporphyrinium cations as cofactors, and a cobalt 5‐oxaporphyrinium cation was successfully incorporated into the heme‐acquisition protein (HasA) secreted by Pseudomonas aeruginosa. We hypothesize that the oxaporphyrinium cation strongly binds to the HasA‐specific outer membrane receptor (HasR) due to its cationic charge, which prevents the subsequent acquisition of heme. In fact, the reconstructed HasA inhibited the growth of Pseudomonas aeruginosa and even of multidrug‐resistant P. aeruginosa. [ABSTRACT FROM AUTHOR]

Using artificial hemes for the reconstruction of natural heme proteins represents a fascinating approach to enhance the bioactivity of the latter. We report the synthesis of various metal 5‐oxaporphyrinium cations as cofactors, and a cobalt 5‐oxaporphyrinium cation was successfully incorporated into the heme‐acquisition protein (HasA) secreted by Pseudomonas aeruginosa. We hypothesize that the oxaporphyrinium cation strongly binds to the HasA‐specific outer membrane receptor (HasR) due to its cationic charge, which prevents the subsequent acquisition of heme. In fact, the reconstructed HasA inhibited the growth of Pseudomonas aeruginosa and even of multidrug‐resistant P. aeruginosa. [ABSTRACT FROM AUTHOR]

For the creation of next‐generation organic electronic materials, the integration of π‐systems has recently become a central theme. Such functional materials can be assembled by supramolecular polymerization when aromatic π‐systems are used as monomers, and the properties of the resulting supramolecular polymer strongly depend on the electronic structure of the monomers. Here, we demonstrate the construction of a supramolecular polymer consisting of an antiaromatic π‐system as the monomer. An amide‐functionalized NiII norcorrole derivative formed a one‐dimensional supramolecular polymer through π‐π stacking and hydrogen‐bonding interactions, ensuring the persistency of the conducting pathway against thermal perturbation, which results in higher charge mobility along the tightly bound linear aggregates than that of the aromatic analogue composed of ZnII porphyrins. [ABSTRACT FROM AUTHOR]

For the creation of next‐generation organic electronic materials, the integration of π‐systems has recently become a central theme. Such functional materials can be assembled by supramolecular polymerization when aromatic π‐systems are used as monomers, and the properties of the resulting supramolecular polymer strongly depend on the electronic structure of the monomers. Here, we demonstrate the construction of a supramolecular polymer consisting of an antiaromatic π‐system as the monomer. An amide‐functionalized NiII norcorrole derivative formed a one‐dimensional supramolecular polymer through π‐π stacking and hydrogen‐bonding interactions, ensuring the persistency of the conducting pathway against thermal perturbation, which results in higher charge mobility along the tightly bound linear aggregates than that of the aromatic analogue composed of ZnII porphyrins. [ABSTRACT FROM AUTHOR]

A diazo-bridgedBODIPY dimer and tetramer were prepared by theoxidative coupling reaction of β-amino-substituted BODIPYs.The structure of the dimer was elucidated by X-ray diffraction analysis,showing its coplanar orientation of two BODIPY units. Effective extensionof π-conjugation was confirmed by optical and electrochemicalinvestigations. [ABSTRACT FROM AUTHOR]

A shapely figure: A [32]octaphyrin(1.0.1.0.1.0.1.0) bis[palladium(II)] complex was selectively obtained through a metal‐templated intermolecular homocoupling of a α,α′‐dibromodipyrrin palladium(II) complex without formation the norcorrole. The weak antiaromatic character of the figure‐eight [32]octaphyrin(1.0.1.0.1.0.1.0) system has been elucidated by spectroscopic measurements and DFT calculations. [ABSTRACT FROM AUTHOR]