BF2 complexes of aryl-substituted dipyrrolyldiketones (3a−c, 5a−d) have been synthesized by the condensation arylpyrroles obtained Suzuki cross-coupling reactions with malonyl chloride, followed treatment BF3·OEt2. The binding constants (Ka11) (3a−c) for various anions (Cl-, Br-, CH3CO2-, H2PO4-, and HSO4-) in CH2Cl2 decrease order Ph (3a) > o-tolyl (3b) 2,6-Me2Ph (3c), possibly because differences planarity number interacting o-CH units at sites. Aryl-substituted receptors exhibit a [1+1]...

Pillars of salts: By combining planar cations and anionic structures based on π-conjugated acyclic dipyrroles containing an anion, charge-by-charge assemblies could be formed (see picture). Not only crystals but also soft materials, such as supramolecular gels thermotropic liquid crystals, made by this method.

Two pentamethine dyes with nearly identical structures but slightly different dipole moments were prepared as ion pairs. The pairs provided charge-segregated assemblies stabilized by dipole-dipole interactions between the positively charged π-electronic systems. stacking structure of bromo-substituted cation was more a larger moment, suggested energy decomposition analysis. Depending on packing arrangements, highly electric conductive properties observed owing to structures, also correlated...

Abstract Anion‐responsive pyrrole‐based linear receptor oligomers were newly synthesized and their anion‐driven dynamic conformation changes investigated. Phenylene‐bridged dimers a tetramer of dipyrrolyldiketone boron complexes as π‐conjugated acyclic anion receptors formed helical structures in the solid solution states. In fact, single‐crystal X‐ray analyses receptor‐anion exhibited various structures, such [1+1]‐ [1+2]‐type single helices [2+2]‐type double helix according to lengths...

Asymmetrie durch Ionenpaare: Auf den Zusatz chiraler Ammoniumchloride und -bromide hin entstehen in Lösungen pyrrolbasierter π-konjugierter linearer Oligomere helikale Strukturen, wobei die Bildung diastereomerer Ionenpaare mit chiralen Kationen für eine asymmetrische Induktion sorgt (siehe Bild). Diese zeigen einen Circulardichroismus (CD) stark circular polarisierte Lumineszenz (CPL) glum-Werten über 0.1.

This feature article summarizes the recent progress in study of ion-pairing assemblies based on π-electronic ion pairs, including anion complexes molecules. Recently, ionic self-assembly (or assembly) has been widely investigated and utilized fabrication various functional materials soft materials, surface morphologies organic-inorganic hybrid materials. It is significantly important to precisely design synthesize charged systems for obtaining highly organized assemblies, but development...

Abstract Ion-pairing assemblies consisting of appropriately designed π-electronic ionic species afford various functional supramolecular including crystals and soft materials based on the anisotropic orientation through electrostatic other weak noncovalent interactions. Organized comprising as dimension-controlled provide unique tunable mesophases electronic properties. As components ion-pairing assemblies, ion pairs are important have been prepared (i) synthesis units bearing substituents,...

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Acyclic anion receptors (BF2 complexes of dipyrrolyldiketones) with heteroaryl moieties synthesized by using cross-coupling reactions have unique electronic states, as observed in UV/vis absorption spectra. Among heteroaryl-substituted derivatives, a pyrrolyl-substituted receptor exhibits an extremely high affinity for anions solution.

Rod-like π-conjugated anion-responsive acyclic oligopyrroles have been reported to form stacked disk-like components that result in the formation of discotic columnar mesophases as thermotropic liquid crystals.

Assemblies of planar ions: Anion complexes appropriately designed pyrrole-based π-conjugated molecules provided liquid crystalline materials by combination with a cation based on charge-by-charge and charge-segregated assemblies (see figure). The series charge-based exhibited well-balanced ambipolar charge carrier transport behavior relatively high mobilities. Detailed facts importance to specialist readers are published as "Supporting Information". Such documents peer-reviewed, but not...

Abstract Pentacyanocyclopentadienide (PCCp − ), a stable π‐electronic anion, provided various ion‐pairing assemblies in combination with cations. PCCp ‐based exist as single crystals and mesophases owing to interionic interactions aliphatic cations variety of geometries, substituents, electronic structures. Single‐crystal X‐ray analysis revealed that formed cation‐dependent arrangements contributions from charge‐by‐charge charge‐segregated assembly modes for ion pairs cations, respectively....

Induced-fit or conformational selection is of profound significance in biological regulation. Biological receptors alter their conformation to respond the shape and electrostatic surfaces guest molecules. Here we report a water-soluble artificial molecular host that can sensitively size, shape, charged state The host, i.e. nanocube, an assembled structure consisting six gear-shaped amphiphiles (GSAs). This nanocube expand contract its size upon encapsulation neutral anionic molecules with...

The prologue and progress of π-electronic ion-pairing assemblies, including synthesis ions, preparation ion pairs, fabrication assemblies as crystals, gels liquid crystals their characteristic properties, are summarized.

Abstract Cationic BN‐embedded polycyclic aromatic hydrocarbons (BN‐PAH + s) were synthesized from a nitrogen‐containing macrocycle via pyridine‐directed tandem C−H borylation. Incorporating BN into PAH resulted in remarkable hypsochromic shift due to an increase the LUMO energy and symmetry changes of HOMO LUMO. Electrophilic substitution or anion exchange BN‐PAH possessing tetrabromoborate as counter ( [BBr 4 − ] ) afforded air‐stable BN‐PAH/PAH s. Of these, [TfO allowed reversible...

Dipyrrolyldiketone BF(2) complexes acting as acyclic anion receptors form supramolecular assemblies with structures and properties that are dependent on the pyrrole β-substituents. In particular, although β-alkyl substituents interfered formation of stable gel states, introduction fluorine moieties induced a when compared to β-unsubstituted receptor.

Porphyrin-AuIII complexes were found to act as π-electronic cations, which can combine with various counteranions, including anions. Single-crystal X-ray analyses revealed the formation of assemblies contributions charge-by-charge and charge-segregated assemblies, depending on geometry electronic state counteranions. possessing aliphatic alkyl chains formed dimension-controlled ion-pairing thermotropic liquid crystals, whose ionic components highly organized by π-π stacking electrostatic...

π-Electronic ion pairs comprising porphyrin-based π-electronic anions have exhibited characteristic assembling modes and resulting electronic properties such as solid-state absorption photoinduced electron transfer.

Quinoidal molecules based on dipyrrolyldiketone boron complexes (QPBs), in which pyrrole units were connected by a partially conjugated system as singlet spin coupler, synthesized. QPB, was stabilized the introduction of benzo unit at β-positions, formed closed-shell tautomer conformation that showed near-infrared absorption. The deprotonated species, monoanion QPB- and dianion QPB2-, showing over 1000 nm absorption, addition bases, providing ion pairs combination with countercations....

In this study, anion‐responsive π‐conjugated macrocycles were synthesized to demonstrate anion‐binding and ion‐pairing properties along with the ordered structures. Ion‐pairing charge‐by‐charge assembly of a [1+2]‐type complex macrocycle as pseudo π‐electronic anion countercation was revealed by single‐crystal X‐ray analysis. Further, two‐dimensional (2D) arrays bearing alkoxy chains, exhibiting anion‐driven disordered structures, constructed on highly oriented pyrolytic graphite (HOPG)...

Journal of Porphyrins and PhthalocyaninesAccepted Papers Free AccessZwitterionic π-electronic system based on porphyrin AuIII complexHiromitsu Maeda, Naoya Hiraishi, Yohei Haketa, Yoichi Kobayashi, Yukihide Ishibashi, Tsuyoshi Asahi, Nobuhiro YasudaHiromitsu Hiraishi Search for more papers by this author , Haketa Kobayashi Ishibashi Asahi Yasuda https://doi.org/10.1142/S1088424625500154Cited by:0 (Source: Crossref) PreviousNext AboutFiguresReferencesRelatedDetailsView articleSupplemental...

Selective iodination at the α-pyrrole positions of dipyrrolyldiketone BF2 complexes is a key procedure to afford mono- and bisiodinated derivatives as starting materials coupling reactions for various utility molecules covalently linked oligomer systems. Iodination can also be applied phenylene-bridging receptor dimer obtain selectively iodinated terminal position(s).

Assemblies comprising anion complexes of π-extended oligopyrrole derivatives and counter cations, as well those anion-free receptor molecules, exhibited the formation mesophases based on columnar structures using electrostatic π-π interactions.

Norcorroles with 3,4,5-trialkoxyphenyl moieties were synthesized to form thermotropic liquid crystals (LCs), in which triple-decker stacking structures formed. The LC state exhibited discotic columnar exhibit high electric conductivity.