Cogwheel Mechanism of Helical Self-Organization is Thermodynamically Controlled, Self-Repairing, and Universal.

The cogwheel mechanism of helical self-organization, reported by us, generates columns with the alkyl chains of their components parallel to the column axis. This mechanism disregards the enantiomeric purity of constituents and, under suitable design, provides the fastest rate of helical self-organization. Here, we investigate the supramolecular structure of a thermodynamically controlled helical self-organization system. Unexpectedly, we found that this system follows a cogwheel mechanism of helical self-organization that does not contain the two key parameters of the cogwheel mechanism: the length of the alkyl group of the self-assembling dendron identical to the helical half-pitch (hhp) of the column and the presence of chiral branches pointing toward the column center. Unpredictably, we uncovered that the presence of chiral branching points and strict alkyl chain lengths is not a requirement of the cogwheel mechanism. A self-repairing process provides access to a constant hhp via a shorter and longer alkyl chain length than the originally exact demanded value, which together with the lack of branching point(s) demonstrates the universality of the cogwheel mechanism of helical self-organization. Applications derived from this concept are envisioned.

Electro-oxidative Methylation of 2-Isocyanobiaryls Using N,N-dimethylformamide (DMF) as Carbon Source: Synthesis of 6-Methylphenanthridines.

A benign electrochemical method to access 6-methylphenanthridines from 2-isocyanobiaryls using N,N-dimethylformamide (DMF) as a methyl source is reported. The protocol operates at ambient temperature without the need for harmful methylating reagents. Mechanistic studies suggested that DMF delivered a methylene synthon, followed by reduction at the cathode and tautomerization. The method offers environmental benefits by avoiding metal-based reagents and harsh conditions.

Base-catalyzed diastereodivergent thia-Michael addition to chiral ß-trifluoromethyl-α,ß-unsaturated N-acylated oxazolidin-2-ones.

Base-catalyzed diastereodivergent thia-Michael addition of thiols to chiral ß-trifluoromethyl-α,ß-unsaturated N-acylated oxazolidin-2-ones is reported. By tuning the base-catalyst (i-Pr2NEt, DABCO, or P2-t-Bu), a range of chiral thia-Michael adducts was synthesized in good yields with high diastereoselectivities. A plausible mechanism was proposed on the basis of the experimental results. This work is complementary to the existing methods offering advantages, e.g., switchable diastereoselectivity using a readily synthesized chiral starting material, a cheap and readily available base catalyst, and a simple and practical operation, enabling synthetic application in organic synthesis.

Cascade Oxidative Trifluoromethylthiolation and Cyclization of 3-Alkyl-1-(2-(alkynyl)phenyl)indoles.

Persulfate-promoted radical cascade trifluoromethylthiolation and cyclization of 3-alkyl-1-(2-(alkynyl)phenyl)indoles with AgSCF3 were investigated. This protocol provides a novel route to CF3S-substituted indolo[1,2-a]quinoline-7-carbaldehydes and CF3S-substituted indolo[1,2-a]quinoline-7-methanone derivatives via the formation of the C-SCF3 bond and C-C bond and benzylic carbon oxidation in a single step. This reaction can accommodate a broad range of functional groups. The single-crystal X-ray diffraction data confirm the chemical structure of the product. A scale-up experiment and radical inhibition experiments were operated in the reaction system. Photophysical properties of some selected 5-((trifluoromethyl)thio)indolo[1,2-a]quinoline-7-carbaldehydes were studied by UV-visible and fluorescence spectroscopy.

Electrochemical trifluoromethylation of 2-isocyanobiaryls using CF3SO2Na: synthesis of 6-(trifluoromethyl)phenanthridines.

An efficient trifluoromethylation of 2-isocyanobiaryls was developed through the constant current electrolysis, employing sodium trifluoromethanesulfinate (CF3SO2Na) as the trifluoromethyl source. The method enabled the syntheses of a series of 6-(trifluoromethyl)phenanthridine derivatives in moderate to high yields under metal- and oxidant-free conditions. A gram-scale synthesis highlights the synthetic versatility of the reported protocol.

Diastereoselective Addition of PhSCF2SiMe3 to Chiral N-tert-Butanesulfinyl Ketimines Derived from Isatins: Synthesis of Enantioenriched gem-Difluoromethylenated Spiro-pyrrolidinyl and Spiro-piperidinyl Oxindoles.

A convenient and efficient synthetic strategy to prepare enantioenriched gem-difluoromethylenated spiro-pyrrolidinyl and spiro-piperidinyl oxindoles is described. Fluoride-mediated diastereoselective nucleophilic addition of PhSCF2SiMe3 to chiral N-tert-butanesulfinyl ketimines derived from isatins was a key step and provided diastereomeric adducts, which were readily separable. Removal of the chiral sulfinyl group followed by structural manipulation afforded chiral gem-difluoromethylenated spiro-pyrrolidinyl and spiro-piperidinyl oxindoles.

Color-tunable emissive heptagon-embedded polycyclic aromatic dicarboximides.

Heptagon-embedded polycyclic aromatic dicarboximides were developed as new push-pull fluorescent dyes through palladium-catalysed [4+3] annulation followed by nucleophilic substitution. The introduction of a seven-membered ring in these push-pull systems can efficiently modulate the optical properties leading to an enhancement of the fluorescence quantum yields up to 0.93 with color tunable emission covering the visible-NIR spectrum.

Self-Sorting Supramolecular Polymerization: Helical and Lamellar Aggregates of Tetra-Bay-Acyloxy Perylene Bisimide.

A new perylene bisimide (PBI), with a fluorescence quantum yield up to unity, self-assembles into two polymorphic supramolecular polymers. This PBI bears four solubilizing acyloxy substituents at the bay positions and is unsubstituted at the imide position, thereby allowing hydrogen-bond-directed self-assembly in nonpolar solvents. The formation of the polymorphs is controlled by the cooling rate of hot monomer solutions. They show distinctive absorption profiles and morphologies and can be isolated in different polymorphic liquid-crystalline states. The interchromophoric arrangement causing the spectral features was elucidated, revealing the formation of columnar and lamellar phases, which are formed by either homo- or heterochiral self-assembly, respectively, of the atropoenantiomeric PBIs. Kinetic studies reveal a narcissistic self-sorting process upon fast cooling, and that the transformation into the heterochiral (racemic) sheetlike self-assemblies proceeds by dissociation via the monomeric state.

Alkanethiol-Mediated Cyclization of o-Alkynylisocyanobenzenes: Synthesis of Bis-Thiolated Indole Derivatives.

Reactions of o-alkynylisocyanobenzenes with a variety of alkanethiols (Alk-SH) provide the corresponding bis-thiolated indole derivatives. The advantages of the reaction include metal-free, room-temperature, mild reaction conditions and broad functional group compatibility. The reaction proceeds via nucleophilic addition of an alkanethiol to an isonitrile moiety, 5-exo cyclization, followed by nucleophilic addition of an alkanethiol to a 3-alkylidene indole intermediate. Density functional calculations on the electronic structures and relative free energies of 5-exo and 6-endo cyclization pathways support that the 5-exo cyclization is preferable.

Synthesis of Indolo- and Benzothieno[2,3-b]quinolines by a Cascade Cyclization of o-Alkynylisocyanobenzene Derivatives.

A new synthetic approach for the synthesis of indolo[2,3-b]quinolines and benzothieno[2,3-b]quinolines has been developed by employing the freshly prepared o-alkynylisocyanobenzenes derived from o-alkynylformamide derivatives as substrates. The synthetic transformations involved chloride-ion-triggered 6-endo cyclization of o-alkynylisocyanobenzenes to generate 2-chloroquinolines in situ, which further cyclized intramolecularly with nitrogen or sulfur atom via a cascade process to provide the corresponding indolo[2,3-b]quinolines and benzothieno[2,3-b]quinolines, respectively, in moderate to excellent yields.

Sequence-Defined Dendrons Dictate Supramolecular Cogwheel Assembly of Dendronized Perylene Bisimides.

A dendronized perylene bisimide (PBI) that self-organizes into hexagonal arrays of supramolecular double helices with identical single-crystal-like order that disregards chirality was recently reported. A cogwheel model of self-assembly that explains this process was proposed. Accessing the highly ordered cogwheel phase required very slow heating and cooling or extended periods of annealing. Analogous PBIs with linear alkyl chains did not exhibit the cogwheel assembly. Here a library of sequence-defined dendrons containing all possible compositions of linear and racemic alkyl chains was employed to construct self-assembling PBIs. Thermal and structural analysis of their assemblies by differential scanning calorimetry (DSC) and fiber X-ray diffraction (XRD) revealed that the incorporation of n-alkyl chains accelerates the formation of the high order cogwheel phase, rendering the previously invisible phase accessible under standard heating and cooling rates. Small changes to the primary structure, as constitutional isomerism, result in significant changes to macroscopic properties such as melting of the periodic array. This study demonstrated how changes to the sequence-defined primary structure, including the relocation of methyl groups between two constitutional isomers, dictate tertiary and quaternary structure in hierarchical assemblies. This led to the discovery of a sequence that self-organizes the cogwheel assembly much faster than even the corresponding homochiral compounds and demonstrated that defined-sequence, which has long been recognized as a determinant for the complex structure of biomacromolecules including proteins and nucleic acids, plays the same role also in supramolecular synthetic systems.

Supramolecular Spheres Self-Assembled from Conical Dendrons Are Chiral.

Frank-Kasper phases and liquid quasicrystals self-organize from supramolecular spheres of dendrimers, block copolymers, surfactants and other self-assembling molecules. These spheres are expected to be achiral due to their isotropic shape. Nevertheless, supramolecular spheres from short helical stacks of crown-like dendrimers self-organize a Pm3̅ n cubic (Frank-Kasper A15) phase which exhibits chirality on the macroscopic scale. However, the chirality of classic isotropic supramolecular micellar-like spheres, generated from conical dendrons, is unknown. Here we report a library of second and third generation biphenylpropyl dendrons with chiral groups at their apex that produces single-handed chiral supramolecular spheres. Up to 480 conical dendrons self-assemble to form micellar-like spheres, with a molar mass of up to 1.1 × 106 g/mol, that self-organize into a Pm3̅ n phase with chirality detectable on the macroscopic scale. This demonstration of chirality in micellar-like spheres of a Frank-Kasper phase raises the fundamental question whether micellar-like spheres forming 3D phases generated from other soft matter such as block copolymers, surfactants, and other molecules are chiral.

Sulfinates and thiocyanates triggered 6-endo cyclization of o-alkynylisocyanobenzenes.

Diverse 2-sulfonyl- and 2-thiocyanato-3-substituted quinolines were synthesized from o-alkynylisocyanobenzenes by nucleophilic addition of the respective sulfinate sodium salts and ammonium thiocyanate to the isocyanide moiety followed by cyclization. The salient features of the methodology include metal-free, ambient temperature and mild reaction conditions, ease of reagent handling, and broad functional group tolerance.

Impact of 2-Ethylhexyl Stereoisomers on the Electrical Performance of Single-Crystal Field-Effect Transistors.

Many organic semiconductors (OSCs) inherit chiral alkyl chains, which ensure the desirable high solubility for solution-processing but may also lead to disorder, inhomogeneous film-formation, as well as interfacial defects due to the presence of mixtures of stereoisomers or diastereomers, which impair their peak performance. Here, single-crystal field-effect transistors (SCFETs) of a diketopyrrolopyrrole-based organic semiconductor with chiral 2-ethylhexyl substituents by sublimation in air and organic ribbon mask method are fabricated. Devices of the mesomer (R/S), both enantiomers (R/R, S/S), as well as mixtures of these three stereoisomers measured under ambient conditions exhibit all appreciable p-channel charge carrier mobilities of > 0.1 cm2 V-1 s-1 despite different packing arrangement in the R/S, R/R (or S/S), and racemate crystal structures. These results suggest a surprising tolerance for isomeric impurities. The highest literature-reported p-channel mobility so far for a diketopyrrolopyrrole-based OSC of 3.4 cm2 V-1 s-1 (Ion /Ioff of 1 × 106 ) is, however, only obtained for the pure R/S mesomer, illustrating the inherent potential of stereochemical purity. These results on SCFETs are further substantiated by studies on organic thin-film transistors (OTFTs) of pure and mixed thin films of the different stereoisomers.

Synthesis of 3-substituted quinolin-2(1H)-ones via the cyclization of o-alkynylisocyanobenzenes.

A facile synthesis of various functionalized 3-substituted quinolin-2(1H)-ones through Ag(i) nitrate-catalyzed cyclization of o-alkynylisocyanobenzenes is described. The reaction allows rapid and convenient access to 3-substituted quinolin-2(1H)-one scaffolds in moderate to good yields.

Self-assembly of multi-stranded perylene dye J-aggregates in columnar liquid-crystalline phases.

Many discoid dyes self-assemble into columnar liquid-crystalline (LC) phases with packing arrangements that are undesired for photonic applications due to H-type exciton coupling. Here, we report a series of crystalline and LC perylene bisimides (PBIs) self-assembling into single or multi-stranded (two, three, and four strands) aggregates with predominant J-type exciton coupling. These differences in the supramolecular packing and optical properties are achieved by molecular design variations of tetra-bay phenoxy-dendronized PBIs with two N-H groups at the imide positions. The self-assembly is driven by hydrogen bonding, slipped π-π stacking, nanosegregation, and steric requirements of the peripheral building blocks. We could determine the impact of the packing motifs on the spectroscopic properties and demonstrate different J- and H-type coupling contributions between the chromophores. Our findings on structure-property relationships and strong J-couplings in bulk LC materials open a new avenue in the molecular engineering of PBI J-aggregates with prospective applications in photonics.

TBAI/TBHP-Mediated Cascade Cyclization toward Sulfonylated Indeno[1,2-c]quinolines.

Treatment of ortho-amino-substituted aryldiyne derivatives with sulfonyl hydrazides in the presence of tetrabutylammonium iodide (TBAI) and tert-butyl hydroperoxide (TBHP) led to a cascade cyclization reaction to yield sulfonylated indeno[1,2-c]quinolines in moderate to good yields. The features of the methodology include metal-free reaction, the ease of reagent handling, and a broad functional group tolerance.

Synthesis of N-alkyl-3-sulfonylindoles and N-alkyl-3-sulfanylindoles by cascade annulation of 2-alkynyl-N,N-dialkylanilines.

An efficient and metal-free approach to N-alkyl-3-sulfonylindoles and N-alkyl-3-sulfanylindoles from 2-alkynyl-N,N-dialkylanilines has been developed. In the presence of iodine and tert-butylhydroperoxide (TBHP), a variety of 2-alkynyl-N,N-dialkylanilines underwent a cascade radical annulation to yield 3-arylsulfonylindoles. In contrast, 3-arylsulfanylindoles were conveniently prepared by iodine mediated electrophilic annulation reactions. The present protocol uses the economical and environmentally friendly I2-TBHP or I2 system, and potentially bioactive N-alkyl-3-sulfonylindoles and N-alkyl-3-sulfanylindoles with various functional groups were successfully synthesized in moderate to good yields.

Self-interrupted synthesis of sterically hindered aliphatic polyamide dendrimers.

2,2-Bis(azidomethyl)propionic acid was prepared in four steps and 85% yield from the commercially available 2,2-bis(hydroxymethyl)propionic acid and used as the starting building block for the divergent, convergent, and double-stage convergent-divergent iterative methods for the synthesis of dendrimers and dendrons containing ethylenediamine (EDA), piperazine (PPZ), and methyl 2,2-bis(aminomethyl)propionate (COOMe) cores. These cores have the same multiplicity but different conformations. A diversity of synthetic methods were used for the synthesis of dendrimers and dendrons. Regardless of the method used, a self-interruption of the synthesis was observed at generation 4 for the dendrimer with an EDA core and at generation 5 for the one with a PPZ core, whereas for the COOMe core, self-interruption was observed at generation 6 dendron, which is equivalent to generation 5 dendrimer. Molecular modeling and molecular-dynamics simulations demonstrated that the observed self-interruption is determined by the backfolding of the azide groups at the periphery of the dendrimer. The latter conformation inhibits completely the heterogeneous hydrogenation of the azide groups catalyzed by 10% Pd/carbon as well as homogeneous hydrogenation by the Staudinger method. These self-terminated polyamide dendrimers are enzymatically and hydrolytically stable and also exhibit antimicrobial activity. Thus, these nanoscale constructs open avenues for biomedical applications.

A Columnar Liquid-Crystal Phase Formed by Hydrogen-Bonded Perylene Bisimide J-Aggregates.

A new perylene bisimide (PBI) dye self-assembles through hydrogen bonds and π-π interactions into J-aggregates that in turn self-organize into liquid-crystalline (LC) columnar hexagonal domains. The PBI cores are organized with the transition dipole moments parallel to the columnar axis, which is an unprecedented structural organization in π-conjugated columnar liquid crystals. Middle and wide-angle X-ray analyses reveal a helical structure consisting of three self-assembled hydrogen-bonded PBI strands that constitute a single column of the columnar hexagonal phase. This remarkable assembly mode for columnar liquid crystals may afford new anisotropic LC materials for applications in photonics.