Preparation and structural properties of 7,8-dioxa[6]helicenes and 7a,14c-dihydro-7,8-dioxa[6]helicenes.

The potentially chiral 7,8-dioxa[6]helicenes 1-1c have been prepared by oxidation of their precursors the 7a,14c-dihydro-7,8-dioxa[6]helicenes 3. The crystal structure determination of 3b cis-7a,14c-dihydro-3,12-dibromo-7,8-dioxa[6]helicene unambiguously confirms the cis configuration of the 7a,-14c hydrogens in compounds 3 as previously implied from NMR measurements and also shows that 3b crystallizes in a chiral conformation in the solid state. Selective deuteration of the sterically crowded 1,14 positions of 7,8-dioxa[6]helicene 1 influenced the crystal structure. The deuterium labeled compound D2-1 exhibits a disordered structure, whereas 1 had been found to crystallize in a complex structure which can be described as an analogous partly ordered modulated superstructure. When dehydrogenation of compound 3 to obtain compound 1 was attempted, harsh synthetic conditions gave the unexpected halogenated compounds 5-chloro-7,8-dioxa[6]helicene 1c and cis-7a,14c-dibromo-7,8-dioxa[6]helicene 3c. Compounds 1d and 3b were identified by solving their crystal structure.     

Local aromaticity of [n]acenes, [n]phenacenes, and [n]helicenes (n = 1-9)

The local aromaticity of the six-membered rings in three series of benzenoid compounds, namely, the [n]acenes, [n]phenacenes, and [n]helicenes for n = 1-9, has been assessed by means of three probes of local aromaticity based on structural, magnetic, and electron delocalization properties. For [n]acenes our analysis shows that the more reactive inner rings are more aromatic than the outer rings. For [n]phenacenes, all indicators of aromaticity show that the external rings are the most aromatic. From the external to the central ring, the local aromaticity varies in a damped alternate way. The trends for the [n]helicene series are the same as those found for [n]phenacenes. Despite the departure from planarity in [n]helicenes, only a very slight loss of aromaticity is detected in [n]helicenes as compared to the corresponding [n]phenacenes. Finally, because of magnetic couplings between superimposed six-membered rings in the higher members of the [n]helicenes series, we have demonstrated that the NICS indicator of aromaticity artificially increases the local aromaticity of their most external rings.     

Compressing a Non-Planar Aromatic Heterocyclic [7]Helicene to a Planar Hetero[8]Circulene

This work describes a synthetic approach where a non-planar aromatic heterocyclic [7]helicene is compressed to yield a hetero[8]circulene containing an inner antiaromatic cyclooctatetraene (COT) core. This [8]circulene consists of four benzene rings and four heterocyclic rings, and it is the first heterocyclic [8]circulene containing three different heteroatoms. The synthetic pathway proceeds via a the flattened dehydro-hetero[7]helicene, which is partially a helicene and partially a circulene: it is non-planar and helically chiral as helicenes, and contains a COT motif like [8]circulenes. The antiaromaticity of the COT core is confirmed by nucleus independent chemical shift (NICS) calculations. The planarization from a helically π-conjugated [7]helicene to a fully planar heterocyclic [8]circulene significantly alters the spectroscopic properties of the molecules. Post-functionalization of the [7]helicenes and the [8]circulenes by oxygenation of the thiophene rings to the corresponding thiophene-sulfones allows an almost complete fluorescence emission coverage of the visible region of the optical spectrum (400–700 nm).     

Hélicènes pontés: Ethano-3,15- et oxa-2-propano-3,15-[7]hélicène. Synthèse,spectrographie 1H-RMN. et étude par diffraction aux rayons X

Bridged helicenes: 3,15-ethano- and 3,15-(2-oxapropano)-[7]helicene The title compounds ( 35 and 33 , see Scheme 4) have been synthesized from a common intermediate: 3,15-dimethoxycarbonyl-[7]helicene ( 26 ). The conformation of the bridged [7]helicenes (X-ray diffraction) and their ¹H-NMR. spectra have been compared to the conformation and ¹H-NMR. spectra of [7]helicene and 3,15-dimethyl-[7]helicene ( 10 ).     

Distinction between homochiral and heterochiral dimers of 1-aza[n]helicenes (n = 1–7) with alkaline cations

A theoretical study of the chiral distinction between the homochiral and heterochiral dimers of the 1-aza[n]helicenes, with n = 1–7, glued with lithium, sodium, and potassium cations has been carried out by means of DFT calculations up to M05-2x/6-311+G(d) computational level. The electronic characteristic of the isolated helicenes has been explored. The chiral distinction is dependent on the size of the helicene and the cation used with the largest values obtained for the 1-aza[6]helicene bound to lithium cation.     

Band gap of carbon-sulfur [N]helicenes

Asymmetric synthesis of (-)-[9]helicene, as well as preparation of its lower homologues, completes the series of carbon-sulfur [5]-, [7]-, [9]-, and [11]helicenes. Spectroscopic and electrochemical studies of this series provide an absorption onset-based band gap, E(g) = 3.40 eV, for a cross-conjugated (C(2)S)(n) helix; this value may be compared to E(g) = 3.59 eV obtained from TD-DFT computed excitation energies for a series of dimethyl-substituted [n]helicenes (n ≤ 31).     

Dinor[7]helicene and Beyond: Divergent Synthesis of Chiral Diradicaloids with Variable Open-Shell Character

Diradicaloid helicenes constructed formally by non-benzenoid double π-extension of phenanthrene were synthesized by a common strategy involving double electrophilic benzannulation. Steric effects in the second benzannulation step led to considerable structural diversity among the products, yielding a symmetrical dinor[7]helicene 1 and two isomeric unsymmetrical double helicenes 2 and 3 , containing a nor[5]helicene and [4]helicene fragment, respectively, in addition to a common nor[6]helicene motif. Geometries, configurational dynamics, and electronic structure of these helicenes were analyzed using solid-state structures, spectroscopic methods, and computational analyses. The open-shell character of the singlet states of these helicenes increases in the order 3 < 1 < 2 , with strongly varying diradicaloid indexes and singlet–triplet gaps. Compounds 1 – 3 displayed narrow optical gaps of 0.79–1.25 eV, resulting in significant absorption in the near infrared (NIR) region. They also exhibit reversible redox chemistry, each of them yielding stable radical cations, radical anions, and dianions, in some cases possessing intense NIR absorptions extending beyond 2500 nm.     

Stereoselective Syntheses,Structures, and Properties of Extremely Distorted Chiral Nanographenes Embedding Hextuple Helicenes

We report a molecular design and concept using π‐system elongation and steric effects from helicenes surrounding a triphenylene core toward stable chiral polycyclic aromatic hydrocarbons (PAHs) with a maximal π‐distortion to tackle their aromaticity, supramolecular and molecular properties. The selective syntheses, and the structural, conformational and chiroptical properties of two diastereomeric large multi‐helicenes of formula C₉₀H₄₈ having a triphenylene core and embedding three [5]helicene units on their inner edges and three [7]helicene units at their periphery are reported based on diastereoselective and, when applicable, enantiospecific Yamamoto‐type cyclotrimerizations of racemic or enantiopure 9,10‐dibromo[7]helicene. Both molecules have an extremely distorted triphenylene core, and one of them exhibits the largest torsion angle recorded so far for a benzene ring (twist=36.9°).     

Stereospecific Synthesis of Enantiopure [6]Helicene Containing a Seven-Membered Ring and [7]Helicene by Acid-Promoted Stepwise Alkyne Annulations of Doubly Axial-Chiral Precursors**

Enantiopure [6]helicene containing an embedded seven-membered ring and carbo[7]helicene (>99 % ee) with opposite helicity were simultaneously and quantitatively (>99 %) synthesized with a perfect stereospecificity through stepwise acid-promoted intramolecular alkyne annulations of doubly axial-chiral cyclization precursors. The helical handedness of the [6]- and [7]helicenes was fully stereocontrolled by the doubly axial chirality of the precursors as a result of complete axial-to-helical chirality transfer. The cyclizations proceeded in a stepwise manner; the first six-membered ring formation was followed by the kinetically controlled seven- or six-membered ring formation with or without helix-inversion of a [4]helicene intermediate generated during the first cyclization step, thus quantitatively producing enantiopure circularly polarized luminescent [6]- and [7]helicenes with opposite helicity.     

Stereoselective Syntheses,Structures, and Properties of Extremely Distorted Chiral Nanographenes Embedding Hextuple Helicenes

We report a molecular design and concept using π-system elongation and steric effects from helicenes surrounding a triphenylene core toward stable chiral polycyclic aromatic hydrocarbons (PAHs) with a maximal π-distortion to tackle their aromaticity, supramolecular and molecular properties. The selective syntheses, and the structural, conformational and chiroptical properties of two diastereomeric large multi-helicenes of formula C₉₀H₄₈ having a triphenylene core and embedding three [5]helicene units on their inner edges and three [7]helicene units at their periphery are reported based on diastereoselective and, when applicable, enantiospecific Yamamoto-type cyclotrimerizations of racemic or enantiopure 9,10-dibromo[7]helicene. Both molecules have an extremely distorted triphenylene core, and one of them exhibits the largest torsion angle recorded so far for a benzene ring (twist=36.9°).     

Cross-conjugated oligothiophenes derived from the (C2S)n helix: asymmetric synthesis and structure of carbon-sulfur [11]helicene

(-)-Sparteine-mediated asymmetric synthesis of di-n-octyl-substituted carbon-sulfur [11]helicene, a helical (C2S)n beta-undecathiophene, is described. The atom-efficient routes rely on one-step tri-annelation or two-step di- and mono-annelation to provide enantiomeric excess of (+)- or (-)-[11]helicene, respectively. X-ray structures for homologous [11] and [7]helicenes indicate similar helical curvatures. The optical band gap, Eg approximately 3.5 eV, is estimated for the (C2S)n helix polymer, with onset of electron localization at n 相似文献   

The synthesis of azoniadithia[6]helicenes

A new short‐step synthesis of 8a‐azonia[6]helicene (1) and the novel dithieno derivatives ( 2 and 3 ) is described. Double photocyclization of 2,8‐distyrylquinolizinium salt (8) gave 1 in 35% yield. Similarly, 2,8‐bis[2‐(2‐thienyl)vinyl]‐ and 2,8‐bis[2‐(3‐thienyl)vinyl]‐quinolizinium salts ( 9 and 10 ) afforded new azonia[6]helicenes containing two thiophene rings at the ends of helix, that is 7a‐azonia‐3,12‐dithia[6]helicene (2) and 7a‐azonia‐1,14‐dithia[6]helicene (3) , in 43 and 35% yields, respectively. The total assignment of their ¹H‐ and ¹³C‐nmr spectra was performed by utilizing two‐dimensional and NOE nmr spectroscopic methods.     

Synthesis of Long Oxahelicenes by Polycyclization in a Flow Reactor

A series of oxahelicenes composed of ortho/meta-annulated benzene/pyridine and 2H-pyran rings were synthesized on the basis of the cobalt(I)-mediated (or rhodium(I)- or nickel(0)-mediated) double, triple, or quadruple [2+2+2] cycloisomerization of branched aromatic hexa-, nona-, or dodecaynes, thus allowing the construction of 6, 9, or 12 rings in a single operation. The use of a flow reactor was found to be beneficial for the multicyclization reactions. The stereogenic centers present in some of the oligoynes steered the helical folding in such a way that the final oxa[9]-, [13]-, [17]- and [19]helicenes were obtained in both enantiomerically and diastereomerically pure form. Specifically, the oxa[19]helicenes beat the current record in the length of a helicene backbone. Single-molecule conductivity was studied by the mechanically controllable break-junction method with a pyridooxa[9]helicene.     

One-Step Simultaneous Synthesis of Circularly Polarized Luminescent Multiple Helicenes Using a Chrysene Framework

A series of multiple helicenes was simultaneously synthesized in one step by intramolecular cyclization of a single chrysene derivative containing two 2-[(4-alkoxyphenyl)ethynyl]phenyl units accompanied by rearrangements of the aryl pendants. The electrophile-induced double cyclization with or without aryl migrations proceeded efficiently under acidic conditions to afford annulative π-extension of the chrysene units and produced quadruple (QH- 2 ), triple (TH- 2 ), and double (DH- 2 ) helicenes containing [4]- and/or [5]helicene frameworks with dynamic and/or static helicene chirality in one step. Three multiple helicenes’ structures were determined by X-ray crystallography and/or density functional theory calculations. The multiple TH- 2 and DH- 2 helicenes were separated into enantiomers because of the stable one and two [5]helicene moieties, respectively, and showed intense circular dichroism and circularly polarized luminescence. Although QH- 2 , which comprises four [4]helicene subunits, was not resolved into enantiomers, the TH- 2 enantiomers were further separated into a pair of diastereomers at low temperature resulting from their substituted [4]helicene chirality.     

Diazadithia[7]helicenes: Synthetic Exploration,Solid‐State Structure,and Properties

Diazadithia[7]helicenes were synthesized from the readily available building block ethyl 7‐chloro‐8‐formylthieno[3,2‐f]quinoline‐2‐carboxylate by a Wittig reaction–photocyclization strategy. The helicene core was functionalized by nucleophilic aromatic substitution with a variety of nucleophiles (e.g., O‐, N‐, and C‐centered) and palladium‐catalyzed reactions such as Suzuki coupling and Buchwald–Hartwig amination. Racemization studies confirmed that the enantiopure forms of these [7]helicenes are conformationally stable compared to their lower analogues. The solid‐state structures of the novel diazadithia[7]helicenes were determined by single‐crystal X‐ray diffraction. The crystal structures of these azathia[7]helicenes show columnar stacking in antiparallel fashion. The HOMO–LUMO gaps of the new compounds were determined on the basis of electrochemical and optical measurements.     

Experimental and Theoretical Structure Elucidation of the [2 : 1] Complex Ion of Carbo[n]helicene with n=6, 7 and 8 and Ag+

Gas-phase complexes of [n]helicenes with n=6, 7 and 8 and the silver(I) cation are generated utilizing electrospray ionization mass spectrometry (ESI-MS). Besides the well-established [1 : 1] helicene/Ag⁺-complex in which the helicene provides a tweezer-like surrounding for the Ag⁺, there is also a [2 : 1] complex formed. Density functional theory (DFT) calculations in conjunction with energy-resolved collision-induced dissociation (ER-CID) experiments reveal that the second helicene attaches via π-π stacking to the first helicene, which is part of the pre-formed [1 : 1] tweezer complex with Ag⁺. For polycyclic aromatic hydrocarbons (PAHs) of planar structure, the [2 : 1] complex with silver(I) is typically structured as an Ag⁺-bound dimer in which the Ag⁺ would bind to both PAHs as the central metal ion (PAH–Ag⁺–PAH). For helicenes, the Ag⁺-bound dimer is of similar thermochemical stability as the π-π stacked dimer, however, it is kinetically inaccessible. Coronene (Cor) is investigated in comparison to the helicenes as an essentially planar PAH. In analogy to the π-π stacked dimer of the helicenes, the Cor−Ag⁺−Cor−Cor complex is also observed. Competition experiments using [n]helicene mixtures reveal that the tweezer complexes of Ag⁺ are preferably formed with the larger helicenes, with n=6 being entirely ignored as the host for Ag⁺ in the presence of n=7 or 8.     

Closed Pentaaza[9]helicene and Hexathia[9]/[5]helicene: Oxidative Fusion Reactions of ortho‐Phenylene‐Bridged Cyclic Hexapyrroles and Hexathiophenes

Oxidative fusion reactions of ortho ‐phenylene‐bridged cyclic hexapyrroles and hexathiophenes furnished novel closed helicenes in a selective manner. X‐Ray diffraction analysis unambiguously revealed the structures to be a closed pentaaza[9]helicene, the longest azahelicene reported so far, and an unexpected double‐helical structure of hexathia[9]/[5]helicene, whose formation was assumed to result from multiple oxidative fusion along with a 1,2‐aryl shift. The pentaaza[9]helicene exhibited well‐defined emission with high fluorescence quantum yield (Φ _F=0.31) among the known [9]helicenes. Chiral resolution of the racemic pentaaza[9]helicene and hexathia[9]/[5]helicene were achieved by chiral‐phase HPLC and the enantiomers were characterized by circular dichroism spectra and DFT calculations.     

Multifunctional and reactive enantiopure organometallic helicenes: tuning chiroptical properties by structural variations of mono- and bis(platinahelicene)s

Acetylacetonato-platina[6]- and -platina[7]helicenes have been prepared from 2-pyridyl-substituted benzophenanthrene ligands by following a two-step cycloplatination reaction. The photophysical properties (UV-visible absorption and emission behavior) and chiroptical properties (circular dichroism and molar rotation) of the resolved enantiomers have been measured. These metallahelicenes constitute a novel family of easily accessible helicene derivatives that exhibit large and tuneable chiroptical properties that can be rationalized theoretically and compared to the parent [6]- and [7]carbohelicenes. Furthermore, they are red phosphors at room temperature and their large chiroptical properties can be modulated by oxidation of the metal center to Pt(IV). Hetero- and homochiral diastereomeric bis(metallahelicene)s that possess a rare Pt(III)-Pt(III) scaffold bridged by benzoato ligands have also been prepared. It is shown that the heterochiral (P,M)-bis(Pt(III)-[6]helicene) 9a(1) can isomerize into the homochiral (P,P)- and (M,M)-bis(Pt(III)-[6]helicene) 9a(2). Spectral assignments and an analysis of the optical rotation of these systems were made with the help of time-dependent density functional theory. The calculations highlight the contributions of the metal centers to the chiroptical properties. For 9a(1) and 9a(2), σ-π conjugation between the helicenes and the Pt-Pt moiety may contribute strongly to the optical rotation and electronic circular dichroism.     

Triggering G-Quadruplex Conformation Switching with [7]Helicenes

The dynamic interplay between two types of chiral structures; fully conjugated racemic hetero[7]helicenes and DNA strands prone to fold into G-quadruplex structures is described. Both the [7]helicenes and the G-quadruplex DNA structures exist in more than one conformation in solution. We show that the structures interact with and stabilise each other, mutually amplifying and stabilising certain conformations at increased temperatures. The [7]helicene ligands L1 and L2 stabilise the parallel conformation of k-ras significantly, whereas hybrid (K⁺) and antiparallel (Na⁺) h-telo G-quadruplexes are stabilised upon conformational switching into altered G-quadruplex conformations. Both L1 and L2 induce parallel G-quadruplexes from hybrid structures (K⁺) and L1 induces hybrid G-quadruplexes from antiparallel conformations (Na⁺). Enantioselective binding of one helicene enantiomer is observed for helicene ligand L2 , and VTCD melting experiments are used to estimate the racemisation barrier of the helicene.     

From central to helical chirality: synthesis of P and M enantiomers of [5]helicenequinones and bisquinones from (SS)-2-(p-tolylsulfinyl)- 1,4-benzoquinone

The reaction of 1,4-divinyl-1,3-cyclohexadiene, 5,8-dimethoxy- or tert-butyldimethylsilyloxy-3-vinyl-1,2-dihydrophenanthrene or 6-vinyl-7,8-dihydro-1,4-phenanthrenequinone with an excess of enantiopure (SS)-2-(p-tolylsulfinyl)-1,4-benzoquinone (2) led to the direct formation of enantioenriched dihydro[5]helicenequinones or bisquinones (50-->98 % ee). A domino Diels-Alder cycloaddition/sulfoxide elimination/partial aromatization process occurs, being the absolute configuration of the final helicene defined in the aromatization step. Both M and P helimers are accessible through a stepwise enantiodivergent process if the pentacyclic dihydroaromatic intermediate resulting in the two first steps is aromatized in the presence of (+/-)-2, DDQ, CAN or DBU.