Enantioselective Synthesis,(Chir)optical Properties,and Postsynthetic Functionalization of Furan-Containing Oxa[5]-,Oxa[6]-,and Dioxa[6]helicenes

An expedient synthesis of a series of configurationally stable oxa[5]helicenes,oxa[6]helicenes,and dioxa[6]helicenes has been developed using an intramolecular,highly enantioselective,Au-catalyzed,alkyne hydroarylation reaction.The absolute configuration of the newly prepared structures has been established by crystallography,their inversion barriers have been determined theoretically and experimentally,and their chiroptical properties have been investigated.Comparison of these data with those reported for thia-or carbohelicenes sharing an otherwise identical helical framework enables the establishment of comprehensive correlations between the nature of the embedded(hetero)atom(s)and the magnitude of these properties.Preliminary studies on the postsynthetic functionalization of the oxahelicenes obtained are also described.Specifically,siteselective bromination at the 15-position in oxa[5]helicene 5d allows its subsequent manipulation into pyridine-containing aza-oxa[7]helicene 13d;while the two termini of oxa[6]helicene 7d have been intramolecularly cyclised into the pleiadeno[1,12,11-bcde]benzofuran derivative 15d by acidic treatment.Both transformations take place without erosion of the enantiopurity.

Synthesis,Structures,and Chiroptical Properties of NBN-Doped Helicenes with Boron Atoms in the Inner Rims

The precise synthesis of helicenes with topologically defined length and specific heteroatomic perturbation in the screw-like conjugated skeletons plays an emerging role in the manipulation of chiral materials.Facile,selective,and programmable routes to helicenes or heterohelicenes are highly desirable yet challenging for structure-chiroptical property relationship studies.Herein,we report the synthesis and characterization of NBN-doped helicenes with boron atoms in the inner rims,enabled by the highly regioselective one-pot borylation of rationally designed precursors with,namely,fold-in or pan-out manner.The incorporation of nonbonded boron and nitrogen atoms resulted in narrow-band emission and improved optical properties for the single-stranded carbon helix.In addition,numbers and arrangement modes of fused six-membered rings have distinct effects on configurational stability and chiroptical properties,revealing that BN-[6]H with strong circular dichroism is a promising candidate for chiral sensors.The combination of experimental and theoretical studies on these helical structures might provide insights into the design of helically chiral small-molecule-based sensors or emitters.

Triple Aza[6]helicenes with Circularly Polarized Luminescence:N-Alkylation as a Tool to Tune the Chiroptical Properties

Recently,multiple helicenes have attracted enormous attention due to their exceptionally distorted conjugated architectures,appealing optical properties and unique spatial stacking patterns.The electronic and optical properties of multiple helicenes could be modulated by heteroatom doping.Herein,the first triple aza[6]helicene was reported by an intramolecular oxidation reaction,which exhibited highly distorted propeller-like geometry revealed by single crystal X-ray diffraction analysis.In comparison to the reported triple oxa[6]helicene,the triple aza[6]helicene demonstrated increased quantum yield(5.5%),and chiroptical properties with a|gabs|value of 0.012 and a|glum|value of 3.0×10^(-3).Furthermore,the stability and chiroptical properties of the triple aza[6]helicene could be enhanced by N-alkylation.

On-surface Synthesis of Multiple Non-benzenoid Carbohelicenes Fused with Fluorene Unit(s)

Comprehensive Summary Carbohelicenes have garnered considerable attention for their inherent chirality and structural flexibility.Increasing multi-helicity and incorporating non-six-membered rings to substitute benzenoid rings within helicenes are effective strategies for introducing unique photoelectric properties.Despite the disclosure of numerous helicenes,the inaccessible precursors and the lack of synthetic routes pose a challenge in achieving desired helicene structures fused with non-benzenoid rings.Herein,we report the synthesis of multiple non-benzenoid carbohelicenes fused with fluorene unit(s)through intramolecular cyclodehydrogenation of 9,10-di(naphthalen-1-yl)anthracene on Au(111)surface.Two potential cyclodehydrogenation manners between naphthyl and anthracene lead to the formation of fluorene-fused[5]helicene and[4]helicene moiety.Consequently,a total of four stable products were observed.The atomic topographies of products are characterized by bond-resolving scanning tunneling microscopy.The chiral helicity of targeted products can be switched by tip manipulation.Density-functional-theory calculations unveils the reaction pathway of four products.The comparative analysis of their respective energy barriers exhibits a correlation with the experimentally determined yields.Furthermore,we synthesize the polymer chains incorporating non-benzenoid carbohelicenes via the Ullmann reaction of 2,6-dibromo-9,10-di(1-naphthyl)anthracene precursors.Our work proposes a synthetic methodology for several novel helicene-like structures fused with fluorene units and the polymer bearing helicene subunits,thus highlighting the immense potential of these compounds in the application fields of luminescent electronic devices.

Unraveling the amplified chiroptical responses of rylene-bladed quintuple[6]helicenes

Unraveling the key structural features to maximize the chiroptical properties is of significance for developing high-performance chiral materials.Here we present our first attempt to elucidate and understand the molecular design of excellent chiroptical properties via the combination of multiplicity and the alignment of subhelicenes.Two stereoisomeric PDI-bladed quintuple[6]helicenes,namely D_(5)-CRP and C_(2)-CRP,were revealed to show distinct spatial arrangements of subhelicenes.Circular dichroism(CD)spectra showed that the Cotton effects(Δε)are reaching 1,412 mol-1L cm-1for D_(5)-CRP and 669 mol^(-1)L cm^(-1)for C_(2)-CRP in the visible spectrum.The greatly amplifiedΔεrelative to the smaller analogue NPDH arises from the circular annulation of helicenes and high molecular symmetry that could significantly regulate the transition dipole moments and thereby make them tend to be(anti)parallel,as supported by TDDFT calculations for the rotatory strength(R).Consequently,the maximal dissymmetry factors(|g_(abs)|and|g_(lum)|)of this kind of chiral molecular carbon imides were estimated to be up to 0.021 and 0.012,respectively.This study provides a deep insight into the chiroptical properties of complicated chiral systems.

Simple Double Hetero[5]helicenes Realize Highly Efficient and Narrowband Circularly Polarized Organic Light-Emitting Diodes

Helicene-based emitters with unique inherent circularly polarized luminescence(CPL)are promising yet remain a formidable challenge for highly efficient circularly polarized organic light-emitting diodes(CP-OLEDs),ascribed to their tough synthesis,low emission efficiency,and easy racemization in the thermal deposition process.Herein,a pair of helicenebased enantiomers,namely(P)-helicene-BN and(M)-helicene-BN,were developed,which merge helical chirality and the B/N/S inserted polycyclic aromatic framework to concurrently feature CPL and narrow thermally activated delayed fluorescence(TADF)characteristics.Benefiting from the excellent thermal/photophysical/chiroptical properties,the narrowband green CP-OLEDs based on enantiomers achieved maximum external quantum efficiencies(EQE_(max))of up to 31.5%,and dissymmetry factor(|g_(EL)|)of 2.2×10^(−3).This work reveals the great potential of helicene-based emitters in CP-OLEDs.

Flag-hinge-like highly luminescent chiral nanographenes with twist geometry

Nanographenes(NGs)with twisted backbones are emerging as new candidates for chiroptical materials.In this work,we describe a new strategy for synthesizing a[10]twistacene-embedded NG which exhibits a rare flag-hinge-like geometry.By neatly creating steric crowding on the[6]helicene breaches of the NG skeleton,the synthesis only provided homochiral isomers without generating the“meso-”isomer.The formed NGs showed high luminescence with quantum yield up to 52%,and promising circularly polarized luminescence(CPL)performance with|glum|up to 5.0×10^(-3).Besides,these NGs also showed outstanding CPL brightness(BCPL)up to 305 L mol^(-1)cm^(-1)among chiral NGs.

Quadruple[6]Helicene Featuring Pyrene Core:Unraveling Contorted Aromatic Core with Larger Effective Conjugation

Multiple helicenes display distinct aromatic cores characterized by highly twisted rings that are shared or fused with constituent helicene moieties.Diversifying these aromatic cores unlocks avenues for creating multiple helicenes with distinct properties and topologies.Herein we report the synthesis of a quadruple[6]helicene featuring pyrene as the aromatic core.The synthesis involved key steps of the annulativeπ-extension reaction and Scholl reaction.By extending multiple helicenes along the axial direction,the degree of contortion of the aromatic core can be controlled from nearly flat to highly twisted.Notably,quadruple[6]-helicene exhibits a significant red-shift of 0.49 eV compared to quadruple[4]-helicenes,of which the red-shift arises from bothπ-extension and augmented effective conjugation due to enhanced twisting.Quantum chemical calculations demonstrate that the degree of contortion in the pyrene core adeptly governs the energy levels of the HOMO and LUMO,which offers an alternative strategy beyond mere enlargement of theπbackbone.An intriguing serendipitous finding reveals the formation of one-molecule-thick supramolecular homochiral nanosheets through selfinterlocking interactions of enantiomers in single crystals,a rare packing motif for multiple helicenes.

Helicene-type β-isoindigo-based boron-dipyrromethene analogs with strong near-infrared chiroptical activity

Near-infrared(NIR)chiroptical response has been less explored because it is chal-lenging to achieve both chirality and NIR absorption/emission.Herein,we describe the design of heterohelicene-typeβ-isoindigo-based boron-dipyrromethene(BOD-IPY)analogs(β-IBs),which shift the absorption peak to 800 nm and produce significant Cotton effects(127.8 M-1 cm-1)and absorbance dissymmetry factors(|gabs|3.5=×10-3).The luminescence dissymmetry factor(glum)and circu-larly polarized luminescence(CPL)brightness(BCPL)of up to 1.24×10-3 and 1.78 M-1 cm-1 were realized beyond 800 nm.Theseβ-IBs are thefirst examples of helicene-type compounds with the highest gabs in the NIR region and CPL beyond 800 nm.Theoretical calculations demonstrate that the strong chiroptical activities are triggered by their large transition magnetic dipole moments.This study not only provides a new approach to the synthesis of a larger variety of unprecedented helicene-type BODIPY analogs but also demonstrates excellent NIR chiroptical properties.

A C2-symmetric triple [5]helicene based on N-annulated triperylene hexaimide for chiroptical electronics

Two diastereoisomers(NTPH-P and NTPH-T1) as a C2-symmetric triple [5]helicene based on N-annulated triperylene hexaimide were synthesized.Aided by nuclear magnetic resonance spectroscopy(NMR) and theoretical calculations,NTPH-P was assigned to three-blade propeller conformation while NTPH-T1 tended to exhibit twisted conformation with pyrrole ring fusing on a bowl-shaped PDI foil.Characterized by circular dichroism(CD) and circular polarized luminescence(CPL) measurements,the enantiomerically pure NTPH-P exhibited fairly good chiral activities both in the absorption and emission range with dissymmetry factors |gabs| of 4.1×10^-3 and |glum| of 1.2×10^-3.The diastereoisomers were further employed as acceptors for organic solar cells with distinct PCEs of 8.11% and 5.24% for NTPH-P and NTPH-T1 based devices,respectively,signifying the prospects in chiroptical electronics by designing molecularly defined aromatics.

On-Surface Stereochemical Characterization of a Highly Curved Chiral Nanographene by Noncontact Atomic Force Microscopy and Scanning Tunneling Microscopy

A highly distorted chiral nanographene structure composed of triple corannulene-fused[5]helicenes is prepared with the help of the Heck reaction and oxidative photocyclization with an overall isolated yield of 28%.The complex three-dimensional(3D)structure of the bowl-helix hybrid nanostructure is studied by a combination of noncontact atomic force microscopy(AFM)and scanning tunneling microscopy(STM)on the Cu(111)surface,density functional theory calculations,AFM/STM simulations,and high-performance liquid chromatography-electronic circular dichroism analysis.This examination reveals a molecular structure in which the three bowl-shaped corannulene bladesd position themselves in a C3-symmetric fashion around a highly twisted triphenylene core.The molecule appears to be shaped like a propeller in which the concave side of the bowls face away from the connected[5]helicene motif.The chirality of the nanostructure is confirmed by the direct visualization of both MMM and PPP enantiomers at the single-molecule level by scanning probe microscopies.These results underline that submolecular resolution imaging by AFM/STM is a powerful real-space tool for the stereochemical characterization of 3D curved chiral nanographene structures.

Extremal hexagonal chains concerning largest eigenvalue

In this paper, we define a roll-attaching operation of a hexagonal chain, and prove Gutman's conjecture affirmatively by using the operation. The idea of the proof is also applicable to the results concerning extremal hexagonal chains for the Hosoya index and Merrifield-Simmons index.

Thermally activated delayed fluorescence materialsensitized helicene enantiomer-based OLEDs:a new strategy for improving the efficiency of circularly polarized electroluminescence

A new strategy of thermally activated delayed fluorescence(TADF)material-sensitized circularly polarized luminescence(CPL)has been proposed for improving the efficiencies of fluorescent circularly polarized organic lightemitting diodes(OLEDs)(CP-OLEDs).Consequently,a pair of helicene enantiomers,(P)-HAI and(M)-HAI,were synthesized.The helicene enantiomers with the rigid helicalπ-skeleton had highly thermal and enantiomeric stabilities,and they also showed excellent photophysical properties,especially,intense mirror-image CPL activities with large luminescence dissymmetry factor(|g_(lum)|)values of about 6×10^(-3).Notably,the CP-OLEDs with the helicene enantiomers as emitters and a TADF molecule as sensitizer not only displayed better performance of lower turn-on voltage(V_(T))of 2.6 V,four-fold maxmium-external quantum efficiency(EQE_(max))of 5.3%,and lower efficiencies roll-off of 1.9%at 1000 cd m^(-2),than those of the devices without TADF sensitizer,but also exhibited intense circularly polarized electroluminescence(CPEL)with the electroluminescence dissymmetry factor(g_(EL))values of-2.3×10^(-3)and+3.0×10^(-3).Meanwhile,this study also represents the first thermally activated sensitized fluorescent CP-OLEDs with markedly enhanced efficiencies and intense CPEL.

A fan-shaped synthetic chiral nanographene

We report the synthesis and characterization of a fan-shaped chiral nanographene 1,which is composed of 6 hexabenzocoronene subunits with 216 conjugated carbon atoms.In the dehydrocyclization reaction,38 C–C bonds are formed simultaneously.1 exhibits strong panchromatic absorption from the ultraviolet to the near-infrared,with an absorption coefficient of 209,000 L mol^(-1)cm^(-1)at 564 nm.Optically pure samples,obtained via chiral HPLC,show distinct ECD signals(|Δε|=704 L mol^(-1)cm^(-1)at 405 nm).Upon excitation,1 emits near-infrared fluorescence at 820 nm with a quantum yield of 5.5%.These photophysical properties of 1 were analyzed with the assistance of DFT calculations.

Reactivity,Regioselectivity,and Synthetic Application of 2-Pyrenyl Units in Scholl Reactions

We herein report the reactivity and regioselectivity of 2-pyrenyl as a coupling unit in Scholl reactions.On the basis of the Scholl reactions of hexaarylbenzene substrates,we have found that pyrenyl units are preferably oxidized over naphthyl and phenyl units under appropriate Scholl reaction conditions,allowing divergent synthesis through a highly controllable intramolecular coupling sequence.We find that the C1 and C3 positions of the 2-pyrenyl unit are the favorable sites for intramolecular coupling while C4 is not reactive to allow further coupling.The reactivity and regioselectivity pattern can be explained by the spin density distribution,which shows that carbon-carbon bonds preferably form at sites with higher positive spin density.Guided by these findings,we successfully synthesized a double helicene and a sextuple helicene through the controlled Scholl reactions of 2-pyrenyl units.

Research Advances in Helicene Structure-Based Chiral Luminescent Materials and Their Circularly Polarized Electroluminescence

Benefited from direct generation of circularly polarized(CP) emission with tunable colors, high efficiencies and facile device architectures, CP organic light-emitting diodes(CP-OLEDs) have attracted great attention and are expected to meet industrial applications. Particularly, CP electroluminescence(CPEL) originated from CP-OLEDs has wide potential applications in 3D displays, optical information storage, quantum communication, and biological sensors. The diverse design strategies of chiral luminescent materials for CP-OLEDs, including small organic emitters, lanthanide and transition-metal complexes and conjugated polymers, have been extensively explored. Helicene with twisted extended π-conjugated molecular structure could exhibit special helical chirality and excellent circularly polarized luminescence properties, which has been employed as the ingenious chirality core for constructing efficient chiral luminescent materials. In addition, significant improvements have been made in terms of CP photoluminescence research, however, the development of CPEL with more application prospects in optoelectronic technology still lags behind. In this review, we systematically summarize the recent advances in chiral luminescent materials based on helicene structure and their CPEL properties, including helicene-based chiral fluorescence molecules, transition metal complexes and thermally activated delayed fluorescence molecules, and discuss current challenges and future perspectives for this hot research field. We believe this progress report will provide a promising perspective of OLEDs based on helicene emitters with CPEL properties for extensive researchers, including chemical, physical and material scientists in different disciplinary fields and attract them to this rapidly developing field.

Comparison of luminescent properties of helicene-like bibenzothiophenes with o-carborane and 5,6-dicarba-nidodecaborane

This article describes comparison of the anchoring effect on electronic properties of the helicene-like bibenzothiophene between o-carborane and 5,6-dicarba-nido-decaborane. The o-carborane and nido-decaborane-fused bibenzothiophenes were simultaneously obtained in the same reaction and successfully isolated. Initially, the X-ray single crystal analysis revealed that the helicene-like distorted structure was realized in the nido-decaborane-fused bibenzothiophene. From optical measurements in the solution state, distinct different characteristics depending on the type of anchors were observed. It was summarized that the absorption and luminescent properties originated from weak π-conjugation at the bibenzothiophene moiety in the o-carboranefused compound were obtained, whereas robust π-conjugation and significant emission from the intramolecular charge transfer state were detected from the nido-decaborane-fused compound. These data can be explained by the theoretical results that π-conjugation was restrictedly developed within the bibenzothiophene moiety in frontier orbitals of the o-carborane-fused compound. In contrast, π-conjugation can be constructed even through the distorted bibenzothiophene because of the nido-decaborane unit. Moreover, the intramolecular charge transfer state should be realized because of electronic interaction involving the nido-decaborane unit in the excited state. Furthermore, it was demonstrated that the nido-decaborane-fused compound possessed solid-state emission and mechanochromic luminescent properties. The π-conjugation on the distorted structure supported by the nido-decaborane anchor should play a significant role in suppressing aggregation-caused quenching followed by presenting solid-state emission with stimuli responsiveness.

Tunable construction of transition metal-coordinated helicene cages

We report a facile and tailored method to prepare globally twisted chiral molecular cages through tunable coordination of bis-bipyridine-terminated helicene ligands to a series of transition metals including Fe(Ⅱ), Co(Ⅱ), Ni(Ⅱ) and Zn(Ⅱ). This system shows an efficient remote transfer of stereogenecity from the helicene core to the bipyridine-metal coordination sites and subsequently the entire cages. While the Fe(Ⅱ), Co(Ⅱ) and Ni(Ⅱ)-derived M_(2)L_(3)(M for metal and L for ligand) cages exhibit quasi-reversible redox features, the Zn(Ⅱ) analogues reveal prominent yellow circularly polarized luminescence. Interestingly,with the addition of Na_(2)SO_(4), the Zn_(2)L_(3)cages reassemble into sextuple-stranded Zn_(6)L_(6)(SO_(4))_(4)cages in which three Zn_(2)L_(2) units are bound together by four sulfates and further coalesced by offset inter-ligandπ-π interactions.

A New Fluorescent Chemodosimeter for Hg2＋ with High Selectivity and Sensitivity in Water

A new fluorescent chemodosimeter based on tetrahydro[5]helicene imide was synthesized,and it showed high selectivity and sensitivity toward Hg2＋ ions over other different tested metal ions in water.The response time was within 0.5 min,and the detection limit of the chemodosimeter for Hg2＋ was estimated to be 2.0 × 10-8 mol·L-1.The Hg2＋ promoted deprotection of dithioacetal groups of 1,which induced water-soluble fluorescent chemodosimeter 1 to form a water-insoluble aldehyde precursor.

A quadruple helicene with a rubicene core: synthesis, structural analyses and properties

We report the synthesis of a quadruple helicene with a rubicene core R1 by a Scholl reaction.Among the 10 stereoisomers including 4 pairs of enantiomers and 2 meso isomers,only 2 pairs of enantiomers and 1 meso isomer have been isolated.The sample structures were unambiguously determined by X-ray crystallography to be(P,P)_(6)-(P,P)_(5)/(M,M)_(6)-(M,M)_(5)-R1-A,which has a propeller-shaped structure,and(M,M)_(6)-(P,P)_(5)/(P,P)_(6)-(M,M)_(5)-R1-B and(M,P)_(6)-(P,M)_(5)-R1-C,which have saddle-shaped structures.The chiral resolutions of R1 were carried out by chiral HPLC,revealing two pairs of chiral stereoisomers(P,P)_(6)-(P,P)_(5)/(P,P)_(6)-(M,M)_(5),(M,M)_(6)-(P,P)_(5)/(M,M)_(6)-(M,M)_(5) as well as a meso isomer(M,P)_(6)-(P,M)_(5),which were further characterized by CD spectroscopy and time-dependent density functional theory(TD-DFT)calculations.Surprisingly,the UV-vis absorption and emission spectra of these resolved stereoisomers and unresolved R1 were almost identical.In addition,the chemical oxidation of R1 led to the formation of radical cations and dications at room temperature.