Effective Conjugation Length Research Articles

Conformation‐Confined Organic Butterfly‐Molecule with High Photoluminescence Efficiency, Deep‐Blue Amplified Spontaneous Emission, and Unique Piezochromic Luminescence

AbstractOrganic fluorophores with tunable π‐conjugated paths have attracted considerable attention owing to their diverse properties and promising applications. Herein, we present a tailored butterfly‐like molecule, 2,2’‐(2,5‐bis (2,2‐diphenylvinyl)‐1,4‐phenylene)dinaphthalene (BDVPN), which exhibits diverse photophysical features in its two polymorphs. The BP phase crystal, with its “aligned wings” conformation, possesses emissive characteristics that are nearly identical to those in dilute solutions. In contrast, the BN phase crystal, which adopts an “orthogonal wings” conformation, exhibits an unusual hypsochromic‐shifted emission compared to its dilute solution counterparts. This intriguing hypsochromic‐shifted emission originates from the reduction in the effective conjugated length of the molecular skeleton. Notably, BN phase crystals also exhibit exceptional optical performance, featuring high‐efficiency emission (76.6 %), low‐loss optical waveguides (0.571 dB mm−1), deep‐blue amplified spontaneous emission (ASE) with narrow full width at half maximum (FWHM: 6.4 nm), and a unique 200 nm bathochromic shift of piezochromic luminescence.

Conformation-Confined Organic Butterfly-Molecule with High Photoluminescence Efficiency, Deep-Blue Amplified Spontaneous Emission, and Unique Piezochromic Luminescence.

Organic fluorophores with tunable π-conjugated paths have attracted considerable attention owing to their diverse properties and promising applications. Herein, we present a tailored butterfly-like molecule, 2,2'-(2,5-bis (2,2-diphenylvinyl)-1,4-phenylene)dinaphthalene (BDVPN), which exhibits diverse photophysical features in its two polymorphs. The BP phase crystal, with its "aligned wings" conformation, possesses emissive characteristics that are nearly identical to those in dilute solutions. In contrast, the BN phase crystal, which adopts an "orthogonal wings" conformation, exhibits an unusual hypsochromic-shifted emission compared to its dilute solution counterparts. This intriguing hypsochromic-shifted emission originates from the reduction in the effective conjugated length of the molecular skeleton. Notably, BN phase crystals also exhibit exceptional optical performance, featuring high-efficiency emission (76.6 %), low-loss optical waveguides (0.571 dB mm-1), deep-blue amplified spontaneous emission (ASE) with narrow full width at half maximum (FWHM: 6.4 nm), and a unique 200 nm bathochromic shift of piezochromic luminescence.

Thiopyran-Fused Polycyclic Aromatic Compounds Synthesized via Pt(II)-Catalyzed One-Pot Ring-Expansion and 6-endo Cyclization Reactions.

A series of thiopyran-fused polycyclic aromatic hydrocarbons (PAHs) have been straightforwardly synthesized from 2,5-di(1-en-3-ynyl)thiophene-containing precursors via one-pot ring-expansion and 6-endo cyclization reactions. The reaction monitoring and the density function theoretical calculation suggest that the ring-expansion reaction occurs prior to 6-endo cyclization. Moreover, the absorption profiles of the thiopyran-fused PAHs suggest that the π-conjugation extension on the side of the cyclopentadiene ring in the cyclopenta[b]thiochromene core is predominant in prolonging the effective conjugation length, while the effect from extension on the other side is negligible. Furthermore, all of the thiopyran-fused PAHs exhibit halochromic properties. Upon the addition of trifluoromethanesulfonic acid, fluorescence "off-on" switches can be found for these thiopyran-fused PAHs. Therefore, this work not only provides a new synthetic approach for one-pot ring-expansion and 6-endo cyclization reactions but also expands the diversity of thiopyran-fused PAHs.

Thickness‐Dependent Formation Capacity and Mechanism of Planar (β)‐Conformation in Polydiarylfluorenes for Stable Deep‐Blue Polymer Light‐Emitting Diodes

AbstractConjugated polymers with p‐orbital overlap show intramolecular‐conformation‐dependent photophysical and electrical properties. Compared to the non‐planar segments, the planar conformation segments have a relatively long effective conjugated length and rigid backbone structure, which are beneficial for the enhancement of optoelectronic properties. Herein, the effect of film thickness on the formation capacity of planar (β) conformations in polyfluorene (poly[4‐(octyloxy)‐9,9‐diphenylfluorene‐2,7‐diyl]‐co‐[5‐(octyloxy)‐9,9‐diphenylfluorene‐2,7‐diyl], PODPF) for the fabrication of stable deep‐blue polymer light‐emitting diodes (PLEDs) is explored. Thickness‐tunable films with thicknesses ranging from 15 to 270 nm by controlling the concentration of precursor solution are prepared. The main observations are as follows. The PODPF chains in thin films are less likely to adopt the β conformations associated with the loose interchain packing in nano‐aggregates than those in thick films. Red‐shifted and well‐resolved emission spectra are observed for the annealed film with a high thickness, indicating the greater presence of β‐conformation segments. More interestingly, interchain aggregation is a necessary but not sufficient condition for the formation of β conformations. Finally, PLEDs based on β‐conformation segments have outstanding brightness, low turn‐on voltage, and stable deep‐blue electroluminescent behavior, confirming the unique advantage of planar conformation for optoelectronic applications.

Low voltage driven P3HT/PS phototransistor for ultra-high power efficiency UV sensing

This study explores the physical properties and electrical characteristics of a regioregular poly 3-hexylthiophene (rr-P3HT) semiconductor blended with the polymer insulator polystyrene. Given the high operating voltage required by conventional P3HT transistors, we employed a hybrid dielectric layer, combining plasma-reacted metal oxide with a polymer pre-layer (AlOx/PMMA and HfOx/PMMA), to reduce the operating voltage of P3HT transistors. As a result, an operating voltage lower than −5 V for the blended sample was achieved. The structural, morphological, and electrical properties of the prepared blended sample were investigated using XRD, AFM, XPS, UV–Visible spectroscopy, Raman spectroscopy, and I–V characteristics. The blended sample exhibits improved crystalline ordering and an extended effective conjugation length, accompanied by an increased formation of dendritic P3HT fibrils that enhance UV absorption. PS captures generated electrons, effectively delaying their recombination with generated holes in P3HT. This leads to heightened UV responsivity in P3HT/PS transistors. The key discovery of this study is the ultra-low power consumption UV sensing device. The blended sample, illuminated with a UV intensity of 550 μW/cm2, exhibited the highest sensitivity of 194.5, nearly 60 times higher than that of pristine P3HT. Consequently, our investigated device shows promise for applications in visible-blind sunlight or environmental monitoring systems, given its ultra-high-power efficiency.

Synthesis of polysaccharide/polyaniline composites by sol–gel method

ABSTRACT In this study, we report a novel synthesis technique for polysaccharides and conducting polymer composites. A series of polysaccharide/polyaniline composites were prepared via double-step polymerization by a sol–gel method developed herein. The chemical structure and the electronic properties of the composites were analyzed through Fourier transform infrared, ultraviolet–visible, and electron spin resonance spectroscopies. Composites with long effective conjugation lengths were obtained because the gelatinized polysaccharide acted as a template and host for the composite.

Chlorinated benzothiadiazole-based donor-acceptor polymers with tunable optoelectronic performances

Chlorinated benzo[c][1,2,5]thiadiazole, a new analogue of benzo[c][1,2,5]thiadiazole (BT), exhibits strong electron-withdrawing ability nature, while also offering advantages of lower cost and easier accessibility compared to its fluorinated analogues. This inspires us to investigate donor-acceptor-type (D-A) conjugated polymers based on chlorinated BT. Therefore, in this work, three D-A-D type monomers (0Cl, 1Cl, and 2Cl) were successfully synthesized with BT and chlorinated BT as acceptor units and EDOT as donor units by Stille coupling reaction. Subsequently, the corresponding D-A polymers (P0Cl, P1Cl, and P2Cl) were obtained via electrochemical polymerization. The results show that the two chlorinated monomers have higher initial oxidation potentials of 1.08 V (1Cl) and 1.09 V (2Cl), which are significantly higher than their non-chlorinated analogue (0.72 V). The two chlorinated polymers demonstrate good redox activity but with relatively poor stability (only 65.7 % and 20.7 % electroactivity are preserved after 100 cycles). Due to the decreased effective conjugation length caused by the deviations from planarity, both absorption spectra of the chlorinated polymers were blue-shifted when compared with P0Cl, leading to an increase in the optical band gap (1.64–1.68 eV). Introducing the Cl atom substitution on the BT unit resulted in the improvement of both the switching time and coloration efficiency. Specifically, the monochlorinated polymer (P1Cl) showed light gray in the neutral state and obvious electrochromic properties in the near-infrared region (optical contrast: 24 %, coloration efficiency: 195.6 cm2 C−1, and quick response time: 0.4 s). This study further expands the selection of chlorinated BT-based acceptor units and the application prospect of D-A electrochromic polymers.

Conjugation Length-Dependent Raman Scattering Intensity of Conjugated Polymers.

Polydiacetylenes, as a class of conjugated polymers with alternating conjugated C═C and C≡C bonds, have emerged as a promising probe material for biomedical Raman imaging, given their ultrastrong Raman scattering intensity. However, the relationship between the structure, especially the molecular length of polydiacetylenes, and their Raman scattering intensity remains unclear. In this work, a series of water-soluble polydiacetylenes, namely poly(deca-4,6-diynedioic acid) (PDDA) with different molecular weights (MWs), is prepared through controlled polymerization and degradation. The ultraviolet-visible (UV-vis) absorption spectroscopic and Raman spectroscopic studies on these polymers reveal that the Raman scattering intensity of PDDA increases nonlinearly with the MW. The MW-Raman scattering intensity relationship in the polymerization process is completely different from that in the degradation process. In contrast, the Raman scattering intensity increases more linearly with the maximal absorbance of the polymer, and the relationship between the Raman scattering intensity and the maximal absorbance of PDDA in the polymerization process is consistent with that in the degradation process. The Raman scattering intensity of PDDA hence exhibits a better dependence on the effective conjugation length of the polymer, which should guide the future design of conjugated polymers for Raman imaging applications.

Conformational Relaxation Dynamics of Poly(3-hexylthiophene) Photoexcited in Solution as Studied by Femtosecond Time-Resolved Stimulated Raman Spectroscopy in 1190-1550 nm Region.

When a conjugated polymer is photoexcited in solution, its effective conjugation length in the singlet exciton state often increases through the conformational relaxation of the polymer main chain and/or hopping of the excitation. We measured femtosecond time-resolved near-IR stimulated Raman spectra of poly(3-hexylthiophene) (P3HT) photoexcited in four organic solvents for understanding the dynamics of the exciton elongation through the conformational relaxation separately from that through the exciton hopping. In the ring CC stretch frequency region, a band appears at around 1415 cm-1 and decays, while a new band rises at around 1370 cm-1. The average time constant of the change is estimated to be 8.7-19 ps and correlated almost linearly with the viscosity of the solvents. These results suggest that the main chain of P3HT in the singlet exciton state relaxes from a twisted form to a planar form in the 0-100 ps range when it surmounts an activation barrier of 5.8-7.8 kJ mol-1, generated possibly by the steric effect of the hexyl side group. When the rise of the 1370 cm-1 band is analyzed in detail, it is reproduced with two exponential rise functions with time constants of 0-3.3 and 16-22 ps. The two rise components suggest that a portion of P3HT forms a cluster in solution, while the other portion of P3HT is isolated.

Effect of conjugation length on fluorescence characteristics of carbon dots.

The influence of sp2- and sp3-hybridized carbon coexisting in carbon cores on fluorescence characteristics of carbon dots (CDs) was revealed by density functional theory calculations. Based on the constructed coronene-like structures, the fluorescence emission spectra, transition molecular orbital pairs and several physical quantities describing the distribution of electrons and holes were investigated. The results indicate that due to the interaction between sp2 and sp3 carbon atoms, two main factors including the hyperconjugative effect and the separation of sp2 domain by sp3 carbon atoms can regulate the fluorescence wavelength. By analyzing the transition molecular orbital pairs, it was found that the fluorescence wavelength has a close correlation with the conjugation length, suggesting that the conjugation length can predict the shift of the emission spectra of CDs. The theoretical results provide a comprehensive understanding of fluorescence mechanism and help to synthesize CDs with expected fluorescence wavelength.

Main-chain engineering of polymer photocatalysts with hydrophilic non-conjugated segments for visible-light-driven hydrogen evolution

Photocatalytic water splitting is attracting considerable interest because it enables the conversion of solar energy into hydrogen for use as a zero-emission fuel or chemical feedstock. Herein, we present a universal approach for inserting hydrophilic non-conjugated segments into the main-chain of conjugated polymers to produce a series of discontinuously conjugated polymer photocatalysts. Water can effectively be brought into the interior through these hydrophilic non-conjugated segments, resulting in effective water/polymer interfaces inside the bulk discontinuously conjugated polymers in both thin-film and solution. Discontinuously conjugated polymer with 10 mol% hexaethylene glycol-based hydrophilic segments achieves an apparent quantum yield of 17.82% under 460 nm monochromatic light irradiation in solution and a hydrogen evolution rate of 16.8 mmol m−2 h−1 in thin-film. Molecular dynamics simulations show a trend similar to that in experiments, corroborating that main-chain engineering increases the possibility of a water/polymer interaction. By introducing non-conjugated hydrophilic segments, the effective conjugation length is not altered, allowing discontinuously conjugated polymers to remain efficient photocatalysis.

Coatable 2D Conjugated Polymers Containing Bulky Macromolecular Guests for Thermal Imaging.

Dynamic properties are derived from the structural flexibility of 2D polymers. Softening layered structures has the potential for tuning and enhancing the dynamic properties. In the present work, the flexibility of layered polydiacetylene (PDA) is tuned by the interlayer polymeric guests with different branching structures. PDA shows thermoresponsive color-change properties through shortening the effective conjugation length with molecular motion. Whereas the blue-to-red color transition is observed at certain threshold temperatures for the layered PDA without the interlayer guest, the intercalation of the bulky polymer guests lowers the starting temperature and widens the temperature range for the thermoresponsive color changes. The resultant layered composite of PDA and bulky polymer affords the homogeneous coating on substrates on the centimeter scale. The thermoresponsive color-change coating is applied to temperature-distribution imaging. The specific heat of liquids is colorimetrically estimated using the coating on the bottle. The coating on a silk cloth visualizes the temperature distribution on a simulated tissue during surgical operation using an ultrasonic coagulation cutting device. The coating can be applied to thermal imaging in a variety of fields. Moreover, the softening strategy contributes to explore dynamic properties of soft 2D materials.

Can Direct-Immersion Aqueous–Aqueous Microextraction Be Achieved When Using a Single-Drop System?

For the analysis of biological analytes in complex matrices, it is difficult to achieve extraction of analytes and enrichment in an aqueous-aqueous single-drop microextraction system. In this study, we proposed a pH-dependent polydopamine (PDA)-coated vesicle/Fe3O4 magnetic aqueous-aqueous in a single-drop microreactor (SDMR) for the direct fluorescence detection of glutathione S-transferase (GST), a metabolic enzyme involved with crucial biological processes, in biological samples. After extracting and enriching the GST target from an aqueous-aqueous single-drop interface, the extraction process was conducted rapidly in 6 s in the SDMR system. The GST was first extracted from the sample solution via the GST-Aptamer on the polydopamine-coated vesicle/Fe3O4 nanospheres (Fe3O4@PDA@GST-Aptamer). Then, as the pH changed from weakly acidic to weakly alkaline in the SDMR system, the GST and GST-Aptamer were released from Fe3O4@PDA@GST-Aptamer nanospheres and captured by polydiacetylene vesicles via the capture probe. These changes altered the effective conjugation length and angle of the vesicle trunk, generating a highly enhanced fluorescence signal. This not only achieved the purpose of target enrichment but also reduced interferences posed by matrix effects. The approach can be used for the direct detection of GST in genuine urine and blood without any sample pretreatment. The linear range was 0.005 to 0.5 μg/mL, and the limit of detection was 0.834 ng/mL. The recoveries of GST in genuine blood samples ranged from 90.8 to 108.0% and in urine from 91.6 to 102.8%. The method has the capability of handling complex samples directly by enabling microextraction in an aqueous-aqueous single-drop system.

A series of selenium-containing non-fullerene acceptors with side chain engineering for organic solar cells

Non-fullerene acceptors (NFAs) have been crucial in improving the efficiency of organic solar cells (OSCs) due to their attractive properties, such as strong light-harvesting ability, easily tunable energy levels, and high crystallinity. Nevertheless, general NFAs have limited light absorption, and studies on the design of NFAs that can absorb a broad range of the solar spectrum and that offer complementary absorption to that of donors should be conducted. Because selenium, a chalcogen element, can induce strong intermolecular Se⋯Se interactions, planarity, and extended effective conjugated length in OSC materials, NFAs with selenium usually exhibit redshifted absorption. Here, we synthesized a series of selenium-containing non-fullerene acceptors with different inner alkyl chain lengths, named Se-Y6-BO (2,2'-((2Z, 2′Z)-((12,13-bis(2-butyloctyl)-3,9-dinonyl-12,13-dihydroselenopheno[2″,3'':4′,5']thieno[2′,3':4,5]pyrrolo[3,2-g]selenopheno[2′,3':4,5]thieno [3,23,2-b] [1,2,5]thiadiazolo [3,43,4-e]indole-2,10-diyl)bis(methanylylidene))bis(5,6-dichloro-3-oxo-2,3-dihydro-1H-indene-2,1-diylidene))dimalononitrile) and Se–Y6-HD (2,2'-((2Z, 2′Z)-((12,13-bis(2-hexyldecyl)-3,9-dinonyl-12,13-dihydroselenopheno[2″,3'':4′,5']thieno[2′,3':4,5]pyrrolo[3,2-g]selenopheno[2′,3':4,5]thieno [3,23,2-b] [1,2,5]thiadiazolo [3,43,4-e]indole-2,10-diyl)bis(methanylylidene))bis(5,6-dichloro-3-oxo-2,3-dihydro-1H-indene-2,1-diylidene))dimalononitrile). The optical absorption of two selenium-containing NFAs was redshifted compared with that of Y6 due to the effect of selenium atoms in the backbone. The PM6:Se-Y6-BO-based devices achieved a power conversion efficiency (PCE) of 13.8% with an open-circuit voltage (VOC) of 0.81 V, short-circuit current density (JSC) of 24.4 mA cm−2, and a fill factor of 0.70. Similarly, the OSCs based on PM6:Se–Y6-HD achieved a PCE of 13.6% and a JSC of 23.7 mA cm−2.

Manipulating Conjugated Polymer Backbone Dynamics through Controlled Thermal Cleavage of Alkyl Side Chains.

The morphological stability of an organic photovoltaic (OPV) device is greatly affected by the dynamics of donors and acceptors occurring near the device's operational temperature. These dynamics can be quantified by the glass transition temperature (Tg ) of conjugated polymers (CPs). Because flexible side chains possess much faster dynamics, the cleavage of the alkyl side chains will reduce chain dynamics, leading to a higher Tg . In this work, the Tg s for CPs are systematically studied with controlled side chain cleavage. Isothermal annealing of polythiophenes featuring thermallycleavable side chains at 140°C, is found to remove more than 95% of alkyl side chains in 24h, and raise the backbone Tg from 23to 75°C. Coarse grain molecular dynamics simulations are used to understand the Tg dependence on side chain cleavage. X-ray scattering indicates that the relative degree of crystallization remains constantduring isothermal annealing process. The effective conjugation length is not influenced by thermal cleavage; however, the density of chromophore is doubled after the complete removal of alkyl side chains. The combined effect of enhancing Tg and conserving crystalline structures during the thermal cleavage process can provide a pathway to improving the stability of optoelectronic properties in future OPV devices.

Oxo-Carotenoids as Efficient Superoxide Radical Scavengers.

Oxo-carotenoids containing conjugated carbonyl groups in their chains were designed to be more efficient superoxide radical scavengers than natural carotenoids, β-carotene and canthaxanthin. A practical chain-extension method for polyene dials (e.g., crocetin dial) was also proposed based on Horner–Wadsworth–Emmons olefination. Double aldol condensation between polyene dials and acetophenones with ring substituents produced oxo-carotenoids with substituted benzene rings. The antioxidant activity of oxo-carotenoids was measured using DPPH (radical) and ABTS (cationic radical) scavenging assays and compared with the analysis with the superoxide (anionic radical) probe. An effective conjugation length by carbon–carbon double bonds is important to provide superior antioxidant activity for oxo-carotenoids, regardless of the type of radical probe used in the assay. Increasing electron density is favorable to strong antioxidant activity in DPPH, and the phenol group is favored in ABTS, whereas electron deficient oxo-carotenoids are very potent in the superoxide radical assay. All oxo-carotenoids exhibited 105~151% better superoxide radical scavenging activity compared to beta-carotene (100%), whereas 38~155% in DPPH and 16~96% in ABTS radical scavenging activities were observed.

Ladder-like Polymer Brushes Containing Conjugated Poly(Propylenedioxythiophene) Chains.

The high stability and conductivity of 3,4-disubstituted polythiophenes such as poly(3,4-ethylenedioxythiophene) (PEDOT) make them attractive candidates for commercial applications. However, next-generation nanoelectronic devices require novel macromolecular strategies for the precise synthesis of advanced polymer structures as well as their arrangement. In this report, we present a synthetic route to make ladder-like polymer brushes with poly(3,4-propylenedioxythiophene) (PProDOT)-conjugated chains. The brushes were prepared via a self-templating surface-initiated technique (ST-SIP) that combines the surface-initiated atom transfer radical polymerization (SI-ATRP) of bifunctional ProDOT-based monomers and subsequent oxidative polymerization of the pendant ProDOT groups in the parent brushes. The brushes prepared in this way were characterized by grazing-angle FTIR, XPS spectroscopy, and AFM. Steady-state and time-resolved photoluminescence measurements were used to extract the information about the structure and effective conjugation length of PProDOT-based chains. Stability tests performed in ambient conditions and under exposure to standardized solar light revealed the remarkable stability of the obtained materials.

From blue fluorescence to red fluorescence: Solid-state oxidative coupling polymerization of fluorene and anthracene or naphthalene

Through the solid-state oxidative coupling polymerization, a series of fluorene-co-anthracene copolymer (PFA) and fluorene-co-naphthalene copolymers (PFN) were synthesized using FeCl3 as the oxidant. The structures of the copolymers were characterized by FT-IR and 1H NMR spectra, showing the random structures composed of fluorene units and 9,10-anthracene units or 1,4-linked naphthalene units. The increasing fluorene units in the backbones resulted in the increasing crystallization of copolymers by XRD patterns. All the copolymers exhibited good thermal stability. The optical properties could be adjusted by using different fluorene and anthracene or naphthalene ratios. Moreover, the polymer concentrations that affected the photoluminescence emission ranged from blue light to red light. The concentration-induced discoloration property also could be observed from the copolymers on the filter paper of TLC plates. This is attributed to the change in the effective conjugation length of a single polymer and the formation of polymer aggregates and excimers. These unique properties endow the PFA and PFN with potential applications in optoelectronics. Especially, these polymers exhibit enhanced emissions and on/off fluorescent switching which senses THF vapor efficiently.

Deciphering the Spectral Tuning Mechanism in Proteorhodopsin: The Dominant Role of Electrostatics Instead of Chromophore Geometry.

Proteorhodopsin (PR) is a photoactive proton pump found in marine bacteria. There are two phenotypes of PR exhibiting an environmental adaptation to the ocean's depth which tunes their maximum absorption: blue‐absorbing proteorhodopsin (BPR) and green‐absorbing proteorhodopsin (GPR). This blue/green color‐shift is controlled by a glutamine to leucine substitution at position 105 which accounts for a 20 nm shift. Typically, spectral tuning in rhodopsins is rationalized by the external point charge model but the Q105L mutation is charge neutral. To study this tuning mechanism, we employed the hybrid QM/MM method with sampling from molecular dynamics. Our results reveal that the positive partial charge of glutamine near the C14−C15 bond of retinal shortens the effective conjugation length of the chromophore compared to the leucine residue. The derived mechanism can be applied to explain the color regulation in other retinal proteins and can serve as a guideline for rational design of spectral shifts.

Doubly linked chiral phenanthrene oligomers for homogeneously \u03c0-extended helicenes with large effective conjugation length

Helically twisted conductive nanocarbon materials are applicable to optoelectronic and electromagnetic molecular devices working on the nanometer scale. Herein, we report the synthesis of per-peri-perbenzo[5]- and [9]helicenes in addition to previously reported π-extended [7]helicene. The homogeneously π-extended helicenes can be regarded as helically fused oligo-phenanthrenes. The HOMO−LUMO gap decreased significantly from 2.14 to 1.15 eV with increasing helical length, suggesting the large effective conjugation length (ECL) of the π-extended helical framework. The large ECL of π-extended helicenes is attributed to the large orbital interactions between the phenanthrene subunits at the 9- and 10-positions, which form a polyene-like electronic structure. Based on the experimental results and DFT calculations, the ultrafast decay dynamics on the sub-picosecond timescale were attributed to the low-lying conical intersection.