Synthesis, Photophysical, and Optical Limiting Properties of Twistacene-Functionalized Arenes.

To realize the relationship of structure and property, four novel twistacene-functionalized arenes, namely, 1,4-bis(2,7-di-tert-butyl-9,14-bis(4-(tert-butyl)phenyl)dibenzo[de,qr]tetracen-11-yl)buta-1,3-diyne (4), 1,4-bis(3,5,10,12-tetra-tert-butyltribenzo[a,d,g]coronen-16-yl)buta-1,3-diyne (7), 1,4-bis(2,7-di-tert-butyl-9,14-bis(4-(tert-butyl)phenyl)dibenzo[de,qr]tetracen-10-yl)buta-1,3-diyne (10), 1,4-bis(3,5,10,12-tetra-tert-butyltribenzo[a,d,g]coronen-15-yl)buta-1,3-diyne (13), linked with butadiyne as π bridges have been strategically synthesized and characterized. The nonlinear optical properties are detailly examined in solution through the open-aperture Z-scan method in a comparative manner, indicating that molecules 4 and 7 exhibit better nonlinear optical responses than 10 and 13. Among them, 4 and 7 exhibit excellent optical limiting responses with limiting thresholds of 0.17 and 0.19 J/cm2, respectively, being superior to the state-of-the-art material C60. The ultrafast transient absorption test and DFT calculations suggest that the nonlinear absorption mechanisms belong to TPA-induced ESA. In addition, the effective percentage calculated from TD-DFT can provide a brief glance to evaluate the optical limiting performance.

Coumarin-embedded [5]helicene derivatives: synthesis, X-ray analysis and photoconducting properties.

Two novel coumarin-embedded π-extended [5]helicene derivatives (3a and 6a) have been strategically synthesized and characterized, and the structure of 3a was determined via single crystal X-ray analysis. Both of them exhibit green fluorescence in dichloromethane. In addition, molecule 3a can aggregate to form a large quantity of nanowires through the re-precipitation method. More importantly, the photoelectric conversion properties of 3a nanowire-C60 based films are much better than those of the thin film of bulk 3a-C60, indicating that the ordered nanostructures are a crucial factor for enhancing device performance.

Self-Assembly of Functionalized Twistarenes into Supramolecular Assemblies with Chiroptical Property and Photoconductive Behavior.

A pair of novel chiral 1-phenylethylamine-modified twistarenes (4 and 11; compound 4 = 9,14-di-tert-butyl-7,16-diphenyl-2-(1-phenylethyl)-1H-benzo[8',9']triphenyleno[2',3':6,7]fluoreno[2,1,9-def]isoquinoline-1,3(2H)-dione) have been synthesized and characterized, and how the solvent component affects the chirality transfer of their self-assembled processes is investigated in mixtures with THF and H2O. The ordered assembly of 11 exhibits circular dichroism response. In addition, both 11a and 11b display positive photoconducting behavior.

Straightforward Synthesis of Pentagon-Embedded Expanded [11]Helicenes for Radiative Cooling Property.

Two new pentagon-embedded carbo[11]helicenes have been designed and synthesized in a three-step process, which are the first example of carbo[11]helicenes through the post-functionalization of twistacene. TD-DFT analyses indicate that both of them possess high enantiomerization barriers of 42.29 kcal/mol and 40.76 kcal/mol, respectively. They emit strong red fluorescence and can be chemically oxidized into stable cationic radicals upon addition of AgSbF6 evidenced by the bathochromic-shifted absorption spectra and the appearance of electronic paramagnetic resonance (EPR) signals. In addition, such helical derivatives can be chosen as radiative cooling materials in a glass model house, and the maxima of 5.4 °C for the former and 6.5 °C for the latter are found in the comparative tests, which might be caused by the NIR reflective response.

Heptagon-Embedded Helicene Derivatives: Synthesis, Crystal Structural Analyses, and Circularly Polarized Luminescence.

Two pairs of isomers of heptagon-embedded helical arenes (3/6 and 10/13) have been strategically prepared, where the molecular structures of 3 and 13 have been identified through single crystal X-ray diffraction analysis. The effect of the heptagon unit on the physical properties of 3, 6, 10, and 13 is investigated in a comparative manner, and the results indicate that the optical enantiomers of 13 obtained from HPLC exhibit promising chiroptical properties.

Facile Synthesis of Helicene-Containing Arenes for Optical Limiting Devices.

A helicene-containing arene and its linear analogue have been successfully synthesized and characterized, where the single-crystal X-ray diffraction analysis indicates that the former can arrange in an offset packing style with a π-π overlap. The introduction of pentagon-rings into the parent skeletons in the resulting compounds can boost the stability, and such helicene-containing molecule possesses higher solubility in organic solvent than the linear analogue. The structural difference has significantly influenced the optical limiting performance. The former in solution and in doped gel glass presents higher optical limiting response towards 532 nm laser than the latter. This study can enrich the functionalization of helicene, which can possess a positive effect in terms of nonlinear optical property.

Synthesis, Photoswitching Behavior and Nonlinear Optical Properties of Substituted Tribenzo[a,d,g]coronene.

A family of tribenzocoronene derivatives bearing various substituents (3) were constructed through the Diels-Alder reaction, followed by the Scholl oxidation, where the molecular structure of 3b was determined via single crystal X-ray diffraction analysis. The effect of substitution on the optical and electrochemical property was systematically investigated, with the assistance of theoretical calculations. Moreover, the thin films of the resulting molecules 3b and 3e complexed with fullerene produced strong photocurrent response upon irradiation of white light. In addition, 3b and 3e exhibit a positive nonlinear optical response resulting from the two-photon absorption and excited state absorption processes.

Ring-Opening Oligomerization Mechanism of a Vanillin-Furfurylamine-Based Benzoxazine and a Mono-Azomethine Derivative.

Exploring the ring-opening polymerization (ROP) mechanism of benzoxazines is a fundamental issue in benzoxazine chemistry. Though some research papers on the topic have been reported, the ROP mechanism of mono-benzoxazines is still elusive. The key point for mechanistic studies is to determine and characterize the structure and formation pathways of the products generated in ROP. In this paper, the ROP of a vanillin-furfurylamine-based benzoxazine and a mono-azomethine derivative is studied with differential scanning calorimetry, fourier transform infrared spectroscopy, nuclear magnetic resonance, and electrospray ionization mass spectrometry, respectively. The results show that the products consist of a range of cationic species, zwitterions, fragments, and series of cyclic and linear oligomers of varying molecular sizes. It is proposed that both mono-benzoxazines undergo thermally activated cationic ring-opening oligomerization via zwitterion intermediates. Upon thermal induction, multi-bond-cleavage takes place to form various zwitterionic intermediates, which react with a monomer, a fragment, or a second zwitterion by several pathways to generate cyclic and linear oligomers.

Synthesis, Crystal Analysis, and Physical Properties of Double [6]helicene-Containing Heteroarenes with Circularly Polarized Luminescence.

Two novel helical heteronanographenes bearing a [6]helicene unit (3a and 5a) have been synthesized, and their molecular structures are unambiguously determined via single-crystal X-ray diffraction analyses. Density functional theory calculations suggest that the as-prepared compounds have isomerization barriers of 29.02 kcal/mol for 3a and 34.07 kcal/mol for 5a, respectively. Optical enantiomers of 5a exhibit appealing chiroptical properties.

Enhanced Ultrafast Broadband Reverse Saturable Absorption in Twistacenes with Enlarged π-Conjugated Central Bridge.

Optical nonlinearities of two all-carbon twistacenes, DPyA and DPyN, with the different π-conjugated central bridges were investigated. The nonlinear absorption properties of these compounds were measured using the femtosecond Z-scan with wavelengths between 650 and 900 nm. It has been found that the nonlinear absorption originated from two-photon absorption (TPA) and TPA-induced excited state absorption (ESA), wherein DPyA demonstrates higher performance than DPyN. The TPA cross section of DPyA (4300 GM) is nearly 4.3 times larger than that of DPyN at 650 nm. Moreover, the different central structures modulate the intensity of ESA at 532 nm, and DPyA exhibits an excellent ESA at 532 nm with multi-pulse excitation. Meanwhile, the result of data fitting and quantum chemistry calculation shows that the enhancement of nonlinear absorption in DPyA is due to the extended π- conjugated bridge and improved delocalization of π-electrons. These all-carbon twistacenes could yield potential applications in optical power limiting (OPL) technology.

Synthesis and Ultrafast Broadband Optical Limiting Properties of a Two-Branched Twistacene.

A novel two-branched twistacene (PyDN) has been designed and synthesized for application on ultrafast optical limiting. This twistacene exhibits excellent two photon absorption and two photon absorption-induced excited singlet state absorption, which was systematically investigated with a femtosecond Z-scan experiment, transient absorption spectrum, and two-photon excited fluorescence experiments. The admirable two photon absorption is attributed to the high degree of π electron delocalization in twistacene which is caused by introduction of two strong donors. The excited singlet state absorption cooperates with two-photon absorption to provide an excellent ultrafast optical limiting behavior with high linear transmittance, where the thresholds are 2.3-5.3 mJ/cm2 in the spectral region of 532-800 nm of femtosecond laser and 133 mJ/cm2 for picosecond pulse at 532 nm. These thresholds are lower than that of most of the optical limiters reported previously, which indicates PyDN is a promising candidate for ultrafast optical limiting.

Effect of Annulation Mode of Twistarene on the Physical Property and Self-Assembly Behavior of Functionalized Curved Aromatic Molecules.

Four novel curved polycyclic aromatic hydrocarbons 3 a, 5, 8, 15 a have been synthesized and characterized, where molecules 3 a and 15 a bear [5]carbohelicene units. X-ray single crystal analyses indicate that compound 3 a shows offset packing arrangements of (P5 )- and (M5 )-isomers, and 15 a has a symmetrical plane and looks like a butterfly. In comparison, 8 exhibits a slightly curved structure, in which the significant convex-to-convex π-overlap with the shortest distance of 3.42 Šoccurs. In addition, the effect of annulation mode of twistarenes on the physical properties, self-assembly behaviors, and switchable photoconductivity of the as-prepared curved aromatic compounds were further examined in a comparative manner.

3D Carbiyne Nanospheres Boosting Excellent Lithium and Sodium Storage Performance.

Reasonable design of electrode materials with specific morphology and structure can efficiently improve the metal ions storage and transmission properties of metal ion batteries. Here the preparation of spirobifluorene-based three-dimensional carbiyne nanosphere (SBFCY-NS) that is composed of spirobifluorene (SBF) and alkyne bonds is reported. Benefiting from the rigid spatial structure of SBF, numerous precursors are coupled through the connection of acetylene bonds, extending to form solid nanospheres. Abundant storage spaces and convenient multi-directional transmission paths for metal ions are available inside the three-dimensional (3D) carbiyne structure. Thus, SBFCY-NS is applied as efficient anode for lithium-ion battery and sodium-ion battery. The good stability of SBFCY-NS-based electrode and its improved Coulombic efficiency can be attributed to the special morphology of nanospheres, which can easily form thin and stable solid electrolyte interface film on the surface. Those results further promote the preparation of spherical carbon-based materials with abundant pores that can be applied in the field of electrodes.

Double π-Extended Helicene Derivatives Containing Pentagonal Rings: Synthesis, Crystal Analyses, and Photophysics.

Two novel double π-extended [n]helicene (n = 5, 6) derivatives (7b and 9) including pentagonal rings have been synthesized and characterized. Both of them have three isomers containing two enantiomers (P6), (M6), and a diastereoisomer in a meso form (P,M). X-ray single crystal analyses suggest that molecules 7b and 9 exhibit offset packing models of (P6,P5)- and (M6,M5)-isomers. Optical resolution of the resultant compound 7b was finished, and their chiroptical properties, as well as the DFT calculations, were also examined.

Pentagon-Containing π-Expanded Systems: Synthesis and Photophysical Properties.

We have designed and synthesized three novel twistacene-modified enlarged pentagon-containing π-systems (6 and 9) with mismatched structures. The introduction of electron-withdrawing cyclopenta rings in the parent skeleton effectively stabilizes the electron-rich arenes. Their optoelectronic properties were studied via ultraviolet-visible (UV-vis) absorption spectra, fluorescence spectra, cyclic voltammetry, and density functional theory (DFT) calculation. In addition, chemical oxidation of the as-prepared compounds with nitrosonium hexafluoroantimonate could form the corresponding cationic radicals.

An investigation of broadband optical nonlinear absorption and transient nonlinear refraction in a fluorenone-based compound.

A novel fluorenone derivative, FO52, is designed and synthesized. The fluorenone group is introduced to provide the central π-conjugated system in the molecule and triphenylamine is substituted at both sides. Intramolecular Charge Transfer (ICT) from the terminal groups to the molecular center is confirmed via DFT calculations. Ultrafast optical nonlinearities are investigated via Z-scan and transient absorption spectroscopy (TAS) studies with a 190 fs laser. Reverse saturable absorption, two-photon induced excited-state absorption, and pure two-photon absorption are observed at 532 nm, 650 nm, and 800 nm, respectively. The different mechanisms at these wavelengths are discussed and interpreted with assistance from the results from TAS. Furthermore, strong excited-state refraction and ultrafast negative refraction from the bound electron response are resolved and discussed in phase object pump probe (POPP) experiments. The results suggest that the ICT-enhanced optical nonlinearities provide FO52 with strong optical limiting capabilities at visible wavelengths and ultrafast refraction with tiny attenuation in the near infrared region. The combination of these properties in one compound could be attractive for applications like laser protection and low-loss all-optical switching.

Tuning Nonlinear Optical Behavior by Incorporation of the Chalcogenophene into Twistacenes.

Four chalcogenophene-fused acenes containing O, S, Se, or Te, respectively, were presented, and the chalcogenophene effect on linear and nonlinear optics was systematically investigated. Their excited-state absorption performance and two-photon absorption (TPA) capacity could be modulated by the incorporating chalcogen atoms. The experimental results showed that the heavy chalcogen facilitated the intersystem crossing resulting in the presence of the triplet state absorption for PyPSe and PyPTe, and the TPA capacity gradually increased with the atomic size of the chalcogens. The theoretical calculation inferred that their nonlinear optical performance was closely related to the contributions of the chalcogenophene component to heterotwistacenes in the final excited state. In addition, PyPTe was able to work under various laser pulses from femtoseconds to nanoseconds.

Expanded benzofuran-decorated twistacene derivatives: synthesis, characterization and single-component white electroluminescence.

Two novel phenanthro[9,10-b]benzofuran and pyreno[4,5-b]benzofuran modified twistacene derivatives, 9 and 10, have been successfully synthesized via Suzuki coupling and then characterized. The photophysical properties were examined and DFT calculations were carried out in a comparative manner, and both molecules emitted strong blue light in organic solvents and in the solid state. Impressively, fabricated electroluminescent devices based on these single emitters radiate pure white light.

Stable Double and Quadruple [5]Helicene Derivatives: Synthesis, Structural Analysis, and Physical Properties.

Two novel [5]helicene derivatives (labeled 5 and 8) have been successfully synthesized and characterized. The structural analyses, photophysical properties, along with density functional theory calculations for unveiling the helicity inversion and equilibrium of the diastereomers, were investigated in a comparative manner. In addition, chemical oxidation of them indicated that molecule 8 exhibited the formation of the radical cation at room temperature.

Electron-Rich Twistacene-Modified Arylboron Donor-Acceptor Systems: Synthesis, Photophysics, and Electroluminescence with Hot Exciton Response.

A series of twistacene-functionalized donor (D)-π-acceptor (A) derivatives (2-5) have been designed and synthesized, in which twistacene can be regarded as a promising platform for electron-rich systems for fluorescence emitters. The connecting modes and various acceptors are also examined to investigate the effect of structural changes on the photophysical, electrochemical, and thermal properties. The strong electron-withdrawing capability of the arylboron-modified benzonitrile unit can effectively separate the HOMO and LUMO energy levels of 4/5, which is beneficial for the formation of thermally activated delayed fluorescence (TADF) molecules. Cyan and orange organic light-emitting diodes based on 4 and 5 exhibit promising electroluminescence with a maximum brightness of 7643 cd m-2 for device-4 and 14871 cd m-2 for device-5.