Search

A series of novel monodisperse, structurally well defined vinylene‐linked phenothiazine oligomers containing up to 7 phenothiazine units have been designed and synthesized by Heck reaction and McMurry reaction with a convergent approach. These conjugated oligomers showed a progressive bathochromic shift of the absorption maxima and high fluorescence quantum yields in solutions. Notably, the oligomers without strong donor and acceptor units exhibit two‐photon absorption properties, and the two‐photon absorption cross sections (δ) increase with the number of covalently linked phenothiazine units, and δ reaches up to 2071 GM for the one with 7 phenothiazine units at 800 nm. The oligomers might be used as models to study structure–property relationship for their corresponding polymers or applied in organic electronic materials. [ABSTRACT FROM AUTHOR]

Abstract: Four new well-defined monodisperse linear oligofluorenes with anthracene core An-OFVn (n =1–4) have been synthesized through Heck and Wittig reaction. These conjugated oligomers exhibit good solubility in common organic solvents. It is found that the conjugation length of the oligomers can be extended and the formation of excimers can be suppressed with increasing the number of fluorene–vinylene units linked in the 9,10-positions of anthracene. [Copyright &y& Elsevier]

Abstract: A series of linear monodisperse vinylene-linked phenothiazine oligomers have been synthesized by alternate Heck reaction and Wittig reaction in good yields. It was found that their absorption and fluorescence emission bands red-shifted with increasing phenothiazine units due to extending of the conjugated degree. The fluorescent quantum yield increased from OPTZ1 to OPTZ6, and the Φ F of OPTZ6 was close to phenothiazine-based polymers. [Copyright &y& Elsevier]

Abstract: Novel monodisperse linear 3,9-linked oligocarbazoles (OCAs) were prepared stepwise using Ullmann coupling reaction in seal-tubes. The resulting OCAs were soluble in common organic solvents. The UV–vis spectra of OCAs exhibited small red shift and their intensities increased linearly with the increase of the carbazole moieties, suggesting that no intramolecular π-interactions appeared at ⩽8-mer. All the OCAs gave strong fluorescence and it was found that the conjugated degree of linear OCAs would be saturated when the number of carbazole units reaches four. [Copyright &y& Elsevier]

Abstract: To meet the need for rapid and low-cost chemical sensing of explosive, new fluorescence chemosensors based on oligophenothiazines for probing vapor-phase nitro compounds have been developed. The phenothiazine-based trimer P3 and pentamer P5 have been synthesized via Heck and Wittig reactions by convergent approach. It was found that they can detect the vapors of nitro compounds, including p-nitrotoluene ( p -NT), 2,4-dinitrotoluene (DNT), 2,4,6-trinitrotoluene (TNT) with good sensitivity and reversibility. And the sensor of P3 film gave a linear fluorescence quenching response to 7–800ppb TNT with the detection limit of 4ppb. For DNT vapor, a linear working range of the sensor was 2–24ppm with the detection limit of 40ppb. Meanwhile, the interferents, including common organic solvents, p-nitrophenol and 2,4-dinitrophenylhydrazine cannot lead to obvious fluorescence quenching, meaning that the film based on oligophenothiazines exhibited good specificity of fluorescence response to explosive. Based on the fluorescence lifetime and UV–vis absorption measurements, we suggested that the fluorescence quenching of oligophenothiazine-based films exposed to the vapors of nitro compounds was due to the formation of non-fluorescent charge-transfer complex between oligophenothiazine and nitro compounds. [ABSTRACT FROM AUTHOR]

New branched benzothiadiazole-cored conjugated oligomers with terminal carbazoles 1 and 2 have been synthesized. It was found that no obvious shifts of the maximal absorption bands for 1 and 2 were detected in the films compared with those in solutions, indicating weak π-π stacking occurred in the solid states on account of site isolation effect of the branched architectures. Hence, the synthesized oligomers could emit strong red light in the films. Notably, the emission of the films based on 1 and 2 could be quenched obviously upon exposed to gaseous TNT and DNT. The fluorescence quenching efficiency of the oligomer 2 -based film reached 91% when exposed to the saturated vapor of DNT for 3 min at 55 °C. The linear Stern–Volmer plot and the decrease of the fluorescence lifetime of 2 induced by DNT suggested the fluorescence sensing mechanism was due to the photo-induced electron transfer. [ABSTRACT FROM AUTHOR]

The effects of π-spacer and electron donor groups on the photophysical behaviors of fluorenone-based linear conjugated oligomers have been systemically investigated. Solvent-dependent steady-state measurements exhibit that the fluorene vinylene ( FV) spacer and the electron-donating ability of donor group are able to modulate the spectral features of oligomers and the fluorescence quantum yield could decrease with the increasing of the solvent polarity. Meanwhile, quantum chemical calculation simulates their absorption spectra, and analyzes their electron transition components simultaneously. The transient absorption measurements focus on the photoexcitation dynamics of these oligomers in the toluene solution, which show that an intramolecular charge transfer state exists in the relaxation process of excited states, and its generation process could accelerate with the introduction of FV spacer and the enhancement of donor strength. [ABSTRACT FROM AUTHOR]

Highlights: [•] Two fluorine (F) based oligomers are synthesized and investigated in detail. [•] F units modulate the steady-state spectra of oligomers. [•] DFT calculations analyze molecular structure and the electronic transition. [•] F units increase the TPF efficiency and the TPA cross-section of oligomers. [•] F units shorten the lifetime of excited oligomers. [Copyright &y& Elsevier]

Highlights: [•] π-Spacer dependent optical properties of fluorenone-based oligomers are studied. [•] Fluorene–ethylene (FE) spacer could modulate the steady-state spectra of oligomers. [•] DFT calculations confirm the ICT nature in the HOMO–LUMO transition. [•] FE spacer could increase the TPPL efficiency and TPA cross-section of oligomers. [•] TA measurement confirms the ICT state exists in the relaxation of excited oligomer. [Copyright &y& Elsevier]

Abstract: We compare the effects of fluorene–ethylene (FE) spacers on the photo-physical properties of fluorenone-based conjugated oligomers. The introduction of FE spacer could modulate the steady-state spectra and weaken the difference between donor-dependent spectral features. Meanwhile, the quantum chemical calculations exhibit that the electron transition mechanism modulated by FE unit is variable with the donor of oligomers. The FE π-spacer mainly rises the HOMO and facilitates the electron delocalization in the fluorene end-capped oligomer, while it lowers the LUMO and enhances the donor effect in the triphenylamine end-capped one. The time-resolved fluorescence measurement exhibits that the difference between donor-dependent excited state lifetimes of oligomers becomes less obvious after the introduction of FE units. Moreover, the nonlinear optical measurements show that the FE spacer is able to improve the two-photon fluorescence efficiency and enhance the two-photon absorption cross-section of oligomers simultaneously, but the difference in two-photon characteristics between oligomers with different donors is also decreased. [Copyright &y& Elsevier]

Abstract: We systemically investigate the photophysical properties of two star-shaped truxene based oligomers with different oligo(fluorene-vinylene) arms (Tr-OFV1 and Tr-OFV3) in solution system. The chemical quantum calculation exhibits that the electronic transition depends on the number of fluorene-vinylene (FV) groups in oligomers. The transient absorption (TA) data exhibits that increasing of FV groups in branch arms could accelerate the relaxation of excited oligomers, and the intensity-dependent exciton–exciton annihilation behavior could appear in the relaxation process of excited Tr-OFV3 and disappear in that of Tr-OFV1, indicating that their photophysical behavior is also closed to the number of FV unit. [Copyright &y& Elsevier]

Abstract: Experimental and theoretical studies on the donor-dependent optical characteristics of two D–π–A–π–D type linear fluorenone-based conjugated oligomers are presented, where fluorene and triphenylamine act as the donors, respectively. Because of the strong electron-donating ability, the triphenylamine chromophores lead to red-shifts of spectral features, shorten the excited state lifetime, and enhance the two-photon fluorescence efficiency and two-photon absorption cross-section in comparison with fluorene groups. Quantum chemical calculations provide complementary information regarding the molecular structures and the frontier orbitals, which can provide a deep insight into the electronic structure and properties of oligomers. [Copyright &y& Elsevier]