Three symmetrical donor–acceptor–donor (D–A–D) luminophores (C1, C2, and C3) with pyrazine derivatives as electron-withdrawing groups have been developed for multistimuli-responsive luminescence switching. For comparison, reference compounds R1 and R2 without the pyrazine moiety have also been synthesized. Intramolecular charge transfer (ICT) interactions can be found for all D–A–D luminophores owing to the electron-withdrawing properties of the two imine nitrogen atoms in the pyrazine ring and the electron-donating properties of the other two amine nitrogen atoms in the two triphenylamine units. Moreover, luminophores C1, C2, and C3 exhibit “on–off–on” luminescence switching properties in mixtures of water/tetrahydrofuran with increasing water content, which is different from the “on–off” switching for typical aggregation-caused quenching (ACQ) materials and “off–on” switching for traditional aggregation-induced emission (AIE) materials. Additionally, upon grinding the pristine samples, luminophores C1, C2, and C3 display bathochromically shifted photoluminescence maxima that can be recovered by either solvent fuming or thermal annealing treatments. The piezofluorochromic (PFC) properties are more pronounced than those for reference compounds R1 and R2, which indicates that D–A molecules have the ability to amplify the PFC effect by tuning the ICT interactions upon tiny structural changes under pressure. Furthermore, the target luminophores demonstrate acid-responsive photoluminescence spectra that can be recovered in either basic or ambient environments. These results suggest that D–A complexes are potential candidates for multistimuli-responsive luminescence switching because their ICT profiles can be facilely tuned with tiny external stimuli.

Two series of regioisomeric luminophores that contained a dithieno[2,3-a:3′,2′-c]phenazine (DTP) unit as an electron acceptor have been designed and synthesized. To investigate the effect of substitution pattern on the optoelectronic properties of these luminophores, electron donors (N,N-dihexylaniline or N,N-dihexyl-4-vinylaniline) were incorporated at the 2,5-, 8,11-, and 9,10-positions of the DTP unit. We found that the optoelectronic properties of the regioisomeric luminophores were greatly affected by the substitution pattern: functionalization at the 8,11-positions of the DTP unit was superior to the other two substitution patterns in extending the effective π-conjugation and strengthening the intramolecular charge-transfer interactions. Moreover, the insertion of vinyl groups between the DTP and N,N-dihexylaniline units narrowed the energy band-gap for isomers 4 and 5. However, hypsochromically shifted absorption and photoluminescence maxima were observed for isomeric luminophore 6, in which electron donors were substituted at the 2,5-positions of the DTP unit. These results should facilitate greater understanding of the structure–property relationships in regioisomeric semiconductors and present a new way to design optoelectronic materials with effective substitution patterns.

A series of novel metal-free organic dyes containing the thiazolo[5,4-d]thiazole moiety were designed and synthesized for quasi-solid-state dye-sensitized solar cells (DSSCs). Different alkoxy chains were introduced into the electron donor part of the dye molecules for comparison. The optical, electrochemical, and photovoltaic properties for all sensitizers were systematically investigated. It was found that the sensitizers with the different alkoxy groups have similar photophysical and electrochemical properties, such as absorbance and energy levels, owing to their close chemical structures. However, the quasi-solid-state DSSCs based on the resulting sensitizers exhibit different performance parameters. The quasi-solid-state DSSC based on sensitizer FNE74 with two octyloxy chains possessed the highest solar energy conversion efficiency of 5.10 % under standard AM 1.5G sunlight illumination without the use of coadsorbant agents.

Thieno[3,4-c]pyrrole-4,6-dione-based organic sensitizers with triphenylamine (FNE38 and FNE40) or julolidine (FNE39 and FNE41) as electron-donating unit have been designed and synthesized. A linear hexyl group or a branched alkyl chain, the 2-ethylhexyl group, is incorporated into molecular skeleton of the dyes to minimize intermolecular interactions. The absorption, electrochemical, and photovoltaic properties for these sensitizers were then systematically investigated. It is found that the sensitizers have similar photophysical and electrochemical properties, such as absorption spectra and energy levels, owing to their close chemical structures. However, the quasi-solid-state dye-sensitized solar cells (DSSCs) based on the two types of sensitizers exhibit very different performance parameters. Upon the incorporation of the short ethyl group on the hexyl moiety, enhancements in both open-circuit voltage (V_oc) and short-circuit current (J_sc) are achieved for the quasi-solid-state DSSCs. The V_oc gains originating from the suppression of charge recombination were quantitatively investigated and are in good agreement with the experimentally observed V_oc enhancements. Therefore, an enhanced solar energy conversion efficiency (η) of 6.16 %, constituting an increase by 23 %, is achieved under standard AM 1.5 sunlight without the use of coadsorbant agents for the quasi-solid-state DSSC based on sensitizer FNE40, which bears the branched alkyl group, in comparison with that based on FNE38 carrying the linear alkyl group. This work presents a design concept for considering the crucial importance of the branched alkyl substituent in novel metal-free organic sensitizers.