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Triphenylamine functionalized salicylaldimine difluoroboron complexes bearing different substituents have been synthesized. The photophysical results showed that these complexes exhibited intramolecular charge transfer (ICT) emission and solvatochromism. The fluorescence of these complexes could be well-tuned by the substituents in the ligands. The introduction of tert-butyl groups causes the complex TST to show obvious aggregation-induced emission (AIE) activity. In particular, the complexes without other substitutions or with the substitutions of bromo, tert-butyl and methoxyl on salicylaldimine moieties displayed reversible mechanofluorochromic (MFC) behaviors. XRD patterns and DSC curves of the complexes in different solid states suggested that the transformation between crystalline and amorphous states was responsible for the MFC properties. The relationship between the molecular structures and MFC properties suggested that the high polarity of the conjugated skeletons in difluoroboron complexes was beneficial for realizing high-contrast performance in mechanofluorochromism. [ABSTRACT FROM AUTHOR]

New D–π–A-type triphenylamine-containing benzimidazoles, benzoxazoles and benzothiazoles have been synthesized. It was found that the introduction of a cyano group in vinyl and methyl in triphenylamine was favorable for producing mechanofluorochromism of the fused heterocyclic derivatives. The single crystal X-ray diffraction data revealed that the intermolecular interactions of the H-bonding formed from the cyano group and the C–H…π interaction formed from the methyl group would rigidify the molecular conformations, leading to strong solid-state emission. Interestingly, the solid-state emission of the synthesized triphenylamine-containing fused heterocycles bearing cyano and/or methyl groups could be tuned by external mechanical forces on account of the transition between crystalline and amorphous states or between a highly ordered crystalline state and a less ordered state. [ABSTRACT FROM AUTHOR]

Cyanostyrene-based D–π–A type conjugated compounds bearing triphenylamine units (G1, G1-N and G2) have been synthesized. By tuning the conjugated skeleton and the electron withdrawing ability of the acceptor, green, orange and red light emitters were achieved. It is interesting that although their emissions in solutions were weak, we observed strong emission in solid states. For example, the ΦF of the dendritic molecule G2 in powder reached 0.67, which was more than 20 times of that in THF. The single crystal X-ray diffraction data revealed that the intermolecular H-bonds of C–H…O, C–H…N and C–H…π led to the increased rigidity of the molecular skeleton, which would restrict the intramolecular rotation, yielding high ΦF in solid states. These AIE compounds may become candidates for emitting materials. [ABSTRACT FROM AUTHOR]

Abstract New D-π-A type quinoline derivatives (CbzVQ and TPAVQ) were synthesized via Knoevenagel condensation reactions. They exhibited reversible high-contrast mechanofluorochromic (MFC) behavior under grinding/fuming treatment. Taking CbzVQ as an example, its fluorescence could be switched from blue to greyish green by grinding the as-synthesized sample into ground powders, and the fluorescence emission was red-shifted from 449 nm (with shoulders at 475 nm and 520 nm) to 578 nm (with shoulders at ca. 450 nm and 500 nm). Such large shift of the maximal emission peak during MFC processes was rare reported. In addition, the casting films of CbzVQ and TPAVQ emitted blue and green light, respectively, which was turned to red rapidly induced by TFA (trifluoroacetic acid) vapor. Moreover, the emission could be recovered stimulated by TEA (triethylamine) vapor, so the quinoline derivatives exhibited reversible fluorescent sensory properties. TPAVQ showed better performance in the detection of TFA vapor than CbzVQ due to the strong electron-donating ability of triphenylamine compared with carbazole. The detection limit and the decay time of TPAVQ towards TFA vapor were 163 ppb and 0.22 s, respectively. Apparently, the D-π-A type quinoline derivatives are candidates as multi-stimuli responsive fluorescent materials. Graphical abstract Image 1 Highlights • New D-π-A type quinoline derivatives bearing carbazole and triphenylamine are synthesized. • Quinoline derivatives show reversible high-contrast mechanofluorochromism. • The shift of the maximal emission for CbzVQ reaches 129 nm during mechanofluorochromic processes. • The emitting color of quinoline derivatives is turn to red from blue or green rapidly stimulated by TFA vapor. [ABSTRACT FROM AUTHOR]

Two push-pull compounds, which are comprised of triphenylamine (TPA) (electron donor units) and functionalized β-diketones difluorboron complexes (electron acceptor units) are probed by many spectroscopies, which offers the relationship between electron acceptor and the intrinsic excited state properties of push–pull chromophores. We found that the photoluminescence (PL) intensity would enhance with the number of electron acceptor. Transient absorption (TA) data shows that intramolecular charge transfer (ICT) process really exists in the two molecules after photoexcitation and this process would be prolonged through increasing the electron-acceptor, which would be responsible for the improvement of PL property. [ABSTRACT FROM AUTHOR]

Abstract: Two new star-shaped difluoroboron β-diketonate complexes (TBC) 3 Ph and (TBF) 3 Ph, in which the terminal groups of triphenylamine functionalized difluoroboron β-diketonates were bridged by carbazole or fluorene to the core of 1,3,5-benzene, have been synthesized. It was found that they gave high molar extinction coefficients, meaning strong light-harvesting ability, and emitted intense yellow light with fluorescence quantum yields (Φ F) of 0.73 and 0.67 for (TBC) 3 Ph and (TBF) 3 Ph, respectively, in toluene as well as red light in solid states with Φ F of 0.36 and 0.27, respectively. The electrochemical behaviors suggested that they had considerably higher electron affinities than tris(8-hydroxyquinoline)aluminum (AlQ3), which indicated that they could be used as electron-transporting materials besides emitting materials. [Copyright &y& Elsevier]

Abstract: Three new donor-π-acceptor (D-π-A) metal-free organic dyes, in which dendritic triphenylamine acts as donor, and furan, thiophene and benzene as π-linkers, were synthesized, characterized and used for the application of dye sensitized solar cell (DSSC). Among the fabricated DSSCs, the device based on the furan as π-linker exhibited a short circuit current density of 14.56 mA cm−2, an open circuit photo voltage of 0.71 V and a fill factor of 0.59, implying a power conversion efficiency (η) of 6.10%. The devices sensitized by dyes with thiophene and benzene as π-linker possessed relative lower η, 5.92% and 4.97%, respectively. [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]

Abstract: Three new triphenylamine-based dyes with Y-shaped conformation bearing triphenylamino-vinyl, 10-octyl-10H-phenothiazine-vinyl and 9-octyl-9H-carbazole-vinyl as arms (TT, TP, and TC) have been synthesized. From electrochemical investigations it is found that they can be employed in DSSCs due to the balanced HOMO and LUMO energy levels. Notably, the photo-to-electrical conversion efficiency of the DSSCs sensitized with branched TT, TP, and TC reach 5.12%, 4.84%, and 3.63%, which are higher than that sensitized with T (2.79%), and the DSSC sensitized with TT shows higher IPCE response and better photovoltaic performances (J sc=12.37mA/cm2, V oc=0.72V and ff=0.58) than others. These results reveal that the introduction of branched Y-shaped extended π-conjugated donors to D-π-A dyes cannot only enlarge the spectral response range, but also suppress the molecular aggregation on TiO2 films to a certain extent, which would enhance the performance of DSSCs. [Copyright &y& Elsevier]

Abstract: We have synthesized a series of new dipolar organic dyes Bn (n=0, 1, 2) employing triarylamine as the electron-donor, 2-cyanoacrylic acid as the electron-acceptor, and fluorenevinylene as the conjugated bridge, which were used as sensitizers in dye-sensitized solar cells. It is found that the solar-energy-to-electricity conversion efficiencies of the prepared DSSCs are in the range of 2.79–5.56%, which reach 35–70% of a standard device based on N719 fabricated and measured under the same conditions. The DSSC sensitized with B1 with balanced length of conjugated bridge shows the highest photo-to-electrical energy conversion efficiency and the open-circuit photovoltage (V oc) of 0.86 V. [Copyright &y& Elsevier]