Push-pull fluorophores exhibiting pronounced intramolecular charge transfer have a low fluorescence quantum yield. Here we report a new series of D-π-A push-pull fluorophores containing a unified 2,2'-bipyridine domain acceptor with...

Carbazole/fluorene substituted 5-phenyl-2,2'-bipyridine D-π-A fluorophores: Photophysical data, hyperpolarizability and CT-indices

Pyridine-based derivatives Py-1, Py-2, and Py-3 were synthesized by the Suzuki cross-coupling reaction, and the effect of different substituents at the ortho position of the pyridine ring was investigated. In the molecular framework of push–pull compounds, electron acceptor (A) pyridine was substituted with an electron donor (D) dimethoxy triphenylamine unit. The effect of passing from a dipolar (D-A, Py-1) to a quadrupolar (D-A-D, Py-3) structure as well as the impact of functionalizing the pyridine with a bromine in the dipolar structure (D-A-Br, Py-2) was investigated. All the pyridine derivatives were found to be highly emissive both in solution and in the solid state, with fluorescence properties markedly sensitive to the environment and responsive to external stimuli. The spectral and photophysical properties in solution were investigated through conventional steady-state and advanced time-resolved spectroscopies with nanosecond and femtosecond temporal resolution. The expected efficient intersystem crossing for the heavy-atom-containing molecule was surprisingly not highlighted by our experiments, but an increased push–pull character was enabled by functionalizing the pyridine acceptor with the bromine. The ultrafast spectroscopic study revealed a peculiar excited state deactivation mechanism for the Br derivative among the others, involving photoinduced intramolecular charge transfer accompanied by twisting of the molecular structure (population of a TICT excited state). Similarly, a significant color change in the solid-state emission was observed for Py-2 upon mechanical grinding, suggesting a mechanochromic luminescence behavior in this case. Our findings suggest introducing heavy atoms in organic fluorophores as a new design strategy to obtain mechanoluminescent materials. 

Enabling Peculiar Photophysics and Mechanochromic Luminescence by Introducing Bromine in Push–Pull Pyridine Derivatives

Triphenylamine (TPA) substituted π-conjugated chromophores TPA1-TPA5 were designed and synthesized via Pd-catalysed Sonogashira cross-coupling followed by [2 + 2] cycloaddition-retroelectrocyclization (CA-RE) reactions. The effects of acceptor 1,1,4,4-tetracyanobutadiene (TCBD) and cyclohexa-2,5-diene-1,4-diylidene-expanded TCBD (DCNQ) units in the photophysical studies and the HOMO-LUMO energy levels of the phenothiazine sulfones TPA1-TPA5 were evaluated. The absorption spectra of chromophores TPA4 and TPA5 show a significant change due to the incorporation of DCNQ units, resulting in bathochromically shifted broad absorption in the NIR region. The photophysical studies revealed that DCNQ-based chromophores TPA4 and TPA5 have a better D-A interaction than the TCBD functionalized TPA2 and TPA3. Density functional theory calculations and electrochemical studies were performed to examine the molecular geometry and frontier energy levels of the sulfone-based chromophores. Systematic structural modification of the chromophore TPA1 modulated the electrochemical properties and successively tuned the energy gaps for TPA2-TPA5. The theoretically estimated HOMO-LUMO gaps for TPA1-TPA5 exhibit good agreement with the experimental data calculated from the electrochemical studies. The chromophore TPA1 exhibits solvatochromism and aggregation-induced emission (AIE) behavior owing to the emission in the solid state.

Near-IR absorbing 1,1,4,4-tetracyanobutadiene-functionalized phenothiazine sulfones.

Molecular Tailoring of Pyridine Core-Based Hole Selective Layer for Lead Free Double Perovskite Solar Cells Fabrication

The stronger push–pull character of the phenothiazine relative to the phenothiazine-dioxide derivatives is crucial to achieve negligible S1–T1 energy gap and enable reverse intersystem crossing followed by red Thermally Activated Delayed Fluorescence.

Enabling red thermally activated delayed fluorescence by increasing the push–pull strength in naphthalimide-phenothiazine derivatives

Prolonging the lifetime of charge-separated states (CSS) is of paramount importance in artificial photosynthetic donor-acceptor (DA) constructs to build the next generation of light-energy-harvesting devices. This becomes especially important when the DA constructs are closely spaced and highly interacting. In the present study, we demonstrate extending the lifetime of the CSS in highly interacting DA constructs by making use of the triplet excited state of the electron donor and with the help of excitation wavelength selectivity. To demonstrate this, π-conjugated phenothiazine sulfone-based push-pull systems, PTS2-PTS6 have been newly designed and synthesized via the Pd-catalyzed Sonogashira cross-coupling followed by [2 + 2] cycloaddition-retroelectrocyclization reactions. Modulation of the spectral and photophysical properties of phenothiazine sulfones (PTZSO2) and terminal phenothiazines (PTZ) was possible by incorporating powerful electron acceptors, 1,1,4,4-tetracyanobutadiene (TCBD) and cyclohexa-2,5-diene-1,4-diylidene-expanded TCBD (exTCBD). The quadrupolar PTS2 displayed solvatochromism, aggregation-induced emission, and mechanochromic behaviors. From the energy calculations, excitation wavelength-dependent charge stabilization was envisioned in PTS2-PTS6, and the subsequent pump-probe spectroscopic studies revealed charge stabilization when the systems were excited at the locally excited peak positions, while such effect was minimal when the samples were excited at wavelengths corresponding to the CT transitions. This work reveals the impact of wavelength selectivity to induce charge separation from the triplet excited state in ultimately prolonging the lifetime of CCS in highly interacting push-pull systems.

Manju Sheokand

Papers

Enabling Peculiar Photophysics and Mechanochromic Luminescence by Introducing Bromine in Push–Pull Pyridine Derivatives

Near-IR absorbing 1,1,4,4-tetracyanobutadiene-functionalized phenothiazine sulfones.

Molecular Tailoring of Pyridine Core-Based Hole Selective Layer for Lead Free Double Perovskite Solar Cells Fabrication

Enabling red thermally activated delayed fluorescence by increasing the push–pull strength in naphthalimide-phenothiazine derivatives

Excitation Wavelength-Dependent Charge Stabilization in Highly Interacting Phenothiazine Sulfone-Derived Donor-Acceptor Constructs.