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Unexpectedly Long Lifetime of the Excited State of Benzothiadiazole Derivative and Its Adducts with Lewis Acids.

ABSTRACT: We report a study of photoluminescent properties of 4-bromo-7-(3-pyridylamino)-2,1,3-benzothiadiazole (Py-btd) and its novel Lewis adducts: (PyH-btd)₂(ZnCl₄) and [Cu₂Cl₂(Py-btd)₂{PPO}₂]·2C₇H₈ (PPO = tetraphenyldiphosphine monoxide), whose crystal structure was determined by X-ray diffraction analysis. Py-btd exhibits a lifetime of 9 microseconds indicating its phosphorescent nature, which is rare for purely organic compounds. This phenomenon arises from the heavy atom effect: the presence of a bromine atom in Py-btd promotes mixing of the singlet and triplet states to allow efficient singlet-to-triplet intersystem crossing. The Lewis adducts also feature a microsecond lifetime while emitting in a higher energy range than free Py-btd, which opens up the possibility to color-tune luminescence of benzothiadiazole derivatives.

SUBMITTER: Sukhikh TS

PROVIDER: S-EPMC8038179 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Project description:A novel zinc phthalocyanine derivative [2(3), 9(10), 16(17), 23(24) tetrakis-4-((4-(1,4,5-triphenyl-1H-imidazol-2-yl)phenyl)ethynyl)phthalocyanine zinc(ii) (PBIPC)] was synthesized by incorporating a triphenyl imidazole moiety at its peripheral positions. The detailed mechanisms of absorption, emission, electrochemical, nonlinear optical (NLO) and photophysical (excited state dynamics) properties of PBIPC were explored. The absorption and emission properties of the compound were studied in different solvents. The incorporation of a triphenyl imidazole moiety at the peripheral position of the zinc phthalocyanine slightly broadened the Soret band. The emission studies revealed fluorescence quantum yields to be in the range of 0.11-0.22. The time-resolved fluorescence data established the radiative lifetimes to be in the nanosecond range. The oxidation and reduction processes were found to be ring centered, which were studied using the cyclic voltammetry (CV) technique. The energy optimized structures and HOMO-LUMO levels were calculated using DFT, TD-DFT analysis and were employed by means of hybrid functional theory (B3LYP) at 6-31G (d,p) basis set in the Gaussian 09 package. Two-photon absorption was observed in the NLO studies performed in the visible wavelength range of 600-800 nm while the nonlinear absorption was dominated by three- and four-photon absorption processes in the NIR wavelength range (1.0-1.5 μm). The molecule exhibited self-focusing behavior for all the wavelengths. Finally, the excited state dynamics of the title molecule PBIPC were investigated using femtosecond transient absorption spectroscopy and the results obtained were understood on the basis of a simple three kinetic model, for excitation wavelengths of 400 nm (Soret band) and 650 nm (Q-band). Both the spectra demonstrated a broad positive transient absorption (TA) data which overlapped with the ground state bleach (GSB), which in turn displayed a red shift over a delay of ∼2 ns. The lifetimes revealed a possibility of intersystem crossing (τ > 1 ns) owing to the triplet state transition.

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Unexpectedly Long Lifetime of the Excited State of Benzothiadiazole Derivative and Its Adducts with Lewis Acids.

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