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

Overview

Journal Molecules

Publisher MDPI

Specialty Biology

Date 2021 Apr 30

PMID 33918327

Citations 1

Authors

Taisiya S Sukhikh

Radmir M Khisamov

Sergey N Konchenko

Affiliations

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Abstract

We report a study of photoluminescent properties of 4-bromo-7-(3-pyridylamino)-2,1,3-benzothiadiazole () and its novel Lewis adducts: ()(ZnCl) and [CuCl(-){}]·2CH ( = tetraphenyldiphosphine monoxide), whose crystal structure was determined by X-ray diffraction analysis. - 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 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 , which opens up the possibility to color-tune luminescence of benzothiadiazole derivatives.

Citing Articles

Tris(2-Pyridyl)Arsine as a New Platform for Design of Luminescent Cu(I) and Ag(I) Complexes.

Demyanov Y, Sadykov E, Rakhmanova M, Novikov A, Bagryanskaya I, Artemev A Molecules. 2022; 27(18).

PMID: 36144790 PMC: 9503387. DOI: 10.3390/molecules27186059.

References

Liu C, Hamzehpoor E, Sakai-Otsuka Y, Jadhav T, Perepichka D . A Pure-Red Doublet Emission with 90 % Quantum Yield: Stable, Colorless, Iodinated Triphenylmethane Solid. Angew Chem Int Ed Engl. 2020; 59(51):23030-23034. DOI: 10.1002/anie.202009867. View

Khisamov R, Sukhikh T, Bashirov D, Ryadun A, Konchenko S . Structural and Photophysical Properties of 2,1,3-Benzothiadiazole-Based Phosph(III)azane and Its Complexes. Molecules. 2020; 25(10). PMC: 7288126. DOI: 10.3390/molecules25102428. View

Li Q, Tang Y, Hu W, Li Z . Fluorescence of Nonaromatic Organic Systems and Room Temperature Phosphorescence of Organic Luminogens: The Intrinsic Principle and Recent Progress. Small. 2018; 14(38):e1801560. DOI: 10.1002/smll.201801560. View

Plasser F . TheoDORE: A toolbox for a detailed and automated analysis of electronic excited state computations. J Chem Phys. 2020; 152(8):084108. DOI: 10.1063/1.5143076. View

Smithen D, Monro S, Pinto M, Roque 3rd J, Diaz-Rodriguez R, Yin H . Bis[pyrrolyl Ru(ii)] triads: a new class of photosensitizers for metal-organic photodynamic therapy. Chem Sci. 2021; 11(44):12047-12069. PMC: 7953431. DOI: 10.1039/d0sc04500d. View

Shimogawa H, Yoshikawa O, Aramaki Y, Murata M, Wakamiya A, Murata Y . 4,7-Bis[3-(dimesitylboryl)thien-2-yl]benzothiadiazole: Solvato-, Thermo-, and Mechanochromism Based on the Reversible Formation of an Intramolecular B-N Bond. Chemistry. 2017; 23(15):3784-3791. DOI: 10.1002/chem.201606041. View

Zhan G, Liu Z, Bian Z, Huang C . Recent Advances in Organic Light-Emitting Diodes Based on Pure Organic Room Temperature Phosphorescence Materials. Front Chem. 2019; 7:305. PMC: 6514089. DOI: 10.3389/fchem.2019.00305. View

Goswami S, Winkel R, Schanze K . Photophysics and Nonlinear Absorption of Gold(I) and Platinum(II) Donor-Acceptor-Donor Chromophores. Inorg Chem. 2015; 54(20):10007-14. DOI: 10.1021/acs.inorgchem.5b01767. View

He G, Du L, Gong Y, Liu Y, Yu C, Wei C . Crystallization-Induced Red Phosphorescence and Grinding-Induced Blue-Shifted Emission of a Benzobis(1,2,5-thiadiazole)-Thiophene Conjugate. ACS Omega. 2019; 4(1):344-351. PMC: 6648371. DOI: 10.1021/acsomega.8b02805. View

10.

Neto B, Carvalho P, Correa J . Benzothiadiazole Derivatives as Fluorescence Imaging Probes: Beyond Classical Scaffolds. Acc Chem Res. 2015; 48(6):1560-9. DOI: 10.1021/ar500468p. View

11.

Chan K, Tong G, To W, Yang C, Du L, Lee Phillips D . The interplay between fluorescence and phosphorescence with luminescent gold(i) and gold(iii) complexes bearing heterocyclic arylacetylide ligands. Chem Sci. 2017; 8(3):2352-2364. PMC: 5365001. DOI: 10.1039/c6sc03775e. View

12.

Sun L, Chen Y, Kuang S, Li G, Guan R, Liu J . Iridium(III) Anthraquinone Complexes as Two-Photon Phosphorescence Probes for Mitochondria Imaging and Tracking under Hypoxia. Chemistry. 2016; 22(26):8955-65. DOI: 10.1002/chem.201600310. View

13.

Gutierrez G, Sazama G, Wu T, Baldo M, Swager T . Red Phosphorescence from Benzo[2,1,3]thiadiazoles at Room Temperature. J Org Chem. 2016; 81(11):4789-96. PMC: 4892972. DOI: 10.1021/acs.joc.6b00789. View

14.

Jia W, Wang Q, Shi H, An Z, Huang W . Manipulating the Ultralong Organic Phosphorescence of Small Molecular Crystals. Chemistry. 2019; 26(20):4437-4448. DOI: 10.1002/chem.201904500. View

15.

KUBELKA P . New contributions to the optics of intensely light-scattering materials. J Opt Soc Am. 1948; 38(5):448-57. DOI: 10.1364/josa.38.000448. View

16.

Zhang Y, Chen Z, Wang X, He J, Wu J, Liu H . Achieving NIR Emission for Donor-Acceptor Type Platinum(II) Complexes by Adjusting Coordination Position with Isomeric Ligands. Inorg Chem. 2018; 57(22):14208-14217. DOI: 10.1021/acs.inorgchem.8b02220. View

17.

Wang Z, Wang Z, Lu P, Wang Y . Preparation and Photoluminescent Properties of Three 5-Amino Benzothiadiazoles (5-amBTDs). Chem Asian J. 2020; 15(21):3519-3526. DOI: 10.1002/asia.202000980. View

18.

Mohanty M, Madhu C, Reddy V, Paramasivam M, Bangal P, Jayathirtha Rao V . Direct observation of the rise of delayed fluorescence in dithienylbenzothiadiazole and its role in the excited state dynamics of a donor-acceptor-donor molecule. Phys Chem Chem Phys. 2017; 19(13):9118-9127. DOI: 10.1039/c7cp00261k. View

19.

Zhu Z, Tian D, Gao P, Wang K, Li Y, Shu X . Cell-Penetrating Peptides Transport Noncovalently Linked Thermally Activated Delayed Fluorescence Nanoparticles for Time-Resolved Luminescence Imaging. J Am Chem Soc. 2018; 140(50):17484-17491. DOI: 10.1021/jacs.8b08438. View

20.

Grimme S, Ehrlich S, Goerigk L . Effect of the damping function in dispersion corrected density functional theory. J Comput Chem. 2011; 32(7):1456-65. DOI: 10.1002/jcc.21759. View