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Opto-electrochemistry of pyridopyrazino[2,3-b]indole Derivatives

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Abstract

Here, pyridopyrazino[2,3-b]indole based D–A assembly was designed and synthesized with modulation of various electron-donating/withdrawing substituent and characterized by various spectroscopic methods. Pyridopyrazino[2,3-b]indole derivatives show inbuilt intramolecular charge transfer (ICT) transition which established D–A building in molecules and induces blue-green emission in the solution state. However, solid-state emission characteristics explore the emission property of some molecules towards aggregation-induced emission (AIE) effect which leads to the formation of emissive nano aggregates in THF/H2O mixture. Alteration of substituent on pyridopyrazino[2,3-b]indole segment effectively tune electrochemical property and resulting LUMO energy level was found to be comparable with reported electron transporting/n-type materials. These properties and good thermal stability indicate that molecules have the potential to be used as solid-state emitter and n-type materials in optoelectronic devices.

Graphical Abstract

Pyridopyrazino[2,3-b]indole derivatives possess inbuilt intramolecular charge-transfer to reveal donor-acceptor assembly within a molecule. Opto-electrochemical properties of it greatly influenced by an inductive and mesomeric effect caused by a substituted group. Strong solid-state emission owned by some molecule display AIE phenomenon. Additionally, LUMO value of derivatives exhibits electron-transporting ability hence could be used in organic electronics.

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References

  1. Tang C W and VanSlyke S A 1987 Organic electroluminescent diodes Appl. Phys. Lett. 51 913

    CAS  Google Scholar 

  2. Anthony J E 2008 The larger acenes: versatile organic semiconductors Angew. Chem. Int. Ed. 47 452

    CAS  Google Scholar 

  3. Tao S, Li L, Yu J, Jiang Y, Zhou Y, Lee C S, Lee S T, Zhang X and Kwon O 2009 Bipolar molecule as an excellent hole-transporter for organic-light emitting devices Chem. Mater. 21 1284

    CAS  Google Scholar 

  4. Kraft A, Grimsdale A C and Holmes A B 1998 Electroluminescent conjugated polymers seeing polymers in a new light Angew. Chem. Int. Ed. 37 402

    Google Scholar 

  5. Jenekhe S A and Osaheni J A 1994 Excimers and exciplexes of conjugated polymers Science 265 765

    CAS  PubMed  Google Scholar 

  6. Jayanty S and Radhakrishnan T P 2004 Enhanced fluorescence of remote functionalized diaminodicyanoquinodimethanes in the solid state and fluorescence switching in a doped polymer by solvent vapors Chem. Eur. J. 10 791

    CAS  Google Scholar 

  7. Jares-Erijman E A and Jovin T M 2003 FRET imaging Nat. Biotechnol. 21 1387

    CAS  PubMed  Google Scholar 

  8. Luo J, Xie Z, Lam J W Y, Cheng L, Chen H, Qiu C, Kwok H S, Zhan X, Liu Y, Zhu D and Tang B Z 2001 Aggregation-induced emission of 1-methyl-1,2,3,4,5-pentaphenylsilole Chem. Commun. 18 1740

    Google Scholar 

  9. Hong Y, Lama J W Y and Tang B Z 2009 Aggregation-induced emission: phenomenon, mechanism and applications Chem. Commun. 29 4332

    Google Scholar 

  10. Hong Y, Lam J W Y and Tang B Z 2011 Aggregation-induced emission Chem. Soc. Rev. 40 5361

    CAS  PubMed  Google Scholar 

  11. Sakamoto Y, Suzuki T, Kobayashi M, Gao Y, Fukai Y, Inoue Y, Sato F and Tokito S 2004 Perfluoropentacene: High-Performance p–n junctions and complementary circuits with pentacene J. Am. Chem. Soc. 126 8138

    CAS  PubMed  Google Scholar 

  12. Liang Z, Tang Q, Xu J and Miao Q 2011 Soluble and Stable N‐Heteropentacenes with High Field‐Effect Mobility Adv. Mater. 23 1535

    CAS  Google Scholar 

  13. Thomas K R J, Lin J T, Tao Y T and Ko C W 2001 Light-emitting carbazole derivatives: potential electroluminescent materials J. Am. Chem. Soc. 123 9404

    CAS  PubMed  Google Scholar 

  14. Zhuang J, Su W, Li W, Zhou Y, Shen Q and Zhou M 2012 Configuration effect of novel bipolar triazole/carbazole-based host materials on the performance of phosphorescent OLED devices Org. Electron. 13 2210

    CAS  Google Scholar 

  15. Thomas K R J, Lin J T, Tao Y T and Chuen C H 2002 Quinoxalines incorporating triarylamines: potential electroluminescent materials with tunable emission characteristics Chem. Mater. 14 2796

    CAS  Google Scholar 

  16. Chang D W, Ko S J, Kim J Y, Dai L and Baek J B 2012 Multifunctional quinoxaline containing small molecules with multiple electron-donating moieties: Solvatochromic and optoelectronic properties Synth. Met. 162 1169

    CAS  Google Scholar 

  17. Shaikh A M, Sharma B K and Kamble R M 2015 Synthesis, Photophysical, Electrochemical and Thermal Studies of Triarylamines based on benzo[g]quinoxalines J. Chem. Sci. 127 1571

    CAS  Google Scholar 

  18. Shaikh A M, Sharma B K and Kamble R M 2016 Electron-deficient molecules: photophysical, electrochemical, and thermal investigations of naphtho[2,3-f]quinoxaline-7,12-dione derivatives Chem. Heterocycl. Compd. 52 110

    CAS  Google Scholar 

  19. Shaikh A M, Sharma B K, Chacko S and Kamble R M 2016 Synthesis and optoelectronic investigations of triarylamines based on naphtho[2,3-f]quinoxaline-7,12-dione core as donor–acceptors for n-type materials RSC Adv. 6 60084

  20. Kanekar D N, Chacko S and Kamble R M 2019 Quinoxaline based amines as blue-orange emitters: Effect of modulating donor system on optoelectrochemical and theoretical properties Dyes Pigm. 167 36

    CAS  Google Scholar 

  21. Singh P S, Chacko S and Kamble R M 2019 The design and synthesis of 2,3-diphenylquinoxaline amine derivatives as yellow-blue emissive materials for optoelectrochemical study New J. Chem. 43 6973

    CAS  Google Scholar 

  22. Mahadik S S, Chacko S and Kamble R M 2019 2,3-Di(thiophen-2-yl)quinoxaline Amine Derivatives: Yellow-Blue Fluorescent Materials for Applications in Organic Electronics ChemistrySelect 4 10021

  23. Przyjazna B, Kucybała Z and Czkowski J P 2004 Development of new dyeing photoinitiators based on 6H-indolo[2,3-b]quinoxaline skeleton Polymer 45 2559

  24. Thomas K R J and Tyagi P 2010 Synthesis, Spectra, and Theoretical Investigations of the Triarylamines Based on 6H-indolo[2,3-b]quinoxaline J. Org. Chem. 75 8100

    CAS  PubMed  Google Scholar 

  25. Sharma B K, Shaikh A M, Chacko S and Kamble R M 2017 Synthesis, Spectral, Electrochemical and Theoretical Investigation of indolo[2,3-b]quinoxaline dyes derived from Anthraquinone for n–type materials J. Chem. Sci. 129 483

    CAS  Google Scholar 

  26. Kamble R M, Sharma B K, Shaikh A M and Chacko S 2018 Design, Synthesis, Opto–Electrochemical and Theoretical Investigation of Novel Indolo[2, 3-b]naphtho[2, 3-f]quinoxaline Derivatives for n–Type Materials in Organic Electronics ChemistrySelect 3 6907

  27. Singh P S, Badani P M and Kamble R M 2019 Impact of the donor substituent on the optoelectrochemical properties of 6H-indolo[2,3-b]quinoxaline amine derivatives New J. Chem. 43 19379

    CAS  Google Scholar 

  28. Kim R, Oh D H, Hwang M C, Baek J Y, Shin S C, Kwon S K and Kim Y H 2012 New Pyridopyrazine Skelecton-Based Electron-Transporting Materials J. Nanosci. Nanotechnol. 12 4370

    CAS  PubMed  Google Scholar 

  29. Zhao H, Wei Y, Zhao J and Wang M 2014 Three donor-acceptor polymeric electrochromic materials employing 2,3-bis(4-(decyloxy)phenyl)pyrido[4,3-b]pyrazine as acceptor unit and thiophene derivatives as donor units Electrochim. Acta 146 231

    CAS  Google Scholar 

  30. Okamoto T, Terada E, Kozaki M, Uchida M, Kikukawa S and Okada K 2003 Facile synthesis of 5,10-diaryl-5,10-dihydrophenazines and application to EL devices Org. Lett. 5 373

    CAS  Google Scholar 

  31. Kanekar D N, Chacko S and Kamble R M 2018 Synthesis, Opto-electrochemical and Theoretical Investigation of Pyrazino[2,3-b]phenazine Amines for Organic Electronics ChemistrySelect 3 4114

  32. Kanekar D N, Chacko S and Kamble R M 2020 Synthesis and investigation of the photophysical, electrochemical and theoretical properties of phenazine–amine based cyan blue-red fluorescent materials for organic electronics New J. Chem. 44 3278

    CAS  Google Scholar 

  33. Buu-Hoi N P and Saint-Ruf G 1960 Condensation of isatins with asymmetric aromatic and heterocyclic o-diamines Bull. Soc. Chim. Fr. 1920

    Google Scholar 

  34. Bergman J and Charlotta D 1996 Synthesis of pyridopyrazino[2,3-b] indoles and 10H-indolo [3,2-g]pteridins Recl. Trav. Chim. Pays-Basb. 115 31

    CAS  Google Scholar 

  35. Andrieu B M and Mdrour J Y 1998 Reactions of 3-([(Trifluoromethyl)sulfonyl]oxy)-lH-indole derivatives with diamines and carbon nucleophiles. Synthesis of 6H-Indolo[2,3-b]quinoxaline derivatives Tetrahedron 54 11095

  36. Alphonse F A, Routier S, Coudert G and Merour J Y 2001 A straightforward synthesis of pyridopyrazino[2,3-b]indoles and indolo[2,3-b]Quinoxaline Heterocycles 55 925

  37. Jamrozy K, Szymoniak K and Ostrowska K 2008 The regioselective synthesis of 2H-pyrido[2,3-b]pyrrolo[2,3-e]pyrazin-2-one Heterocycles 75 2275

  38. Dandia A, Parewa V, Maheshwari S and Rathore K S 2014 Cu doped CdS nanoparticles: A versatile and recoverable catalyst for chemoselective synthesis of indolo[2,3-b]quinoxaline derivatives under microwave irradiation J. Mol. Catal. A Chem. 394 244

    CAS  Google Scholar 

  39. Seth M, Bhaduri A P, Khanna N M and Dhar M L 1974 Antiamoebic agents. Syntheses of substituted indophenazines, azaindophenazines, and azaquinoxalines Indian J. Chem. 12 124

  40. Beauchard A, Ferandin Y, Frere S, Lozach O, Blairvacq M, Meijer L, Thiery V and Besson T 2006 Synthesis of novel 5-substituted indirubins as protein kinases inhibitors Bioorg. Med. Chem. 14 6434

    CAS  Google Scholar 

  41. Reichardt C 1979 Empirical parameters of solvent polarity as linear free-energy relationships Angew. Chem. Lnt. Ed. Engl. 18 98

    Google Scholar 

  42. Reichardt C 1994 Solvatochromic dyes as solvent polarity indicators Chem. Rev. 94 2319

    CAS  Google Scholar 

  43. Forbes W F and Audrey S R 1956 Light Absorption Studies: Part V. The Relation Of Mesomeric Effects And Ultraviolet Light Absorption Spectra Can. J. Chem. 34 1447

  44. Lohmann W 1974 Halogen-substitution effect on the optical absorption bands of uracil Z. Naturforsch. 29 493

    CAS  Google Scholar 

  45. Law K Y 1987 Squaraine chemistry: effects of structural changes on the absorption and multiple fluorescence emission of bis[4-(dimethylamino)phenyl]squaraine and its derivatives J. Phys. Chem. 91 5184

    CAS  Google Scholar 

  46. D’Aleo A, Saul A, Attaccalite C and Fages F 2019 Influence of halogen substitution on aggregation-induced near infrared emission of borondifluoride complexes of 2′-hydroxychalcones Mater. Chem. Front. 3 86

    Google Scholar 

  47. Norman S A, Michele E, Femando C, Teresa C, Maria B P and Arthur G 1997 Photochemistry and photocuring activities of novel substituted 4′-(4-methylphenylthio)benzophenones as photoinitiators J. Photochem. Photobiol. A 110 183

    Google Scholar 

  48. Pant G J N, Singha P, Rawat B S, Rawat M S M and Joshi G C 2011 Synthesis, characterization and fluorescence studies of 3,5-diaryl substituted 2-pyrazolines Spectrochim. Acta A 78 1075

    Google Scholar 

  49. Sun S S and Carl E B 2005 In Organic Photovoltaics: Mechanisms, Materials, and Device S S Sun and N S Sariciftci (Eds.) (Boca Raton: CRC Press/Taylor and Francis) p.183

  50. Kasai H, Nalwa H S, Oikawa H, Okada S, Matsuda H, Minami N, Kakuta A, Ono K, Mukoh A and Nakanishi H 1992 A Novel Preparation Method of Organic Microcrystals Jpn. J. Appl. Phys. 31 L1132

    CAS  Google Scholar 

  51. Yang Z W, Qin W Y L, Jacky S, Chen H Y, Herman D W I and Tang B Z 2013 Fluorescent pH sensor constructed from a heteroatom-containing luminogen with tunable AIE and ICT characteristics Chem. Sci. 4 3725

    CAS  Google Scholar 

  52. Luis S A, Manuela M, Bjorn O R and Roland L 1995 Theoretical Study of the Internal Charge Transfer in Aminobenzonitriles J. Am. Chem. Soc. 117 3189

    Google Scholar 

  53. Mei J, Leung N L C, Kwok R T K, Lam J W Y and Tang B Z 2015 Aggregation-induced emission: together we shine, united we soar! Chem. Rev. 115 11718

    CAS  PubMed  Google Scholar 

  54. Luo X, Li J, Li C, Heng L, Dong Y Q, Liu Z, Bo Z and Tang B Z 2011 Reversible switching of the emission of diphenyldibenzofulvenes by thermal and mechanical stimuli Adv. Mater. 23 3261

    CAS  Google Scholar 

  55. Tang B Z, Geng Y, Lam J W Y, Li B, Jing X, Wang X, Wang F, Pakhomov A and Zhang X X 1999 Processible Nanostructured Materials with Electrical Conductivity and Magnetic Susceptibility: Preparation and Properties of Maghemite/Polyaniline Nanocomposite Films Chem. Mater. 11 1581

    CAS  Google Scholar 

  56. Mei J, Wang J, Sun J Z, Zhao H, Yuan W, Deng C, Chen S, Herman H Y S, Lu P, Qin A, Kwok H S, Ma Y, Williams I D and Tang B Z 2012 Siloles symmetrically substituted on their 2,5-positions with electron-accepting and donating moieties: facile synthesis, aggregation-enhanced emission, solvatochromism, and device application Chem. Sci. 3 549

    CAS  Google Scholar 

  57. Fukuda T, Kanbara T, Yamamoto T, Ishikawa K, Takezoe H and Fukuda A 1996 Polyquinoxaline as an excellent electron injecting material for electroluminescent device Appl. Phys. Lett. 68 2346

    CAS  Google Scholar 

  58. Tonzola C J, Alam M M, Kaminsky W and Jenekhe S A 2003 New n-Type Organic Semiconductors: Synthesis, Single Crystal Structures, Cyclic Voltammetry, Photophysics, Electron Transport, and Electroluminescence of a Series of Diphenylanthrazolines J. Am. Chem. Soc. 125 13548

    CAS  PubMed  Google Scholar 

  59. Usta H, Facchetti A and Marks T J 2011 n-Channel Semiconductor Materials Design for Organic Complementary Circuits Acc. Chem. Res. 44 501

    CAS  Google Scholar 

  60. Sharma B K, Shaikh A M, Chacko S and Kamble R M 2018 Synthesis and optoelectronic investigation of triarylamines based on imidazoanthraquinone as donor–acceptors for n-type materials J. Chem. Sci. 130 49

    Google Scholar 

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Acknowledgements

The authors are greatly thankful to Micro-Analytical Laboratory, Department of Chemistry, University of Mumbai, Mumbai for providing instrumental facilities, TIFR-Mumbai for providing MALDI-TOF.

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  1. Department of Chemistry, University of Mumbai, Santacruz (E), Mumbai, 400 098, India

    Pooja S Singh, Akshata J Shirgaonkar, Bhargavi K Chawathe & Rajesh M Kamble

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  1. Pooja S Singh
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  2. Akshata J Shirgaonkar
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Singh, P.S., Shirgaonkar, A.J., Chawathe, B.K. et al. Opto-electrochemistry of pyridopyrazino[2,3-b]indole Derivatives. J Chem Sci 132, 150 (2020). https://doi.org/10.1007/s12039-020-01851-9

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