Advertisement

Synthesis of Strongly Fluorescent Imidazole Derivatives: Structure Property Studies, Halochromism and Fluorescent Photoswitching

  • Anu Kundu
  • Subramanian Karthikeyan
  • Dohyun MoonEmail author
  • Savarimuthu Philip AnthonyEmail author
ORIGINAL ARTICLE
  • 79 Downloads

Abstract

New series of methoxy and hydroxyl group substituted triphenylamine (TPA)-imidazole fluorescent molecules (5-(diphenylamino)-2-(1H-phenanthro[9,10-d]imidazol-2-yl)phenol (1), 5-(diphenylamino)-2-(1-phenyl-1H-phenanthro[9,10-d]imidazol-2-yl)phenol (2), 5-(diphenylamino)-2-(4,5-diphenyl-1H-imidazol-2-yl)phenol (3), 5-(diphenylamino)-2-(1,4,5-triphenyl-1H-imidazol-2-yl)phenol (4), N-(3-methoxy-4-(1H-phenanthro[9,10-d]imidazol-2-yl)phenyl)-N-phenylbenzenamine (5), N-(3-methoxy-4-(1-phenyl-1H-phenanthro[9,10-d]imidazol-2-yl)phenyl)-N-phenylbenzene amine (6), and N-(3-methoxy-4-(4,5-diphenyl-1H-imidazol-2-yl)phenyl)-N-phenylbenzenamine (7)) have been synthesized that exhibited strong solution fluorescence and molecular structure and conformation controlled fluorescence photoswitching, solid state fluorescence and halochromism. Hydroxyl substituted molecules (1–4) showed moderate to strong fluorescence in solution depend on solvent polarity and very weak solid state fluorescence. Methoxy substituted molecules (5–7) displayed strong fluorescence both in solution and solid state. Solid state structural studies revealed strong intramolecular H-bonding in the crystal lattice. Interestingly, highly twisted structure (6) showed rare light induced reversible fluorescence switching in CHCl3. The observation of isobestic point in time dependent fluorescence photoswitching studies indicated structural isomer conversion. Further, acid sensitive imidazole nitrogen has been made use to demonstrate solid state fluorescence switching via halochromism. Thus the present studies attempted to develop new fluorescent molecules and establish structure-property relationship for designing fluorescence switching materials.

Graphical Abstract

Molecular structure controlled solid state fluorescence, halochromism and a rare fluorescence photoswitching in chloroform have been observed with triphenylamine-imidazole derivatives.

Keywords

Fluorescence switching Halochromism Fluorescence photoswitching Solid state fluorescence 

Notes

Acknowledgments

Financial support from the Science and Engineering Research Board (SERB), New Delhi, India (SERB No. EMR/2015/00-1891) is acknowledged with gratitude. “X-ray crystallography at the PLS-II 2D-SMC beamline was supported in part by MSIP and POSTECH.

Supplementary material

10895_2019_2437_MOESM1_ESM.pdf (5.1 mb)
ESM 1 (PDF 5246 kb)

References

  1. 1.
    Chi Z, Zhang X, Xu B, Zhou X, Ma C, Zhang Y, Liu S, Xu J (2012) Recent advances in organic mechanofluorochromic materials. Chem Soc Rev 41:3878–3896CrossRefPubMedPubMedCentralGoogle Scholar
  2. 2.
    Sagara Y, Kato T (2009) Mechanically induced luminescence changes in molecular assemblies. Nat Chem 1:605–610CrossRefGoogle Scholar
  3. 3.
    Sagara Y, Yamane S, Mitani M, Weder C, Kato T (2016) Mechanoresponsive luminescent molecular assemblies: an emerging class of materials. Adv Mater 28:1073–1095CrossRefGoogle Scholar
  4. 4.
    Ito H, Saito T, Oshima N, Kitamura N, Ishizaka S, Hinatsu Y, Wakeshima M, Kato M, Tsuge K, Sawamura M (2008) Reversible Mechanochromic luminescence of [(C6F5Au)2(μ-1,4-Diisocyanobenzene)]. J Am Chem Soc 130:10044–10045CrossRefGoogle Scholar
  5. 5.
    (2014) Mechanochromic Fluorescent Materials: Phenomena, Materials and Applications, ed. Xu J, Chi Z, vol. 8, RSC, CambridgeGoogle Scholar
  6. 6.
    Weder C (2011) Mechanoresponsive materials. J Mater Chem 21:8235–8236CrossRefGoogle Scholar
  7. 7.
    Ciardelli F, Ruggeri G, Pucci A (2013) Dye-containing polymers: methods for preparation of mechanochromic materials. Chem Soc Rev 42:857–870CrossRefGoogle Scholar
  8. 8.
    Saragi TPI, Spehr T, Siebert A, Fuhrmann-Liekerand T, Salbeck J (2007) Spiro compounds for organic optoelectronics. Chem Rev 107:1011–1065CrossRefGoogle Scholar
  9. 9.
    Liang J, Tang BZ, Liu B (2015) Specific light-up bioprobes based on AIEgen conjugates. Chem Soc Rev 44:2798–2811CrossRefGoogle Scholar
  10. 10.
    Yuan L, Lin WY, Zheng KB, He WL, Huang MW (2013) Far-red to near infrared analyte-responsive fluorescent probes based on organic fluorophore platforms for fluorescence imaging. Chem Soc Rev 42:622–661CrossRefPubMedPubMedCentralGoogle Scholar
  11. 11.
    Zhu YX, Wei ZW, Pan M, Wang HP, Zhang JY, Su CY (2016) A new TPE-based tetrapodal ligand and its ln(III) complexes: multi-stimuli responsive AIE (aggregation-induced emission)/ILCT(intra ligand charge transfer)-bifunctional photoluminescence and NIR emission sensitization. Dalton Trans 45:943–950CrossRefPubMedPubMedCentralGoogle Scholar
  12. 12.
    Zheng R, Mei XF, Lin ZH, Zhao Y, Yao HM, Lv W, Ling QD (2015) Strong CIE activity, multi-stimuli-responsive fluorescence and data storage application of new diphenyl maleimide derivatives. J Mater Chem C 3:10242–10248CrossRefGoogle Scholar
  13. 13.
    Xu B, Xie M, He J, Xu B, Chi Z, Tian W, Jiang L, Zhao F, Liu S, Zhang Y, Xu Z, Xu J (2013) An aggregation-induced emission luminophore with multi-stimuli single- and two-photon fluorescence switching and large two-photon absorption cross section. Chem Commun 49:273–275CrossRefGoogle Scholar
  14. 14.
    Kishimura A, Yamashita T, Yamaguchi K, Aida T (2005) Rewritable phosphorescent paper by the control of competing kinetic and thermodynamic self-assembling events. Nat Mater 4:546–549 40:2400–2408CrossRefGoogle Scholar
  15. 15.
    Hirata S, Watanabe T (2006) Reversible Thermoresponsive recording of fluorescent images (TRF). Adv Mater 18:2725–2729CrossRefGoogle Scholar
  16. 16.
    Kwon MS, Gierschner J, Yoon SJ, Park SY (2012) Unique Piezochromic fluorescence behavior of Dicyanodistyrylbenzene based donor–acceptor–donor triad: mechanically controlled photo-induced Electron transfer (eT) in molecular assemblies. Adv Mater 24:5487–5492CrossRefGoogle Scholar
  17. 17.
    Sun H, Liu S, Lin W, Zhang KY, Lv W, Huang X, Huo F, Yang H, Jenkins G, Zhao Q, Huang W (2014) Smart responsive phosphorescent materials for data recording and security protection. Nat Commun 5:3601–3609CrossRefGoogle Scholar
  18. 18.
    Lee H, Sohn J, Hwang J, Park SY (2004) Triphenylamine-cored bifunctional organic molecules for two-photon absorption and Photorefraction. Chem Mater 16:456–465CrossRefGoogle Scholar
  19. 19.
    Sonntag M, Kreger K, Hanft D, Strohriegl P (2005) Novel star-shaped Triphenylamine-based molecular glasses and their use in OFETs. Chem Mater 17:3031–3039CrossRefGoogle Scholar
  20. 20.
    Li H, Fang M, Tang R, Hou Y, Liao Q, Mei A, Han H, Li Q, Li Z (2016) The introduction of conjugated isolation groups into the common acceptor cyanoacrylic acid: an efficient strategy to suppress the charge recombination in dye sensitized solar cells and the dramatically improved efficiency from 5.89% to 9.44%. J Mater Chem A 4:16403–16409CrossRefGoogle Scholar
  21. 21.
    Shih PI, Chien CH, Wu FI, Shu CF (2007) A novel Fluorene-Triphenylamine hybrid that is a highly efficient host material for blue-, green-, and red-light-emitting Electrophosphorescent devices. Adv Funct Mater 17:3514–3520CrossRefGoogle Scholar
  22. 22.
    Kundu A, Karthikeyan S, Moon D, Anthony SP (2017) Self-reversible thermofluorochromism of D–A–D triphenylamine derivatives and the effect of molecular conformation and packing. CrystEngComm 19:6979–6985CrossRefGoogle Scholar
  23. 23.
    Woo SJ, Kim Y, Kim MJ, Baek JY, Kwon SK, Kim YH, Kim JJ (2018) Strategies for the molecular Design of Donor–Acceptor-type Fluorescent Emitters for efficient deep blue organic light emitting diodes. Chem Mater 30:857–863CrossRefGoogle Scholar
  24. 24.
    Ning ZJ, Chen Z, Zhang Q, Yan YL, Tian H (2007) Aggregation-induced emission (AIE)-active starburst Triarylamine fluorophores as potential non-doped red emitters for organic light-emitting diodes and Cl2 gas Chemodosimeter. Adv Funct Mater 17:3799–3807CrossRefGoogle Scholar
  25. 25.
    Chi ZG, Zhang XQ, Xu BJ, Zhou X, Ma CP, Zhang Y, Liu SW, Xu JR (2012) Recent advances in organic mechanofluorochromic materials. Chem Soc Rev 41:3878–3896CrossRefPubMedPubMedCentralGoogle Scholar
  26. 26.
    Ning Z, Tian H (2009) Triarylamine: a promising core unit for efficient photovoltaic materials. Chem Commun:5483–5495Google Scholar
  27. 27.
    Malagoli M, Bredas JL (2000) Density functional theory study of the geometric structure and energetics of triphenylamine-based hole-transporting molecules. Chem Phys Lett 327:13–17CrossRefGoogle Scholar
  28. 28.
    Yuan WZ, Gong Y, Chen S, Shen XY, Lam JW, Lu P, Lu Y, Wang Z, Hu RR, Xie N, Kwok HS, Zhang YM, Sun JZ, Tang BZ (2012) Efficient solid emitters with aggregation-induced emission and intramolecular charge transfer characteristics: molecular design, synthesis, Photophysical behaviors, and OLED application. Chem Mater 24:1518–1528CrossRefGoogle Scholar
  29. 29.
    Cao Y, Xi W, Wang L, Wang H, Kong L, Zhou H, Wu J, Tian Y (2014) Reversible piezofluorochromic nature and mechanism of aggregation-induced emission-active compounds based on simple modification. RSC Adv 4:24649CrossRefGoogle Scholar
  30. 30.
    Fang M, Yang J, Liao Q, Gong Y, Xie Z, Chi Z, Peng Q, Li Q, Li Z (2017) Triphenylamine derivatives: different molecular packing and the corresponding mechanoluminescent or mechanochromism property. J Mater Chem C 5:9879–9885CrossRefGoogle Scholar
  31. 31.
    Gong Y, Tan Y, Liu J, Lu P, Feng C, Yuan WZ, Lu Y, Sun JZ, He G, Zhang Y (2013) Twisted D–π–a solid emitters: efficient emission and high contrast mechanochromism. Chem Commun 49:4009–4011CrossRefGoogle Scholar
  32. 32.
    Gong Y, Liu J, Zhang Y, He G, Lu Y, Fan WB, Yuan WZ, Sun JZ, Zhang Y (2014) AIE-active, highly thermally and morphologically stable, mechanochromic and efficient solid emitters for low color temperature OLEDs. J Mater Chem C 2:7552–7560CrossRefGoogle Scholar
  33. 33.
    Hariharan PS, Gayathri P, Kundu A, Karthikeyan S, Moon D, Anthony SP (2018) Synthesis of tunable, red fluorescent aggregation-enhanced emissive organic fluorophores: stimuli-responsive high contrast off–on fluorescence switching. CrystEngComm 20:643–651CrossRefGoogle Scholar
  34. 34.
    Wang K, Zhang H, Chen S, Yang G, Zhang J, Tian W, Su Z, Wang Y (2014) Organic polymorphs: one-compound-based crystals with molecular- conformation- and packing-dependent luminescent properties. Adv Mater 26:6168–6173CrossRefGoogle Scholar
  35. 35.
    Li C, Duan R, Liang B, Han G, Wang S, Ye K, Liu Y, Yi Y, Wang Y (2017) Deep-red to near-infrared thermally activated delayed fluorescence in organic solid films and electroluminescent devices. Angew Chem Int Ed 56:11525–11529CrossRefGoogle Scholar
  36. 36.
    Gangopadhyay M, Mandal AK, Maity A, Ravindranathan S, Rajamohanan PR, Das A (2016) Tuning emission responses of a Triphenylamine derivative in host–guest complexes and an unusual dynamic inclusion phenomenon. J Organomet Chem 81:512–521CrossRefGoogle Scholar
  37. 37.
    Anthony SP, Varughese S, Draper SM (2009) Switching and tuning organic solid-state luminescence via a supramolecular approach. Chem Commun:7500–7502Google Scholar
  38. 38.
    Anthony SP, Draper SM (2010) Nano/microstructure fabrication of functional organic material: polymorphic structure and tunable luminescence. J Phys Chem C 114:11708–11716CrossRefGoogle Scholar
  39. 39.
    Li W, Wang S, Zhang Y, Gao Y, Dong Y, Zhang X, Song Q, Yang B, Ma Y, Zhang C (2017) Highly efficient luminescent E- and Z-isomers with stable configurations under photoirradiation induced by their charge transfer excited states. J Mater Chem C 5:8097–8104CrossRefGoogle Scholar
  40. 40.
    Zhang Z, Wu Z, Sun J, Yao B, Xue P, Lu R (2016) β-Iminoenolate boron complex with terminal triphenylamine exhibiting polymorphism and Mechanofluorochromism. J Mater Chem C 4:2854–2861CrossRefGoogle Scholar
  41. 41.
    Hu J, Jiang B, Gong Y, Liu Y, He G, Yuan WZ, Wei C (2018) A novel triphenylacrylonitrile based AIEgen for high contrast mechanchromism and bicolor electroluminescence. RSC Adv 8:710–716CrossRefGoogle Scholar
  42. 42.
    Hariharan PS, Mothi EM, Moon D, Anthony SP (2016) Halochromic Isoquinoline with MechanochromicTriphenylamine: smart fluorescent material for rewritable and self-erasable fluorescent platform. ACS Appl Mater Interfaces 8:33034–33042CrossRefGoogle Scholar
  43. 43.
    Hariharan PS, Moon D, Anthony SP (2015) Reversible fluorescence switching and topochemical conversion in an organic AEE material: polymorphism, defection and nanofabrication mediated fluorescence tuning. J Mater Chem C 3:8381–8388CrossRefGoogle Scholar
  44. 44.
    Hariharan PS, Gayathri P, Kundu A, Karthikeyan S, Moon D, Sagara Y, Anthony SP (2018) Drastic modulation of stimuli-responsive fluorescence by a subtle structural change of organic fluorophore and polymorphism controlled Mechanofluorochromism. Cryst Growth Des 18:3971–3979CrossRefGoogle Scholar
  45. 45.
    Hariharan PS, Mothi EM, Moon D, Anthony SP (2017) Crystallization-induced reversible fluorescence switching of alkyl chain length dependent thermally stable supercooled organic fluorescent liquids. CrystEngComm 19:6489–6497CrossRefGoogle Scholar
  46. 46.
    Hariharan PS, Venkataramanan NS, Moon D, Anthony SP (2015) Self-reversible Mechanochromism and Thermochromism of a Triphenylamine-based molecule: tunable fluorescence and nanofabrication studies. J Phys Chem C 119:9460–9469CrossRefGoogle Scholar
  47. 47.
    Hariharan PS, Gayathri P, Moon D, Anthony SP (2017) Tunable and switchable solid state fluorescence: alkyl chain length-dependent molecular conformation and self-reversible Thermochromism. ChemistrySelect 2:7799–7807CrossRefGoogle Scholar
  48. 48.
    Kundu A, Karthikeyan S, Moon D, Anthony SP (2018) Molecular conformation- and packing-controlled excited state intramolecular proton transfer induced solid-state fluorescence and reversible Mechanofluorochromism. ChemistrySelect 3:7340–7345CrossRefGoogle Scholar
  49. 49.
    Kundu A, Karthikeyan S, Moon D, Anthony SP (2018) Excited state intramolecular proton transfer induced fluorescence in triphenylamine molecule: role of structural conformation and reversible Mechanofluorochromism. J Mol Struct 1169:1–8CrossRefGoogle Scholar
  50. 50.
    Ge Z, Hayakawa T, Ando S, Ueda M, Akiike T, Miyamoto H, Kajita T, Kakimoto M (2008) Spin-coated highly efficient phosphorescent organic light-emitting diodes based on bipolar Triphenylamine-Benzimidazole derivatives. Adv Funct Mater 18:584–590CrossRefGoogle Scholar
  51. 51.
    Zhuang S, Shangguan R, Jin J, Tu G, Wang L, Chen J, Ma D, Zhu X (2012) Efficient nondoped blue organic light-emitting diodes based on phenanthroimidazole-substituted anthracene derivatives. Org Electron 13:3050–3059CrossRefGoogle Scholar
  52. 52.
    Kautny P, Wu Z, Eichelter J, Horkel E, Stöger B, Chen J, Ma D, Fröhlich J, Lumpi D (2016) Indolo[3,2,1-jk]carbazole based planarized CBP derivatives as host materials for PhOLEDs with low efficiency roll-off. Org Electron 34:237–245CrossRefGoogle Scholar
  53. 53.
    Ghodbane A, Saffon N, Blanc S, Fery-Forgues S (2015) Influence of the halogen atom on the solid-state fluorescence properties of 2-phenyl-benzoxazole derivatives. Dyes Pigments 113:219–226CrossRefGoogle Scholar
  54. 54.
    Gao Y, Xu W, Ma H, Obolda A, Yan W, Dong S, Zhang M, Li F (2017) Novel luminescent Benzimidazole-substituent Tris(2,4,6-trichlorophenyl)methyl radicals: Photophysics, stability, and highly efficient red-Orange electroluminescence. Chem Mater 29:6733–6739CrossRefGoogle Scholar
  55. 55.
    Yadav AK, Pradhan B, Ulla H, Nath S, De J, Pal SK, Satyanarayan MN, Achalkumar AS (2017) Tuning the self-assembly and photophysical properties of bi-1,3,4-thiadiazole derivatives through electron donor–acceptor interactions and their application in OLEDs. J Mater Chem C 5:9345–9358CrossRefGoogle Scholar
  56. 56.
    Sakai KI, Tsuchiya S, Kikuchi T, Akutagawa T (2016) An ESIPT fluorophore with a switchable intramolecular hydrogen bond for applications in solid-state fluorochromism and white light generation. J Mater Chem C 4:2011–2016CrossRefGoogle Scholar
  57. 57.
    Mutai T, Tomoda H, Ohkawa T, Yabe Y, Araki K (2008) Switching of polymorph-dependent ESIPT luminescence of an Imidazo[1,2-a]pyridine derivative. Angew Chem Int Ed 47:9522–9524CrossRefGoogle Scholar
  58. 58.
    Anthony SP (2011) Polymorph-dependent solid-state fluorescence and selective metal-ion-sensor properties of 2-(2-Hydroxyphenyl)-4(3H)-quinazolinone. Chem Asian J 7:374–379CrossRefGoogle Scholar
  59. 59.
    Padalkar VS, Seki S (2016) Excited-state intramolecular proton-transfer (ESIPT)-inspired solid state emitters. Chem Soc Rev 45:169–202CrossRefGoogle Scholar
  60. 60.
    Tagare J, Ulla H, Satyanarayan MN, Vaidyanathan S (2018) Synthesis, photophysical and electroluminescence studies of new triphenylamine-phenanthroimidazole based materials for organic light emitting diodes. J Lumin 194:600–609CrossRefGoogle Scholar
  61. 61.
    Ekbote A, Han SH, Jadhav T, Mobin SM, Lee JY, Misra R (2018) Stimuli responsive AIE active positional isomers of phenanthroimidazole as non-doped emitters in OLEDs. J Mater Chem C 6:2077–2087CrossRefGoogle Scholar
  62. 62.
    Li Y, Xue L, Xia H, Xu B, Wen S, Tian W (2008) Synthesis and properties of polythiophene derivatives containing triphenylamine moiety and their photovoltaic applications. J Polymer Sci Part A: Polym Chem 46:3970–3984CrossRefGoogle Scholar
  63. 63.
    Matoliukstyte A, Grazulevicius JV, Jankauskas V (2007) Glass-forming hole-transporting Triphenylamine-based Hydrazones with reactive functional groups. Mol Cryst Liq Cryst 466:85–100CrossRefGoogle Scholar
  64. 64.
    Gao Z, Wang K, Liu F, Feng C, He X, Li J, Yang B, Zou B, Lu P (2017) Enhanced sensitivity and Piezochromic contrast through single-direction extension of molecular structure. Chem Eur J 23:773–777CrossRefGoogle Scholar
  65. 65.
    Szymański W, Beierle JM, Kistemaker HAV, Velema WA, Feringa BL (2013) Reversible Photocontrol of biological systems by the incorporation of molecular Photoswitches. Chem Rev 113:6114–6178CrossRefPubMedPubMedCentralGoogle Scholar
  66. 66.
    Raskosova A, Sto¨ßer R, Abraham W (2013) Molecular photoswitches based on spiro-acridans. Chem Commun 49:3964–3966CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, LLC, part of Springer Nature 2019

Authors and Affiliations

  1. 1.School of Chemical & BiotechnologySASTRA Deemed UniversityThanjavurIndia
  2. 2.PG and Research department of chemistryKhadirMohideen CollegeAdirampattinamIndia
  3. 3.Beamline Department, Pohang Accelerator LaboratoryPohangSouth Korea

Personalised recommendations