Journal of Fluorescence

, Volume 29, Issue 1, pp 279–291 | Cite as

Novel 4,4′-Fluoresceinoxy Bisphthalonitrile Showing Aggregation-Induced Enhanced Emission and Fluorescence Turn off Behavior to Fe3+ Ions

  • G. S. Amitha
  • Vijisha K. Rajan
  • K. Muraleedharan
  • Suni VasudevanEmail author


A novel 4,4′-fluoresceinoxy bisphthalonitrile FPN is synthesized from fluorescein and 4-nitrophthalonitrile by aromatic nucleophilic ipso nitro substitution reaction. The structure of FPN constitutes phthalonitrile-fluorescein-phthalonitrile, acceptor-donor-acceptor, A-D-A form and the solvatochromic study of newly synthesized compound FPN was done in hexane, cyclohexane, CHCl3, DCM, DMF, acetonitrile, ethanol and in methanol. The aggregation behavior of FPN was investigated in good-poor solvent mixture DMF-water in various proportions and the molecule was found to be exhibiting Aggregation Induced Emission Enhancement AIEE for volume percentage of water beyond 50% with a significant hypsochromic shift of 70 nm in the emission maxima from 458 to 388 nm. This phenomenon is termed as Aggregation Induced Blue Shifted Emission Enhancement AIBSEE and was reported in substituted phthalonitrile for the first time. The chemo sensing activity of FPN with various transition metal ions also has been checked by fluorescence spectroscopy where the new molecule FPN exhibited fluorescence turn OFF behaviour towards Fe3+ ion in acetonitrile-methanol ACN-MeOH solution. The binding stoichiometry of FPN with Fe3+ was verified by Job’s plot analysis and Density Functional Theory DFT-B3LYP computational methodology by using Gaussian 09 software.

Graphical Abstract

A novel 4,4′-fluoresceinoxy bisphthalonitrile FPN was synthesized by base catalyzed coupling reaction of fluorescein with 4 nitrophthalonitrile. The newly synthesized compound has been characterized using UV-vis, FTIR, 1HNMR, fluorescence spectral data and single crystal X-ray diffraction studies. The compound FPN was found to be exhibiting positive solvatochromism in various organic solvents and Aggregation Induced Blue Shifted Emission Enhancement AIBSEE in DMF-aqueous mixture when water volume exceed above 50%. As a metal ion chemo sensor FPN exhibited a selective fluorescence turn OFF behavior towards Fe3+ ion in the stoichiometric ratio 1:2 in acetonitrile-methanol mixture and limit of detection LOD of Fe3+ by FPN was calculated to be 3.665 μM.


4,4′-fluoresceinoxy bisphthalonitrile FPN Aggregation induced blue shifted emission enhancement AIBSEE Substituted phthalonitrile Chemo sensing Fe3+ ion 



Amitha G S is thankful to NCB-GATE for research fellowship and Suni Vasudevan would like to thank SERB – Dept. of Science and Technology (Grant Sanction No. SERB/F/3600/2013-14) for financial support. The co-author Vijisha K. Rajan expresses sincere gratitude to UGC for the financial support and Central Sophisticated Instrumentation Facility (CSIF) of University of Calicut for the Gaussian 09 software support. The authors would like to acknowledge Sophisticated Test Instrumentation Centre (STIC) of Cochin University of Science and Technology (CUSAT) for providing single crystal XRD facility. The Crystallographic Information File (CIF) of single crystal of FPN was deposited in Cambridge Crystallographic Data Centre with CCDC No. 1828283.

Compliance with Ethical Standards

Conflict of Interest

The authors declare no conflict of interest.

Supplementary material

10895_2018_2338_MOESM1_ESM.docx (498 kb)
ESM 1 (DOCX 498 kb)


  1. 1.
    MacCormac A, O’Brien E, O’Kennedy R (2010) Classroom activity connections: lessons from fluorescence. J Chem Educ 87:685–686. CrossRefGoogle Scholar
  2. 2.
    Blitz JP, Sheeran DJ, Becker TL, Danielson ND (2006) Classroom demonstrations of concepts in molecular fluorescence. J Chem Educ 83:758. CrossRefGoogle Scholar
  3. 3.
    Özçeşmeci I, Tekin A, Gül A (2014) Synthesis and aggregation behavior of zinc phthalocyanines substituted with bulky naphthoxy and phenylazonaphthoxy groups: An experimental and theoretical study. Synth Met 189:100–110. CrossRefGoogle Scholar
  4. 4.
    Hua F, Ruckenstein E (2004) Fluorescence study of aggregation in water of PEO-grafted polydiphenylamine. Langmuir 20:3954–3961. CrossRefGoogle Scholar
  5. 5.
    Forster KK (1954) Konzentrationsabhängigkeit Fluoreszenzspek-. Z Phys Chem 1:275Google Scholar
  6. 6.
    Birks JB (1970) Photophysics of aromatic molecules. Wiley-Interscience, LondonGoogle Scholar
  7. 7.
    Zhang L, Liang K, Dong L, Yang P, Li Y, Feng X, Zhi J, Shi J, Tong B, Dong Y (2017) Aggregation-induced emission enhancement and aggregation-induced circular dichroism of chiral pentaphenylpyrrole derivatives and their helical self-assembly. New J Chem 41:8877–8884. CrossRefGoogle Scholar
  8. 8.
    Venkatramaiah N, Kumar GD, Chandrasekaran Y, Ganduri R, Patil S (2018) Efficient blue and yellow organic light-emitting diodes enabled by aggregation-induced emission. ACS Appl Mater Interfaces 10:3838–3847. CrossRefGoogle Scholar
  9. 9.
    Ong KH, Liu B (2017) Applications of fluorogens with rotor structures in solar cells. Molecules 22.
  10. 10.
    Ma H, Yang M, Zhang C, Ma Y, Qin Y, Lei Z, Chang L, Lei L, Wang T, Yang Y (2017) Aggregation-induced emission (AIE)-active fluorescent probes with multiple binding sites toward ATP sensing and live cell imaging. J Mater Chem B 5:8525–8531. CrossRefGoogle Scholar
  11. 11.
    Luo J, Xie Z, Lam JWY, Cheng L, Tang BZ, Chen H, Qiu C, Kwok HS, Zhan X, Liu Y, Zhu D (2001) Aggregation-induced emission of 1-methyl-1,2,3,4,5-pentaphenylsilole. Chem Commun 381:1740–1741. CrossRefGoogle Scholar
  12. 12.
    An B, Kwon S, Jung S, Park SY (2002) Enhanced emission and its switching in fluorescent organic nanoparticles. J Am Chem Soc 124:14410–14415. CrossRefGoogle Scholar
  13. 13.
    Mei J, Hong Y, Lam JWY, Qin A, Tang Y, Tang BZ (2014) Aggregation-induced emission: the whole is more brilliant than the parts. Adv Mater 26:5429–5479. CrossRefGoogle Scholar
  14. 14.
    Wang H, Zhao E, Lam JWY, Tang BZ (2015) AIE luminogens: emission brightened by aggregation. Mater Today 18:365–377. CrossRefGoogle Scholar
  15. 15.
    Tong H, Hong Y, Dong Y, Ren Y, Häussler M, Lam JWY, Wong KS, Tang BZ (2007) Color-tunable, aggregation-induced emission of a butterfly-shaped molecule comprising a pyran skeleton and two cholesteryl wings. J Phys Chem B 111:2000–2007. CrossRefGoogle Scholar
  16. 16.
    Shen XY, Wang YJ, Zhao E, Yuan WZ, Liu Y, Lu P, Qin A, Ma Y, Sun JZ, Tang BZ (2013) Effects of substitution with donor-acceptor groups on the properties of tetraphenylethene trimer: aggregation-induced emission, solvatochromism, and mechanochromism. J Phys Chem C 117:7334–7347. CrossRefGoogle Scholar
  17. 17.
    Palakollu V, Kanvah S (2014) α-Cyanostilbene based fluorophores: aggregation-induced enhanced emission, solvatochromism and the pH effect. New J Chem 38:5736–5746. CrossRefGoogle Scholar
  18. 18.
    Qin A, Lam JWY, Mahtab F, Jim CKW, Tang L, Sun J, Sung HHY, Williams ID, Tang BZ (2009) Pyrazine luminogens with “free” and “locked” phenyl rings: understanding of restriction of intramolecular rotation as a cause for aggregation-induced emission. Appl Phys Lett 94:2007–2010. Google Scholar
  19. 19.
    de Meijere A (2005) Adolf von Baeyer: winner of the Nobel prize for chemistry 1905. Angew Chemie Int Ed 44:7836–7840. CrossRefGoogle Scholar
  20. 20.
    Song A, Zhang J, Zhang M, Shen T, Tang J’ (2000) Spectral properties and structure of fluorescein and its alkyl derivatives in micelles. Colloids Surfaces A Physicochem Eng Asp 167:253–262. CrossRefGoogle Scholar
  21. 21.
    Jampol LM, Cunha-Vaz J (1984) Diagnostic Agents in Ophthalmology: Sodium Fluorescein and Other Dyes. Springer, Berlin, Heidelberg, pp 699–714Google Scholar
  22. 22.
    Kanade S, Nataraj G, Ubale M, Mehta P (2016) Fluorescein diacetate vital staining for detecting viability of acid-fast bacilli in patients on antituberculosis treatment. Int J Mycobacteriology 5:294–298. CrossRefGoogle Scholar
  23. 23.
    Grimm JB, Sung AJ, Legant WR, Hulamm P, Matlosz SM, Betzig E, Lavis LD (2013) Carbo fl uoresceins and Carborhodamines as Sca ff olds for high- contrast Fluorogenic probes. ACS Chem Biol 8:1303–1310. CrossRefGoogle Scholar
  24. 24.
    Kitley WR, Santa Maria PJ, Cloyd RA, Wysocki LM (2015) Synthesis of high contrast fluorescein-diethers for rapid bench-top sensing of palladium. Chem Commun 51:8520–8523. CrossRefGoogle Scholar
  25. 25.
    Feng S, Liu D, Feng W, Feng G (2017) Allyl fluorescein ethers as promising fluorescent probes for carbon monoxide imaging in living cells. Anal Chem 89:3754–3760. CrossRefGoogle Scholar
  26. 26.
    Jeong Y, Yoon J (2012) Recent progress on fluorescent chemosensors for metal ions. Inorganica Chim Acta 381:2–14. CrossRefGoogle Scholar
  27. 27.
    Kobayashi T, Nishizawa NK (2014) Iron sensors and signals in response to iron deficiency. Plant Sci 224:36–43. CrossRefGoogle Scholar
  28. 28.
    Brugnara C (2003) Iron deficiency and erythropoiesis: new diagnostic approaches. Clin Chem 49:1573–1578. CrossRefGoogle Scholar
  29. 29.
    Chemate S, Sekar N (2015) A new rhodamine based OFF-ON fluorescent chemosensors for selective detection of Hg2+and Al3+in aqueous media. Sensors Actuators B Chem 220:1196–1204. CrossRefGoogle Scholar
  30. 30.
    An J, Yan M, Yang Z, Li TR, Zhou QX (2013) Dyes and pigments a turn-on fl uorescent sensor for Zn ( II ) based on fl uorescein-coumarin conjugate. Dyes Pigments 99:1–5. CrossRefGoogle Scholar
  31. 31.
    Venkatesan P, Thirumalivasan N, Wu S (2017) RSC advances a rhodamine-based chemosensor with diphenylselenium for highly selective fl uorescence. RSC Adv 7:21733–21739. CrossRefGoogle Scholar
  32. 32.
    Durmu M, Nyokong T (2007) Synthesis, photophysical and photochemical studies of new water-soluble indium(iii) phthalocyanines. Photochem Photobiol Sci 6:659. CrossRefGoogle Scholar
  33. 33.
    Köysal Y, Şamil I, Akdemir N, Erbil A, McKee V (2003) 4-(8-Quinolinoxy)phthalonitrile. Acta Crystallogr Sect E Struct Reports Online 59:o1423–o1424. CrossRefGoogle Scholar
  34. 34.
    Ogunsipe A, Nyokong T (2005) Effects of central metal on the photophysical and photo- chemical properties of non-transition metal sulfophthalo- cyanine. 121–129Google Scholar
  35. 35.
    Sen P, Atmaca GY, Erdoʇmuş A et al (2015) The synthesis, characterization, crystal structure and photophysical properties of a new meso-BODIPY substituted phthalonitrile. J Fluoresc 25:1225–1234. CrossRefGoogle Scholar
  36. 36.
    Rusakowicz R, Testa AC (1968) 2-Aminopyridine as a standard for low-wavelength spectrofluorimetry. J Phys Chem 72:2680–2681. CrossRefGoogle Scholar
  37. 37.
    Dumur F, Gautier N, Gallego-Planas N, Şahin Y, Levillain E, Mercier N, Hudhomme P, Masino M, Girlando A, Lloveras V, Vidal-Gancedo J, Veciana J, Rovira C (2004) Novel fused D-A dyad and A-D-A triad incorporating Tetrathiafulvalene and p-benzoquinone. J Org Chem 69:2164–2177. CrossRefGoogle Scholar
  38. 38.
    Heiner Detert VS (2004) No TitleQuadrupolar donor–acceptor substituted oligo(phenylenevinylene)s—synthesis and solvatochromism of the fluorescence. J Phys Org Chem 17:1051–1056CrossRefGoogle Scholar
  39. 39.
    Wen P, Gao Z, Zhang R, Li A, Zhang F, Li J, Xie J, Wu Y, Wu M, Guo KP (2017) A-π-D-π-a carbazole derivatives with remarkable solvatochromism and mechanoreponsive luminescence turn-on. J Mater Chem C 5:6136–6143. CrossRefGoogle Scholar
  40. 40.
    Sengupta S, Pandey UK (2018) Dual emissive bodipy-benzodithiophene-bodipy TICT triad with a remarkable stokes shift of 194 nm. Org Biomol Chem 16:2033–2038. CrossRefGoogle Scholar
  41. 41.
    Aydemir M, Haykir G, Türksoy F et al (2015) Synthesis and investigation of intra-molecular charge transfer state properties of novel donor-acceptor-donor pyridine derivatives: the effects of temperature and environment on molecular configurations and the origin of delayed fluorescence. Phys Chem Chem Phys 17:25572–25582. CrossRefGoogle Scholar
  42. 42.
    Lakowicz JR (2006) Principles of Fluorescence Spectroscopy. In: 3rd ed. Springer, Baltimore, USGoogle Scholar
  43. 43.
    Ben Zhong Tang AQ (2013) Aggregation-Induced Emission: Fundamentals and Applications, 1st ed. Wiley, LtdGoogle Scholar
  44. 44.
    Li Q, Qian Y (2016) Aggregation-induced emission enhancement and cell imaging of a novel (carbazol-: N -yl)triphenylamine-BODIPY. New J Chem 40:7095–7101. CrossRefGoogle Scholar
  45. 45.
    Han X, Zhang B, Chen J, Liu SH, Tan C, Liu H, Lang MJ, Tan Y, Liu X, Yin J (2017) Modulating aggregation-induced emission via a non-conjugated linkage of fluorophores to. J Mater Chem B 5:5096–5100. CrossRefGoogle Scholar
  46. 46.
    Mazumdar P, Das D, Sahoo P, et al (2015) Exceptionally large blue shift and its potential. 3343–3354.
  47. 47.
    Gopikrishna P, Raman Adil L, Iyer PK (2017) Bridge-driven aggregation control in dibenzofulvene–naphthalimide based donor–bridge–acceptor systems: enabling fluorescence enhancement, blue to red emission and solvatochromism. Mater Chem Front 1:2590–2598. CrossRefGoogle Scholar
  48. 48.
    Usuki T, Shimada M, Yamanoi Y, Ohto T, Tada H, Kasai H, Nishibori E, Nishihara H (2018) Aggregation-induced emission enhancement from Disilane-bridged donor-acceptor-donor Luminogens based on the Triarylamine functionality. ACS Appl Mater Interfaces 10:12164–12172. CrossRefGoogle Scholar
  49. 49.
    Liu X, Qiao Q, Tian W, Liu W, Chen J, Lang MJ, Xu Z (2016) Aziridinyl fluorophores demonstrate bright fluorescence and superior Photostability by effectively inhibiting twisted intramolecular charge transfer. J Am Chem Soc 138:6960–6963. CrossRefGoogle Scholar
  50. 50.
    Wu Q, Zhang T, Peng Q, Shuai Z (2014) Molecular picture from a QM / MM study. Photochem Photobiol Sci 16:5545–5552. Google Scholar
  51. 51.
    Jiating H, Bin X, Feipeng C et al (2009) Aggregation-induced emission in the crystals of 9,10-distyrylanthracene derivatives: the essential role of restricted intramolecular torsion. J Phys Chem C 113:9892–9899. CrossRefGoogle Scholar
  52. 52.
    Edison TNJI, Atchudan R, Shim JJ, Kalimuthu S, Ahn BC, Lee YR (2016) Turn-off fluorescence sensor for the detection of ferric ion in water using green synthesized N-doped carbon dots and its bio-imaging. J Photochem Photobiol B Biol 158:235–242. CrossRefGoogle Scholar
  53. 53.
    Khateb F, Khatib N, Kubánek D (2012) Low-voltage ultra-low-power current conveyor based on quasi-floating gate transistors. Radioengineering 21:725–735. Google Scholar
  54. 54.
    Önal E, Ay Z, Yel Z, Ertekin K, Gürek AG, Topal SZ, Hirel C (2016) Design of oxygen sensing nanomaterial: synthesis, encapsulation of phenylacetylide substituted Pd(II) and Pt(II) meso-tetraphenylporphyrins into poly(1-trimethylsilyl-1-propyne) nanofibers and influence of silver nanoparticles. RSC Adv 6:9967–9977. CrossRefGoogle Scholar
  55. 55.
    Geng T, Huang R, Wu D (2014) Turn-on fluorogenic and chromogenic detection of Fe3+and Cr3+in a completely water medium with polyacrylamide covalently bonding to rhodamine B using diethylenetriamine as a linker. RSC Adv 4:46332–46339. CrossRefGoogle Scholar
  56. 56.
    García-Beltrán O, Cassels BK, Pérez C, Mena N, Núñez M, Martínez N, Pavez P, Aliaga M (2014) Coumarin-based fluorescent probes for dual recognition of copper(II) and iron(III) ions and their application in bio-imaging. Sensors (Switzerland) 14:1358–1371. CrossRefGoogle Scholar
  57. 57.
    Pan C, Wang K, Ji S, Wang H, Li Z, He H, Huo Y (2017) Schiff base derived Fe3+−selective fluorescence turn-off chemsensors based on triphenylamine and indole: synthesis, properties and application in living cells. RSC Adv 7:36007–36014. CrossRefGoogle Scholar
  58. 58.
    Zhao JL, Tomiyasu H, Ni XL, Zeng X, Elsegood MRJ, Redshaw C, Rahman S, Georghiou PE, Yamato T (2014) Synthesis and evaluation of a novel ionophore based on a thiacalix[4]arene derivative bearing imidazole units. New J Chem 38:6041–6049. CrossRefGoogle Scholar
  59. 59.
    Cramer CJ (2004) Essentials of computational chemistry theories and models, 2nd ed. John Wiley & Sons ltdGoogle Scholar
  60. 60.
    Lewars E (2004) Computational chemistry introduction to the theory and applications of molecular and quantum mechanics. Kluwer Academic PublishersGoogle Scholar
  61. 61.
    Becke AD (1993) Density-functional thermochemistry. III. The role of exact exchange. J Chem Phys 98:5648–5652CrossRefGoogle Scholar
  62. 62.
    Lee C, Yang W, Parr RG (1988) Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density. Phys Rev B 37:785–789CrossRefGoogle Scholar
  63. 63.
    Frisch MJ, Trucks GW, Schlegel HB, et al (2009) GAUSSIAN 09 (Revision A.2) Gaussian, Inc., Wallingford, CTGoogle Scholar
  64. 64.
    R. D. Dennington, T. A. Keith and JMM (2008) , GaussView 5. 0. 8. GaussianGoogle Scholar
  65. 65.
    Kaya EN, Yuksel F, Özpinar GA et al (2014) 7-Oxy-3-(3,4,5-trimethoxyphenyl)coumarin substituted phthalonitrile derivatives as fluorescent sensors for detection of Fe3+ ions: experimental and theoretical study. Sensors Actuators B Chem 194:377–388. CrossRefGoogle Scholar
  66. 66.
    Thasnim P, Bahulayan D (2017) Peptidomimetics as inhibitors of human breast cancer cell line MCF-7. New J Chem 41:13483–13489. CrossRefGoogle Scholar
  67. 67.
    Boo BH, Kim JH (2013) Fluorescence and fluorescence excitation spectroscopy of 5, 8-Dihydroxy-1 , 4-naphtho- quinone . Analysis of the electronic spectra via the time-dependent DFT calculation. Bull Kor Chem Soc 34:309–312CrossRefGoogle Scholar
  68. 68.
    Wong ZC, Fan WY, Chwee TS (2018) Computational modelling of singlet excitation energy transfer: a DFT/TD-DFT study of the ground and excited state properties of a syn bimane dimer system using non-empirically tuned range-separated functionals. New J Chem 42:13732–13743. CrossRefGoogle Scholar

Copyright information

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

Authors and Affiliations

  • G. S. Amitha
    • 1
  • Vijisha K. Rajan
    • 2
  • K. Muraleedharan
    • 2
  • Suni Vasudevan
    • 1
    Email author
  1. 1.Department of ChemistryNational Institute of Technology CalicutCalicutIndia
  2. 2.Department of ChemistryUniversity of CalicutCalicutIndia

Personalised recommendations