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Synthesis and Spectroscopic Investigation of Diketopyrrolopyrrole - Spiropyran Dyad for Fluorescent Switch Application

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Abstract

We report the synthesis and characterization of a new fluorescent dyad SP-DPP-SP(9) via efficient palladium-catalyzed Sonogashira coupling of prop-2-yn-1-yl 3-(3′,3’dimethyl-6-nitrospiro[chromene-2,2′-indolin]-1′-yl)propanoatespiropyran, SP(8), a well known photochromic accepter, with 3,6-bis(5-bromothiophen-2-yl)-2,5-bis((R)-2-ethylhexyl)-2,5-dihydropyrrolo[3,4-c]pyrrole-1,4-dione, DPP(4), a highly fluorescent donor. Under visible light exposure the SP unit is in a closed hydrophobic form, whereas under UV irradiation it converts to a polar, hydrophilic open form named Merocyanine (MC), which is responsible for functioning of photo-switch application. The photochemistry pertaining to fluorescence switch, ‘on/off’ behaviour, of model dyad SP-DPP-SP(9) is experimentally analyzed in solution as well as in solid state in polymer matrices by photoluminescence(PL) and absorption spectroscopy. After absorption of UV light the spiropyran unit of the dyad under goes the rupture of the spiro C-O bond leading to the formation of MC. The absorption band of MC fairly overlaps to the fluorescence of DPP unit resulting quenching of fluorescence via fluorescence resonance energy transfer from exited DPP unit to ground state MC. In contrary, the fluorescence of DPP is fully regained upon transformation of MC to SP by exposure to visible light or thermal stimuli. Hence, the fluorescence intensity of dyad 9 is regulated by reversible conversion among the two states of the photochromic spiropyran units and the fluorescence resonance energy transfer (FRET) between the MC form of SP and the DPP unit. Conversely, these scrutiny of the experiment express that the design of dyad 9 is viable as efficient fluorescent switch molecule in many probable commercial applications, such as, logic gates and photonic and optical communications.

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Acknowledgments

D. S thank to CSIR and K. N. S and B. R. K to UGC for providing fellowship. PRB and SPS acknowledge the support from CSIR Network project INTELCOAT, CSC-0114.

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Authors and Affiliations

  1. Inorganic and Physical Chemistry Division, Indian Institute of Chemical Technology, Uppal Road, Tarnaka, Hyderabad, 500007, India

    Siva Doddi & Bheerappagari Ramakrishna

  2. Academy of Scientific and Innovative Research (AcSIR), New Delhi, India

    K. Narayanaswamy, Surya Prakash Singh & Prakriti Ranjan Bangal

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  1. Siva Doddi
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  2. K. Narayanaswamy
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  3. Bheerappagari Ramakrishna
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Correspondence to Surya Prakash Singh or Prakriti Ranjan Bangal.

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UV/Vis absorption of SP (8), absorption and emission of MC, absorption and emission of DPP (4), IR and NMR spectra of SP, DPP and SP-DPP- SP. (DOCX 6549 kb)

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Doddi, S., Narayanaswamy, K., Ramakrishna, B. et al. Synthesis and Spectroscopic Investigation of Diketopyrrolopyrrole - Spiropyran Dyad for Fluorescent Switch Application. J Fluoresc 26, 1939–1949 (2016). https://doi.org/10.1007/s10895-016-1886-0

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