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Journal of Luminescence
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A R T I C LE I N FO A B S T R A C T
Keywords: We report the influence of intermolecular and intramolecular hydrogen bonding on the excited state proton
Bent-core liquid crystals transfer (ESPT) emission behavior of two bent core liquid crystal (BLC) molecules, C54H63NO9 (BLC3) and
Intramolecular hydrogen bond C60H75NO9 (BLC4), having a Schiff-base and two long alkyl chains at its two ends. Fluorescence spectra of these
Intermolecular hydrogen bond BLC molecules dispersed in different solvents show dual emission (at ∼ 365 nm and ∼425 nm) from the keto and
ESPT
enol tautomers. We observed that the population of these keto and enol tautomers and the corresponding in-
Effect of solvents
Photoluminescence
tensities of fluorescence emission are strongly influenced by the solvent polarity. In protic solvents, formation of
intermolecular hydrogen bond with the Schiff-base of the BLC molecules is highly favoured than the in-
tramolecular hydrogen bonding. This intermolecular hydrogen bonding drastically reduces the population of the
keto tautomers in the excited state, resulting in enhanced enol fluoroscence band along with a weak keto emission
band. The observed intensity of the enol fluorescence band is the highest for the most studied polar solvent
(methanol). On the other hand, in aprotic solvents, the intramolecular hydrogen bonding is highly favoured,
which leads to the formation of keto tautomers in the excited state. Hence, an intense keto emission band is
observed for the aprotic solvents along with a weak enol emission band. From the time resolved fluorescence
studies we observed a longer life time for the keto band than that for the enol band. This is also related to the
delayed emission associated with the vibrational bands resulting from the bulky alkyl chains attached to the ends
of the BLC molecules.
1. Introduction enol and excited keto tautomer. The notable properties of the ESIPT dyes
are dual emission, large Stokes shift and ultrafast processes. ESIPT dyes
In recent time photophysical studies of dual emitters remain a very have found applications in many fields such as in chemosensors, elec-
active field of research. These dyes found emerging applications in troluminescent materials, laser dyes, and UV-photostabilisers, white
biological and chemical systems due to red shifted emission which is organic light-emitting diodes (OLED) [17–22]. The spectral properties
highly Stokes shifted [1–12]. In this category, dyes undergoing an ex- of the ESIPT dyes depend mainly on hydrogen bonding, rotamerisation
cited-state intramolecular proton transfer (ESIPT) are chiefly attractive. process and pH of the surrounding medium and the substituents present
ESIPT is a very fast phototautomerisation process taking place along an on donor and acceptor units [23–27]. The fluorescence properties of the
intramolecular hydrogen bond between proton donor and proton ac- ESIPT fluorophores are tunable by changing these parameters. Several
ceptor and that are significantly tuned upon electronic excitation series of compounds undergo ESIPT and they have been investigated
[7,13–17]. The pre–requisite for ESIPT is the presence of intramolecular with both experimental and theoretical approaches [14,28–32]. How-
hydrogen bond between proton donor (–OH and –NH2) and proton ever, the effect of hydrogen bonding on proton transfer process can be
acceptor (=N– and –C]O) groups near each other in a molecule. ESIPT used to tune the excited state emission properties of various dyes, which
usually results in dual fluorescence with emission from both excited attracts a lot of attention [15]. Zhou et al. reported the effects of
∗
Corresponding author.
∗∗
Corresponding author.
E-mail addresses: klsandhya@msrit.edu (K.L. Sandhya), bsahoo@iisc.ac.in (B. Sahoo).
https://doi.org/10.1016/j.jlumin.2019.02.056
Received 22 December 2018; Received in revised form 17 February 2019; Accepted 26 February 2019
Available online 01 March 2019
0022-2313/ © 2019 Elsevier B.V. All rights reserved.
A.K. Satapathy, et al. Journal of Luminescence 210 (2019) 371–375
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A.K. Satapathy, et al. Journal of Luminescence 210 (2019) 371–375
Fig. 3. Mechanistic pathways for the fluorescence emission for the keto (produced from cis-enol) and enol (produced from trans-enol) tautomers.
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A.K. Satapathy, et al. Journal of Luminescence 210 (2019) 371–375
Fig. 6. Fluorescence decay plot for BLC3 (upper panel) and BLC4 (lower panel) for emission wavelength of (a) λem = 365 nm and (b) λem = 425 nm, measured using
n-hexane and methanol as solvent. The instrumental response function (IRF) is also shown in each plot.
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A.K. Satapathy, et al. Journal of Luminescence 210 (2019) 371–375
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