Systematic study of the fluorescence decays of amino‐coumarin dyes in polymer matrices

Felorzabihi, Neda; Haley, Jeffrey C.; Bardajee, Ghasem Rezanejade; Winnik, Mitchell A.

doi:10.1002/polb.21226

Cited by 14 publications

(9 citation statements)

References 36 publications

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“…The environmental effect on fluorescence of simple or complex coumarin derivatives was extensively studied as solvent effect [ 3 , 4 , 5 , 6 , 7 , 8 , 9 , 10 , 11 , 12 , 13 , 14 , 15 , 16 , 17 , 18 ], inside the micelles [ 19 , 20 , 21 , 22 ] and cavities [ 23 , 24 , 25 , 26 , 27 , 28 , 29 , 30 , 31 , 32 , 33 , 34 , 35 , 36 ] and polymer matrices [ 32 , 33 , 34 , 35 , 36 , 37 , 38 , 39 , 40 , 41 , 42 , 43 , 44 ]. The fluorescence of the bichromophoric coumarins is rather sensitive on the environment.…”

Section: Resultsmentioning

confidence: 99%

“…Moreover, they are used as photoinitiators [ 34 ] for building up polymer chains by copolymerization [ 35 ], for estimating polymer solvent effects [ 36 , 37 , 38 ], various structural characterizations [ 39 , 40 ], for monitoring the releasing properties of poly(methylmethacrylate) nanospheres [ 41 ] and for polymeric fluorescent solar collectors [ 42 ]. The influence of the polymer matrix on the decay of fluorescence dialkylamino-substituted coumarins [ 43 ] and the properties of photo-responsive hyperbranched polyesters [ 44 ] have been systemically studied. Coumarins can serve as model compounds for lignin [ 45 ] and for the characterization of the polarity of cellulose surfaces [ 46 ].…”

Section: Introductionmentioning

confidence: 99%

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Influence of Polarity of Solvents on the Spectral Properties of Bichromophoric Coumarins

et al. 2010

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Absorption and fluorescence spectra of bichromophoric coumarins were investigated in different solvents and in polymer matrices. These bichromophoric coumarins were composed of a coumarin dimethylamino-substituted at position 7 or unsubstituted coumarin and phthalimide or a 1,8-naphthylimide linked with an iminomethyl bridge to the position 3 or 8 of the coumarin ring. Absorption spectra of 7-dimethylamino derivatives in position 3 of coumarin were quite similar, exhibiting broad bands around 430-440 nm like the parent compound 7-dimethylaminocoumarin-3-carbaldehyde. For coumarin derivatives substituted in position 8, the absorption maximum was shifted to shorter wavelength as for derivatives without position 7 dimethylamino substitution. The most intense fluorescence was observed for 7-(N,N-dimethylamino)-3-[(N-phtalimidoyl)iminomethyl]coumarin in polar solvent, while intense fluorescence was observed for 7-(N,N-dimethylamino)-3-[N-(1,3-dioxobenz[de]isoquinolinyl)iminomethyl]-coumarin in non polar solvent (chloroform), comparable with the fluorescence of 7-amino-4-methylcoumarin. Spectral measurements of bichromophoric coumarins in polymer matrices revealed that the maxima lies in between those for chloroform and methanol yielding more intense fluorescence then in solutions. Completely different solvent effects were observed for 7-(N,N-dimethylamino)-3-[N-(1,3-dioxobenz[de]isoquinolinyl)imino-methyl]coumarin and 7-(N,N-dimethylamino)-3-[(N-phtalimidoyl)iminomethyl]coumarin. With addition of polar methanol the intensity of fluorescence decreases, yielding a Stern-Volmer-like constant of 0.54 dm3mol−1 for 7-(N,N-dimethylamino)-3-[N-(1,3-dioxo-benz[de]isoquinolinyl)iminomethyl]coumarin and an even higher one of 1.08 dm3mol−1 for 7-dimethylaminocoumarin-3-carbaldehyde compared to the rather low one of 0.024 dm3 mol−1 for 7-amino-4-methylcoumarin. Contrary to this, addition of methanol under identical conditions brings about an increase in fluorescence intensity of 7-(N,N-dimethylamino)-3-[(N-phtalimidoyl)iminomethyl]coumarin (about 60-fold). The reasons for these different solvent effects are discussed.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Influence of Polarity of Solvents on the Spectral Properties of Bichromophoric Coumarins

et al. 2010

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“…Using the data on several polymers, Simha and Boyer concluded that K 1 = 0.113 that is, the fractional free volume at T g for any polymer is 11.3%. This is the reason for calling the T g as the “iso‐free‐volume state.” Techniques, such as ortho‐positronium (oPs) lifetimes and fluorescence probe lifetimes, have been used to measure the free volume in a number of polymers. Since the free volume would be expected to fluctuate with time with the segmental motion of the amorphous polymers, atomistic molecular simulations have been performed to calculate not only the fractional free volume but also its fluctuation.…”

Section: Introductionmentioning

confidence: 99%

Small molecule self‐assembly in polymer matrices

Sundararajan

2017

J Polym Sci B Polym Phys

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Using small molecules in polymer matrices is common in applications such as (i) plasticizing polymers to modify the glass transition and mechanical properties and (ii) dispersion of photoactive or electroactive small molecules in polymer matrices in organic-electronic devices Aggregation of these small molecules and phase separation leading to crystallization often cannot be morphologically controlled. If these are designed with self-assembling codes such as hydrogen bonding or aromatic interactions, their phase separation behavior would be distinctly different. This review summarizes the studies on morphologies in such situations, such as (i) sub-surface assembly in polymer matrices, (ii) controlled polymerizationinduced phase separation to create polymer blends, (iii) using the polymer to direct the assembly of small molecules in liquid crystalline devices, (iv) functionalizing a polymer with selfassembling small molecules to cause organo-gelation which the polymer itself would not by itself, and (v) using such systems as templates to create porous polymer structures. Organic-inorganic hybrids using polymers as templates for nanostructures and imprinted porous membranes is an emerging area. Since self-assembly is one of the dominating area of research with respect to both small molecules, polymers as well as the combination of the two, this review summarizes the studies on the aforementioned topics.

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“…Moreover, they are used as photo-initiators [37], for incorporation into polymer chains by co-polymerization [38], in the estimation of polymer solvent effects [39,40,41], for various structural characterization [42,43], in the monitoring of the releasing properties of poly(methylmethacrylate) nanospheres [44] and for polymeric fluorescent solar collectors [45]. The influence of the polymer matrix on the decay of fluorescence of dialkylamino-substituted coumarins [46] and on the properties of photo-responsive hyperbranched polyesters [47] has been studied systematically. Coumarins may also serve as model compounds for lignin [48] and the characterization of cellulose surface polarity [49].…”

Section: Introductionmentioning

confidence: 99%

Spectral Properties of Substituted Coumarins in Solution and Polymer Matrices

et al. 2012

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Abstract:The absorption and fluorescence spectra of substituted coumarins (2-oxo-2H-chromenes) were investigated in solvents and in polymer matrices. The substitutions involved were: (1) by groups with varying electron donating ability such as CH 3 , OCH 3 and N(CH 3 ) 2 , mainly, but not exclusively, in positions 7 and (2), by either CHO or 4-PhNHCONHN=CH-in position 3. While the spectra of non-substituted coumarin-3-carbaldehyde has absorptions at approximately 305 and 350 nm, substitution at position 7 leads to remarkable changes in the shape of the absorption spectrum and shifts the absorption to a longer wavelength. Similarly, the replacement of the formyl group with a semicarbazide group substantially influences the shape of the absorption spectrum, and coumarins which have only N(CH 3 ) 2 in position 7 experience small changes. These changes are associated with the increasing intramolecular charge transfer (ICT) character and increasing conjugation length of the chromophoric system, respectively, in the studied molecules. The fluorescence is almost negligible for derivatives which have H in this position. With increasing electron donating ability, and the possibility of a positive mesomeric (+M) effect of the substituent in position 7 of the coumarin moiety, the fluorescence increases, and this increase is most intense when N(CH 3 ) 2 substitutes in this position, for both 3-substituted derivatives. Spectral measurements of the studied OPEN ACCESSMolecules 2012, 17 3260 coumarins in polymer matrices revealed that the absorption and fluorescence maxima lay within the maxima for solvents, and that coumarins yield more intense fluorescence in polymer matrices than when they are in solution. The quantum yield of derivatives which have a dimethylamino group in position 7 in polymer matrices approaches 1, and the fluorescence lifetime is within the range of 0.5-4 ns. The high quantum yield of 7-dimethylamino derivatives qualifies them as laser dyes which have k F higher than k nr in the given medium. This is caused by stiffening of the coumarin structure in polar polymer matrices, such as PMMA and PVC, due to higher micro-viscosity than in solution and intermolecular dipole-dipole interaction between chromophore (dopant) and matrix.

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Systematic study of the fluorescence decays of amino‐coumarin dyes in polymer matrices

Cited by 14 publications

References 36 publications

Influence of Polarity of Solvents on the Spectral Properties of Bichromophoric Coumarins

Influence of Polarity of Solvents on the Spectral Properties of Bichromophoric Coumarins

Small molecule self‐assembly in polymer matrices

Spectral Properties of Substituted Coumarins in Solution and Polymer Matrices

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