Abstract
The differently substituted coumarins by synthetic modelling produce a variety of desired molecules with typical photophysical characteristics and nonlinearities. The nonlinear optical (NLO) properties and structural requirement to obtain the nonlinear optical responses in coumarins are discussed in details. Coumarin molecules with donor at 7-position and acceptor at 3-position show strong intramolecular charge transfer (ICT) character along this conjugated path, and such molecular arrangements with D-π-A system result into significant NLO response. This review covers the different types of fluorescent coumarins reported in the literature and comparative study of their NLO properties obtained by different experimental and theoretical methods. Various experimental methods such as EFISH (electric field-induced second harmonic), HRS (hyper-Rayleigh scattering), solvatochromism, solvent-sensitive emission and theoretical approach by DFT (density functional theory) computation are discussed to illustrate the nonlinear optical properties of coumarin chromophores. Bulk nonlinear optical properties of coumarins are investigated by EFISH and Z-scan techniques. Experimental and solvatochromic nonlinear optical properties of coumarins are compared with the theoretical values obtained from DFT calculations. OBO and OBN complex of coumarin chromophores with BF2 unit, azocoumarins, coumarin chalcones, biscoumarins and rigid coumarins studied for their promising NLO properties are covered in this review.
Access this chapter
Tax calculation will be finalised at checkout
Purchases are for personal use only
References
Franken PA, Hill AE, Peters CW, Weinreich G (1961) Generation of optical harmonics. Phys Rev Lett 7:118–119
Tathe AB, Sekar N (2016) Red emitting NLOphoric 3-styryl coumarins: experimental and computational studies. Opt Mater (Amst) 51:121–127
Sahraoui B, Kityk IV, Hudhomme P, Gorgues A (2001) Temperature−pressure anomalies of electrooptic coefficients in C60−TTF derivatives. J Phys Chem B 105:6295–6299
El Ouazzani H, Iliopoulos K, Pranaitis M et al (2011) Second- and third-order nonlinearities of novel push−pull azobenzene polymers. J Phys Chem B 115:1944–1949
Carlotti B, Elisei F, Spalletti A (2011) A peculiar dependence of intersystem crossing of p-nitro-2,5-distyrylfuran on the dielectric properties of the solvent. Phys Chem Chem Phys 13:20787–20793
Kikaš I, Carlotti B, Škorić I et al (2012) Synthesis, spectral properties and photo behaviour of push–pull distyrylbenzene nitro-derivatives. J Photochem Photobiol A Chem 244:38–46
Fortuna CG, Mazzucato U, Musumarra G et al (2010) Photochemistry and DNA-affinity of some stilbene and distyrylbenzene analogues containing pyridinium and imidazolium iodides. J Photochem Photobiol A Chem 216:66–72
Baraldi I, Benassi E, Ciorba S et al (2009) Spectra and photophysics of new organic fluorophores: 2,3-Di(phenylethenyl)benzofuran derivatives. Chem Phys 361:61–67
Pereverzev YV, Gunnerson KN, Prezhdo OV et al (2008) Guest−host cooperativity in organic materials greatly enhances the nonlinear optical response. J Phys Chem C 112:4355–4363
Zhang C, Dalton LR, Oh M-C et al (2001) Low Vπ electrooptic modulators from CLD-1: chromophore design and synthesis, material processing, and characterization. Chem Mater 13:3043–3050
Zyss J (1979) Hyperpolarizabilities of substituted conjugated molecules. III. Study of a family of donor–acceptor disubstituted phenyl-polyenes. J Chem Phys 71:909–916
Oudar JL, Chemla DS (1977) Hyperpolarizabilities of the nitroanilines and their relations to the excited state dipole moment. J Chem Phys 66:2664–2668
Oudar JL (1977) Optical nonlinearities of conjugated molecules. Stilbene derivatives and highly polar aromatic compounds. J Chem Phys 67:446
Zyss J (1979) Hyperpolarizabilities of substituted conjugated molecules. II. Substituent effects and respective σ–π contributions. J Chem Phys 70:3341–3349
Griffiths J, Millar V, Bahra GS (1995) The influence of chain length and electron acceptor residues in 3-substituted 7-N,N-diethylaminocoumarin dyes. Dyes Pigments 28:327–339
Tathe AB, Gupta VD, Sekar N (2015) Synthesis and combined experimental and computational investigations on spectroscopic and photophysical properties of red emitting 3-styryl coumarins. Dyes Pigments 119:49–55
Huang S-T, Jian J-L, Peng H-Z et al (2010) The synthesis and optical characterization of novel iminocoumarin derivatives. Dyes Pigments 86:6–14
Sun Y-F, Wang H-P, Chen Z-Y, Duan W-Z (2013) Solid-state fluorescence emission and second-order nonlinear optical properties of coumarin-based fluorophores. J Fluoresc 23:123–130
Tathe AB, Sekar N (2016) Red-emitting NLOphoric carbazole-coumarin hybrids – synthesis, photophysical properties and DFT studies. Dyes Pigments 129:174–185
Anand B, Roy N, Siva Sankara Sai S, Philip R (2013) Spectral dispersion of ultrafast optical limiting in Coumarin-120 by white-light continuum Z-scan. Appl Phys Lett 102:203302
Lanke SK, Sekar N (2016) Coumarin push-pull NLOphores with red emission: solvatochromic and theoretical approach. J Fluoresc 26:949–962
Kleinman DA (1962) Nonlinear dielectric polarization in optical media. Phys Rev 126:1977–1979
Singer KD, Lalama SL, Sohn JE, Small RD (1987) Nonlinear optical properties of organic molecules and crystals. Academic, Orlando
Zyss J (1994) Molecular nonlinear optics: materials, physics, and devices. Academic, San Diego
Zyss J (2016) Molecular nonlinear optics. Academic, New York
Moerner WE, Silence SM (1994) Polymeric photorefractive materials. Chem Rev 94:127–155
Marder SR (2006) Organic nonlinear optical materials: where we have been and where we are going. Chem Commun:131–134
Albota M, Beljonne D, Brédas J-L et al (1998) Design of organic molecules with large two-photon absorption cross sections. Science (80- ) 281:1653 LP-1656
Kanis DR, Ratner MA, Marks TJ (1994) Design and construction of molecular assemblies with large second-order optical nonlinearities. Quantum Chem Asp Chem Rev 94:195–242
Liu X, Cole JM, Waddell PG et al (2012) Molecular origins of optoelectronic properties in coumarin dyes: toward designer solar cell and laser applications. J Phys Chem A 116:727–737
Moylan CR (1994) Molecular hyperpolarizabilities of coumarin dyes. J Phys Chem 98:13513–13516
García S, Vázquez JL, Rentería M et al (2016) Synthesis and experimental-computational characterization of nonlinear optical properties of triazacyclopentafluorene-coumarin derivatives. Opt Mater (Amst) 62:231–239
Turki H, Abid S, Fery-Forgues S, El Gharbi R (2007) Optical properties of new fluorescent iminocoumarins: part 1. Dyes Pigments 73:311–316
Christie RM, Lui C-H (2000) Studies of fluorescent dyes: part 2. An investigation of the synthesis and electronic spectral properties of substituted 3-(2′-benzimidazolyl)coumarins. Dyes Pigments 47:79–89
Syzova ZA, Doroshenko AO, Lukatskaya LL et al (2004) Bichromophoric fluorescent dyes with rigid molecular structure: fluorescence ability regulation by the photoinduced intramolecular electron transfer. J Photochem Photobiol A Chem 165:59–68
Schill H, Nizamov S, Bottanelli F et al (2013) 4-Trifluoromethyl-substituted coumarins with large stokes shifts: synthesis, bioconjugates, and their use in super-resolution fluorescence microscopy. Chem A Eur J 19:16556–16565
Wagner DB (2009) The use of coumarins as environmentally-sensitive fluorescent probes of heterogeneous inclusion systems. Molecules 14(1):210–237
Cheng LT, Tam W, Stevenson SH et al (1991) Experimental investigations of organic molecular nonlinear optical polarizabilities. 1. Methods and results on benzene and stilbene derivatives. J Phys Chem 95:10631–10643
Momicchioli F, Ponterini G, Vanossi D (2008) First- and second-order polarizabilities of simple merocyanines. An experimental and theoretical reassessment of the two-level model. J Phys Chem A 112:11861–11872
Paley MS, Harris JM (1991) Synthesis and characterization of some pyridinium N-phenoxide betaine dyes for second-harmonic generation. J Org Chem 56:568–574
Leu WCW, Fritz AE, Digianantonio KM, Hartley CS (2012) Push–pull macrocycles: donor–acceptor compounds with paired linearly conjugated or cross-conjugated pathways. J Org Chem 77:2285–2298
Carlotti B, Flamini R, Kikaš I et al (2012) Intramolecular charge transfer, solvatochromism and hyperpolarizability of compounds bearing ethenylene or ethynylene bridges. Chem Phys 407:9–19
Dirk CW, Cheng L-T, Kuzyk MG (1992) A simplified three-level model describing the molecular third-order nonlinear optical susceptibility. Int J Quantum Chem 43:27–36
Isborn CM, Leclercq A, Vila FD et al (2007) Comparison of static first hyperpolarizabilities calculated with various quantum mechanical methods. J Phys Chem A 111:1319–1327
Albert IDL, Marks TJ, Ratner MA (1996) Rational design of molecules with large hyperpolarizabilities. Electric field, solvent polarity, and bond length alternation effects on merocyanine dye linear and nonlinear optical properties. J Phys Chem 100:9714–9725
Capobianco A, Centore R, Noce C, Peluso A (2013) Molecular hyperpolarizabilities of push–pull chromophores: a comparison between theoretical and experimental results. Chem Phys 411:11–16
Erande Y, Sreenath MC, Chitrambalam S et al (2017) Spectroscopic, DFT and Z-scan supported investigation of dicyanoisophorone based push-pull NLOphoric styryl dyes. Opt Mater (Amst) 66:494–511
Tathe AB, Sekar N (2016) Red emitting coumarin—azo dyes : synthesis, characterization, linear and non-linear optical properties-experimental and computational approach. J Fluoresc 26:1279–1293
Lanke SK, Sekar N (2015) Rigid coumarins: a complete DFT, TD-DFT and non linear optical property study. J Fluoresc 25:1469–1480
Prasad MVS, Chaitanya K, UdayaSri N, Veeraiah V (2013) Experimental and theoretical (HOMO, LUMO, NBO analysis and NLO properties) study of 7-hydroxy-4-phenylcoumarin and 5,7-dihydroxy-4-phenylcoumarin. J Mol Struct 1047:216–228
Sankar A, Peramaiyan G, Ambalatharasu S et al (2016) Bulk growth, thermal, linear and nonlinear optical studies of 2-carboxylatopyridinium p-nitrophenol crystal. J Opt 45:175–179
Tambe SM, Tasaganva RG, Jogul JJ et al (2009) Development of polyurethanes with azo-type chromophores for second-order nonlinear optical applications. J Appl Polym Sci 114:2291–2300
Kurtz HA, Stewart JJP, Dieter KM (1990) Calculation of the nonlinear optical properties of molecules. J Comput Chem 11:82–87
Singer KD, Sohn JE, King LA et al (1989) Second-order nonlinear-optical properties of donor- and acceptor-substituted aromatic compounds. J Opt Soc Am B 6:1339–1350
Moylan CR, Twieg RJ, Lee VY et al (1993) Nonlinear optical chromophores with large hyperpolarizabilities and enhanced thermal stabilities. J Am Chem Soc 115:12599–12600
Jayakrishnan K, Joseph A, Mathew P et al (2016) Synthesis, Z-Scan and Degenerate Four Wave Mixing characterization of certain novel thiocoumarin derivatives for third order nonlinear optical applications. Opt Mater (Amst) 58:171–182
Henari FZ, Blau WJ, Milgrom LR et al (1997) Third-order optical non-linearity in Zn(II) complexes of 5,10,15,20-tetraarylethynyl-substituted porphyrins. Chem Phys Lett 267:229–233
Author information
Authors and Affiliations
Corresponding author
Editor information
Editors and Affiliations
Rights and permissions
Copyright information
© 2018 Springer Nature Switzerland AG
About this chapter
Cite this chapter
Erande, Y., Sekar, N. (2018). Fluorescent NLOphoric Coumarins: A Short Review. In: Geddes, C. (eds) Reviews in Fluorescence 2017. Reviews in Fluorescence. Springer, Cham. https://doi.org/10.1007/978-3-030-01569-5_6
Download citation
DOI: https://doi.org/10.1007/978-3-030-01569-5_6
Published:
Publisher Name: Springer, Cham
Print ISBN: 978-3-030-01568-8
Online ISBN: 978-3-030-01569-5
eBook Packages: Biomedical and Life SciencesBiomedical and Life Sciences (R0)