Abstract
Steady-state absorption, fluorescence excitation and emission spectra of 4-(N,N-dimethylamino)benzonitrile (DMABN) have been measured at room temperature in cyclohexane, 1,4-dioxane, dichloromethane, and acetonitrile solutions. The fluorescence spectra of DMABN are found to exhibit dual emission in 1,4-dioxane, dichloromethane, and acetonitrile solutions and single emission in cyclohexane solution. The effect of solvent polarity and excitation wavelength on the emission spectra has also been studied. The fluorescence excitation spectra of DMABN monitored at the emission bands are different. The presence of two different conformations of the same molecule in the ground state has lead to two close lying excited states; local excited (LE) and charge transfer (CT), and thereby results in the dual fluorescence of the compound. The experimental studies were supported by ab initio density functional theory (DFT) calculations performed at the B3LYP/6-31Gd level of theory. On the basis of the experimental results and our theoretical calculations, we suggest that there are two conformers of DMABN, which are stable in the ground state, equilibrated in solution at room temperature that give rise dual fluorescence upon excitation.
Similar content being viewed by others
References
Lippert E, Lüder W, Boos H (1962) In: Mangini A (ed) Advances in molecular spectroscopy. Pergamon, Oxford
Platt J (1949) J Chem Phys 17:4840
Grabowski ZR, Rotkiewicz K, Rettig W (2003) Chem Rev 103:3899–4031
Lippert E, Lüder W, Moll F, Nägele W, Boos H, Prigge H, Seibold-Blankenstein I (1961) Angew Chem 73:695
Rettig W, Bliss B, Dirnberger K (1999) Chem Phys Lett 305:8–14
Rotkiewicz K, Grellmann KH, Grabowski ZR (1973) Chem Phys Lett 19:315–318
Rotkiewicz K, Grellmann KH, Grabowski ZR (1973) Chem Phys Lett 21:212
Grabowski ZR, Rotkiewicz K, Siemarczuk A, Cowley DJ, Baumann W (1979) Nouv J Chim 3:443
Grabowski ZR, Rotkiewicz K, Siemiarczuk A (1979) J Lumin 18:420
Köhler G, Rechthaler K, Rotokiewicz K, Rettig W (1996) Chem Phys 207:85–101
Gude CC, Rettig W (1998) J Phys Chem A 102:7754–7761
Rettig W, Lutze S (2001) Chem Phys Lett 341:263–271
Rettig W (1986) Angew Chem, Int Ed Engl 25:971–988
Lippert E, Rettig W, Bonacic-Koutecky V, Heisel F, Miehé JA (1987) Adv Chem Phys 68:1–173, and references therein
Rettig W (1994) In: Mattay J (ed) Topics in current chemistry, electron-transfer I, vol. 169. Springer, Berlin, pp 253–299
Leinhos U, Kühnle W, Zachariasse KA (1991) J Phys Chem 95:2013–2021
Schuddeboom W, Jonker SA, Warman JH, Leinhos U, Kühnle W, Zachariasse KA (1992) J PhysChem 96:10809–10819
Zachariasse KA, von der Haar T, Hebecker A, Leinhos U, Kühnle W (1993) Pure Appl Chem 65:1745–1750
von der Haar T, Hebecker A, Il’ichev YV, Jiang Y-B, Kühnle W, Zachariasse KA (1995) Recl Trav Chim Pays-Bas 114:430
Zachariasse KA, Grobys M, von der Haar T, Hebecker A, Il’ichev YV, Jiang Y-B, Morawski O, Kühnle W (1996) J Photochem Photobiol, A: Chem 102:59–70
Il’ichev YV, Kühnle W, Zachariasse KA (1998) J PhysChem A 102:5670–5680
Zachariasse KA (2000) Chem Phys Lett 320:8–13
Demeter A, Druzhinin S, George M, Haselbach E, Roulin J-L, Zachariasse KA (2000) Chem Phys Lett 323:351–360
Zachariasse KA, Grobys M, Von der Haar T, Hebecker A, Il’ichev YV, Morawski O, Rückert I, Kühnle W (1997) J Photochem Photobiol A 105:373–383
Chudoba C, Kummrow A, Dreyer J, Stenger J, Nibbering ETJ, Elsaesser T, Zachariasse KA (1999) Chem Phys Lett 309:357–363
Daum R, Druzhinin S, Ernst D, Rupp L, Schroeder J, Zachariasse KA (2001) Chem Phys Lett 341:272–278
Druzhinin SI, Demeter A, Galievsky VA, Yoshihara T, Zachariasse KA (2003) J Phys Chem A 107:8075–8085
Changenet P, Plaza P, Martin MM, Meyer YH (1997) J Phys Chem A 101:8186–8194
Su S-G, Simon JD (1988) J Chem Phys 89:908–919
Okamoto H, Inishi H, Nakamura Y, Kohtani S, Nakagaki R (2001) J Phys Chem A 105:4182–4188
Kwok WM, Ma C, Matousek P, Parker AW, Phillips D, Toner WT, Towrie M, Umapathy S (2001) J Phys Chem A 105:984–990
Ma C, Kwok WM, Matousek P, Parker AW, Phillips D, Toner WT, Towrie M (2002) J Phys Chem A 106:3294–3305
Techert S, Zachariasse KA (2004) J Am Chem Soc 126:5593–5600
Zachariasse KA, Druzhinin SI, Bosch W, Machinek R (2004) J Am Chem Soc 126:1705–1715
Yoshihara T, Druzhinin SI, Zachariasse KA (2004) J Am Chem Soc 126:8535–8539
Fuss W, Pushpa KK, Rettig W, Schmid WE, Trushin SA (2002) Photochem Photobiol Sci 1:255–262
Sudholt W, Sobolewski AL, Domcke W (1999) Chem Phys 250:9–18, and references therein
Serrano-Andrés L, Merchán M, Roos BO, Lindh R (1995) J Am Chem Soc 117:3189–3204
Sobolewski AL, Domcke W (1996) Chem Phys Lett 259:119–127
Sobolewski AL, Domcke W (1996) Chem Phys Lett 250:428–436
Sobolewski AL, Sudholt W, Domcke W (1998) J Phys Chem A 102:2716–2722
Lommatzsch U, Brutschy B (1998) Chem Phys 234:35–57
Parusel ABJ, Köhler G, Grimme S (1998) J Phys Chem A 102:6297–6306
Parusel ABJ, Köhler G, Nooijen M (1999) J Phys Chem A 103:4056–4064
Parusel ABJ, Rettig W, Sudholt W (2002) J Phys Chem A 106:804–815
Dreyer J, Kummrow A (2000) J Am Chem Soc 122:2577–2585
Zilberg S, Haas Y (2002) J Phys Chem A 106:1–11
Rappoport D, Furche F (2004) J Am Chem Soc 126:1277–1284
Köhn A, Hättig C (2004) J Am Chem Soc 126:7399–7410
Gedeck P, Schneider S (1997) J Photochem Photobiol, A: Chem 105:165–181, and references therein
Moro GJ, Nordio PL, Polimeno A (1989) Mol Phys 68:1131–1141
Kato S, Amatatsu Y (1990) J Chem Phys 92:7241–7257
Fonseca T, Kim HJ, Hynes JT (1994) J Mol Liq 60:161–200
Fonseca T, Kim HJ, Hynes JT (1994) J Photochem Photobiol, A: Chem 82:67–79
Broo A, Zerner MC (1995) Theor Chim Acta 90:383–395
Gorse A-D, Pesquer M (1995) J Phys Chem 99:4039–4049
Soujanya T, Saroja G, Samanta A (1995) Chem Phys Lett 236:503–509
Hayashi S, Ando K, Kato S (1995) J Phys Chem 99:955–964
Kim HJ, Hynes JT (1997) J Photochem Photobiol, A: Chem 105:337–343
Mennucci B, Toniolo A, Tomasi J (2000) J Am Chem Soc 122:10621–10630
Dobkowski J, Wojcik J, Kozminski W, Kołs R, Waluk J, Michl J (2002) J Am Chem Soc 124:2406
Cogan S, Zilberg S, Haas Y (2006) J Am Chem Soc 128:3335–3345
Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Montgomery JA Jr, Vreven T, Kudin KN, Burant JC, Millam JM, Iyengar SS, Tomasi J, Barone V, Mennucci B, Cossi M, Scalmani G, Rega N, Petersson GA, Nakatsuji H, Hada M, Ehara M, Toyota K, Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y, Kitao O, Nakai H, Klene M, Li X, Knox JE, Hratchian HP, Cross JB, Adamo C, Jaramillo J, Gomperts R, Stratmann RE, Yazyev O, Austin AJ, Cammi R, Pomelli C, Ochterski JW, Ayala PY, Morokuma K, Voth GA, Salvador P, Dannenberg JJ, Zakrzewski VG, Dapprich S, Daniels AD, Strain MC, Farkas O, Malick DK, Rabuck AD, Raghavachari K, Foresman JB, Ortiz JV, Cui Q, Baboul AG, Clifford S, Cioslowski J, Stefanov BB, Liu G, Liashenko A, Piskorz P, Komaromi I, Martin RL, Fox DJ, Keith T, Al-Laham MA, Peng CY, Nanayakkara A, Challacombe M, Gill PMW, Johnson B, Chen W, Wong MW, Gonzalez C, Pople JA (2003) Gaussian 03, Revision B.01. Gaussian, Inc., Pittsburgh
Becke AD (1993) J Chem Phys 98:5648
Lee C, Yang W, Parr RG (1998) Phys Rev B 37:785
Cammi R, Mennucci B, Tomasi J (2000) J Phys Chem A 104:5631
Böttler CJF (1973) In: Van Belle OC, Bordewijk P, Rip A (eds) Theory of electric polarization, vol. 1. Elsevier, Amsterdam
Onsager L (1936) J Am Chem Soc 58:1486
Lippert E (1955) Z Naturforsch 10a:541
Mataga N, Kaifu Y, Koizumi M (1955) Bull Chem Soc Jpn 28:690
Liptay W (1974) In: Lim EC (ed) Excited states. Academic, New York, p 129
Acknowledgments
Many thanks are due to Prof. Wondemagegn Mammo for providing us access to the fluorescence measurements facilities, and Prof. V.J.T. Raju for valuable discussions.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Atsbeha, T., Mohammed, A.M. & Redi-Abshiro, M. Excitation Wavelength Dependence of Dual Fluorescence of DMABN in Polar Solvents. J Fluoresc 20, 1241–1248 (2010). https://doi.org/10.1007/s10895-010-0675-4
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10895-010-0675-4