Abstract
The electronic excited states corresponding to singlet oxygen generation versus O–O splitting in o-fluorine-phenyl-9-anthracene-9,10-endoperoxide 1 and its 9,10-bisarylanthracene analog 2 have been investigated using theoretical methods. In the case of the smaller endoperoxide 1, the recently developed second-order perturbation theory restricted active space (RASPT2) method has been employed and the results are compared to those from the complete active space (CASPT2), second-order approximated coupled cluster (CC2), and time-dependent density functional theory (TD-DFT) approaches. In addition to the vertical excited states, the photochemical path leading to homolytic O–O dissociation has been computed. This process is governed by a point, where four singlet and four triplet states are almost degenerate and show substantial spin-orbit coupling. The results obtained with RASPT2 indicate that the S 1 state is of π *oo σ *oo character, corresponding to the O–O homolytic dissociation, while higher excited states S n (n ≥ 2) correspond to local and charge transfer excitations and should be correlated to the generation of singlet molecular oxygen. A similar photochemical picture is obtained with CASPT2, although two different active spaces are required to describe different parts of the spectrum. The calculations carried out with CC2 as well as the functionals CAM-B3LYP and the B3LYP(32) containing 32 % of exact exchange show good agreement with the RASPT2 energies, but present a strong mixing of π *oo σ *oo and π *oo π *an excitations in the lowest S 1 state, contradicting the assignment of RASPT2/CASPT2. The use of BP86 is strongly discouraged since it misplaces a large number of charge transfer states below the π *oo σ *oo state. The excited states of 2, calculated with B3LYP(32) are very similar to those of 1, leading to the conclusion that both endoperoxides should show a similar photochemistry, that is, the O–O cleavage seems to be partially quenched and singlet oxygen generation is enhanced, in comparison with the parent compound, anthracene-9,10-endoperoxide.
Graphical abstract
The different electronic excited states of o-fluorine-phenyl-9-anthracene-9,10-endoperoxide have been benchmarked with RASPT2. The lowest excited state corresponds to the homolytic O–O dissociation and higher excited states are connected to singlet oxygen generation.
Similar content being viewed by others
References
DeRosa MC, Crutchley RJ (2002) Coord Chem Rev 233/234:351–357
Aubry JM, Pierlot C, Rigaudy J, Schmidt R (2003) Acc Chem Res 36:668–675
Choea E, Min DB (2006) Crit Rev Food Sci Nutr 46:1–22
Henderson BW, Dougherty T (1992) Photochem Photobiol 55:145–157
Foote CS (1984) Mechanisms of photooxidation. In: Doiron DG, Gomer CJ (eds) Porphyrin localization and treatment of tumors. Alan R. Liss, Inc, pp 3–18
Schmidt R, Schaffner K, Trost W, Brauer HD (1984) J Am Chem Soc 88:956–958
Blumenstock T, Comes FJ, Schmidt R, Brauer HD (1986) Chem Phy Lett 127:452–455
Jesse J, Comes FJ, Schmidt R, Brauer HD (1989) Chem Phy Lett 160:8–12
Jesse J, Markert R, Comes FJ, Schmidt R, Brauer HD (1990) Chem Phy Lett 166:95–100
Brauer HD, Schmidt R (2000) J Phys Chem A 104:164–165
Schmidt R (2012) Photochem Photobiol 11:1004–1009
Eisenthal KB, Turro NJ, Dupuy CG, Hrovat DA, Langan J, Jenny TA, Sitzmann EV (1986) J Phys Chem 90:5168–5173
Klein A, Gudipati MS (1999) J Phys Chem A 103:3843–3853
Corral I, González L, Lauer A, Freyer W, Fidder H, Heyne K (2008) Chem Phys Lett 452:67–71
Gudipati MS, Klein A (2000) J Phys Chem A 104:166–167
Kearns RD (1969) J Am Chem Soc 91:6554–6563
Kearns RD, Khan AU (1969) Photochem Photobiol 10:193–210 /Khan69
Corral I, González L (2008) J Comput Chem 29:1982–1991
Corral I, González L (2007) Chem Phys Lett 446:262–267
Martínez-Fernández L, González L, Corral I (2011) Comput Theoret Chem 975:13–19
Donkers RL, Workentin MS (2004) J Am Chem Soc 126:1688–1698
Fidder H, Lauer A, Freyer W, Koeppe B, Heyne K (2009) J Phys Chem A 104:6289–6296
Rigaudy J, Breliere C, Scribe P (1978) Tetrahedron Lett 7:687–690
Ernsting NP, Schmidt R, Brauer H (1990) J Phys Chem 94:5252–5255
Mollenhauer D, Corral I, González L (2010) J Phys Chem Lett 1:1036–1040
Corral I, González L (2010) Chem Phys Lett 499:21–25
Assmann M, Worth GA, González L (2012) J Chem Phys 137:22A524-1–22A524-12
Lauer A, Dobryakov AL, Kovalenko SA, Fidder H, Heyne K (2011) . Phys Chem Chem Phys 13:8723–8732
Zehm D, Fudicker W, Linker T (2007) Angew Chem Int Ed 46:7689–7692
González L, Escudero D, Serrano-Andrés L (2012) Chem Phys Chem 13:28–51
Dreuw A, Head-Gordon M (2004) J Am Chem Soc 126:4007–4016
Becke AD (1988) Phys Rev A 38:3098–3100
Lee C, Yang W, Parr RG (1988) Phys Rev B 37:785–789
Christiansen O, Koch H, Jørgensen P (1995) Chem Phys Lett 243:409–418
Malmqvist PÅ, Rendell A, Roos BO (1990) J Phys Chem 94:5477–5482
Olsen J, Roos BO, Jørgensen P, Jensen HJA (1988) J Chem Phys 89:2185–2192
Malmqvist PÅ, Pierloot K, Shahi ARM, Cramer CJ, Gagliardi L (2008) J Chem Phys 128:204109-1–204109-10
Manni GL, Aquilante F, Gagliardi L (2011) J Chem Phys 134:034114–034118
Sauri V, Serrano-Andrs L, Shahi ARM, Gagliardi L, Vancoillie S, Pierloot K (2011) J Chem Theory Comput 7:153–168
Escudero D, González L (2012) J Chem Theory Comput 8:203–213
Becke AD (1993) J Chem Phys 98:5648–5652
Hariharan PC, Pople JA (1973) Theor Chim Acta 28:213–222
Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Scalmani G, Barone V, Mennucci B, Petersson GA, Nakatsuji H, Caricato M, Li X, Hratchian HP, Izmaylov AF, J Bloino GZ, Sonnenberg JL, Hada M, Ehara M, Toyota K, Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y, Kitao O, Nakai H, Vreven T, Montgomery JJA, Peralta JE, Ogliaro F, Bearpark M, Heyd JJ, Brothers E, Kudin KN, Staroverov VN, Kobayashi R, Normand J, Raghavachari K, Rendell A, Burant JC, Iyengar SS, Tomasi J, CossiM, Rega N,MillamJM, KleneM, Knox JE, Cross JB, Bakken V, Adamo C, Jaramillo J, Gomperts R, Stratmann RE, O Yazyev AJA, R Cammi CP, Ochterski JW, Martin RL, Morokuma K, Zakrzewski VG, Voth GA, Salvador P, Dannenberg JJ, Dapprich S, Daniels AD, Farkas O, Foresman JB, Ortiz JV, Cioslowski J, Fox DJ (2009) Gaussian 09, Revision A.1, Gaussian, Inc., Wallingford, CT
Yanai T, Tew DP, Handy NC (2004) Chem Phys Lett 393:51–57
Perdew JP (1986) Phys Rev B 33:8822–8824
Feyereisen M, Fitzgerald G, Komornicki A (1993) Chem Phys Lett 208:359–363
T H Dunning J (1971) J Chem Phys 55:716–723
Ahlrichs R, Bar M, Haser M, Horn H, Kolmel C (1989) Chem Phys Lett 162:165–169
Roos BO (1987) In Ab initio methods in quantum chemistry II. Wiley-VCH, Chinester
Finley J, Malmqvist PÅ, Roos BO, Serrano-Andrés L (1998) Chem Phys Lett 288:299–306
Aquilante F, Vico LD, Ferré N, Ghigo G, Malmqvist P, Neogrády P, Pedersen TB, Pitonak M, Reiher M, Roos BO, Serrano-Andrés L, Urban M, Veryazov V, Lindh R (2010) J Comput Chem 31:224–247
Veryazov V, Widmark PO, Serrano-Andrés L, Lindh R, Roos BO (2004). Int J Quantum Chem 100:626–635
Karlström G, Lindh R, Malmqvist PÅ, Roos BO (2003) . Comput Mater Sci 28:222–239
Andersson K, Aquilante F, Bernhardsson A, Blomberg MRA, Cooper DL, Cossi M, Devarajan A, L De Vico NF, Fülscher MP, Gaenko A, Gagliardi L, Ghigo G, de Graaf C, Hess BA, Hagberg D, Holt A, Karlström G, Krogh JW, Lindh R, Malmqvist PÅ, Neogrády P, Olsen J, Pedersen TB, Pitonak M, Raab J, Reiher M, Roos BO, Ryde U, Schapiro I, Schimmelpfennig B, Seijo L, Serrano-Andrés L, Siegbahn PEM, Stålring J, Thorsteinsson T, Vancoillie S, Veryazov V, Widmark PO, Wolf A (2011) MOLCAS, Release 7.6, Department of Theoretical Chemistry, Lund University
Pierloot K, Dumez B, Widmark PO, Roos BO (1995) Theor Chim Acta 90:87–114
Aquilante F, Malmqvist P, Pedersen TB, Ghosh A, Roos BO (2008). J Chem Theory Comput 4:694–702
Anderson K, Roos BO (1995) Chem Phys Lett 245:215–223
Malmqvist P, Roos BO (1989) Chem Phys Lett 155:189–194
Malmqvist P, Roos BO, Schimmelpfennig B (2002) Chem Phys Lett 357:230–240
Acknowledgments
This work is supported by the Deutsche Forschungsgemeinschaft (GO 1059/6-1). All the calculations have been performed at the Universitätsrechenzentrum of the Friedrich-Schiller University of Jena and at the HP computers of the Theoretical Chemistry group at the University of Vienna.
Author information
Authors and Affiliations
Corresponding author
Electronic supplementary material
Below is the link to the electronic supplementary material.
Rights and permissions
About this article
Cite this article
Kupfer, S., Pérez-Hernández, G. & González, L. Singlet oxygen generation versus O–O homolysis in phenyl-substituted anthracene endoperoxides investigated by RASPT2, CASPT2, CC2, and TD-DFT methods. Theor Chem Acc 131, 1295 (2012). https://doi.org/10.1007/s00214-012-1295-7
Received:
Accepted:
Published:
DOI: https://doi.org/10.1007/s00214-012-1295-7