Formation and Direct Detection of Non-Conjugated Triplet 1,2-Biradical from β,γ-Vinylarylketone
H. Dushanee M. Sriyarathne A , Kosala R. S. Thenna-Hewa A , Tianeka Scott A and Anna D. Gudmundsdottir A B
+ Author Affiliations
- Author Affiliations
A Department of Chemistry, University of Cincinnati, Cincinnati, OH 45221, USA.
B Corresponding author. Email: anna.gudmundsdottir@uc.edu
Australian Journal of Chemistry 68(11) 1707-1714 https://doi.org/10.1071/CH15401
Submitted: 4 July 2015 Accepted: 1 September 2015 Published: 9 October 2015
Abstract
Laser flash photolysis of 2-methyl-1-phenylbut-3-en-1-one (1) conducted at irradiation wavelengths of 266 and 308 nm results in the formation of triplet 1,2-biradical 2 that has λmax at 370 and 480 nm. Biradical 2 is formed with a rate constant of 1.1 × 107 s–1 and decays with a rate constant of 2.3 × 105 s–1. Isoprene-quenching studies support the notion that biradical 2 is formed by energy transfer from the triplet-excited state of the ketone chromophore of 1. Density functional theory calculations were used to verify the characterization of triplet biradical 2 and validate the mechanism for its formation. Thus, it has been demonstrated that intramolecular sensitization of simple alkenes can be used to form triplet 1,2-biradicals with the two radical centres localized on the adjacent carbon atoms.
References
[1] See Section 32.3: J. M. Berg, J. L. Tymoczko, L. Stryer, Photoreceptor Molecules in the Eye Detect Visible Light, in Biochemistry 5th edn 2002 (W. H. Freeman and Company: New York, NY).[2] C. Dugave, L. Demange, Chem. Rev. 2003, 103, 2475.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD3sXktFGqtr8%3D&md5=3f0cbe3ec1c1da4e08a5249b654282c0CAS | 12848578PubMed |
[3] E. Merino, M. Ribagorda, Beilstein J. Org. Chem. 2012, 8, 1071.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC38XhtFams77N&md5=87cceba3268c824843c1ef95fd85498fCAS | 23019434PubMed |
[4] P. Klán, T. Šolomek, C. G. Bochet, A. Blanc, R. Givens, M. Rubina, V. Popik, A. Kostikov, J. Wirz, Chem. Rev. 2013, 113, 119.
| Crossref | GoogleScholarGoogle Scholar | 23256727PubMed |
[5] J. Sankaranarayanan, S. Muthukrishnan, A. D. Gudmundsdottir, in Advanced Physical Organic Chemistry (Ed. J. P. Richard) 2009, pp. 39–77 (Academic Press: San Diego, CA).
[6] R. S. Mulliken, J. Chem. Phys. 1979, 71, 556.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaE1MXltFCkt74%3D&md5=5a2fa017a7c3676b92e3205b911e6e49CAS |
[7] P. Farmanara, V. Stert, W. Radloff, Chem. Phys. Lett. 1998, 288, 518.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK1cXjtValt7w%3D&md5=c57d9fc781fe7049e62bd05170b553fdCAS |
[8] J. M. Mestdagh, J. P. Visticot, M. Elhanine, B. Soep, J. Chem. Phys. 2000, 113, 237.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD3cXktlalurc%3D&md5=019741ca5d6a5a01532b30d18e846c6dCAS |
[9] R. A. Caldwell, Pure Appl. Chem. 1984, 56, 1167.
| 1:CAS:528:DyaL2cXlvFSqur8%3D&md5=1453dea54b2abc4f9192bec4cc05f9f1CAS |
[10] D. J. Unett, R. A. Caldwell, Res. Chem. Intermed. 1995, 21, 665.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK2MXosVGqtLk%3D&md5=a539d8b3109eaaa0cf38ba5b64d1e17aCAS |
[11] R. A. A. U. Ranaweera, T. Scott, Q. Li, S. Rajam, A. Duncan, R. Li, A. Evans, C. Bohne, J. P. Toscano, B. S. Ault, A. D. Gudmundsdottir, J. Phys. Chem. A. 2014, 118, 10433.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC2cXhtVymt7jM&md5=bb55fde460c87dc76901cdf8b7824bbcCAS |
[12] R. A. Caldwell, C. V. Cao, J. Am. Chem. Soc. 1982, 104, 6174.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaL38XlvFOks7Y%3D&md5=672bfc2042d8bccf7f9c6d8b80fafd24CAS |
[13] E. García-Expósito, R. González-Moreno, M. Martín-Vilà, E. Muray, J. Rifé, J. L. Bourdelande, V. Branchadell, R. M. Ortuño, J. Org. Chem. 2000, 65, 6958.
| Crossref | GoogleScholarGoogle Scholar | 11031016PubMed |
[14] M. T. Nguyen, M. H. Matus, W. A. Lester, D. A. Dixon, J. Phys. Chem. A 2008, 112, 2082.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD2sXhtlKlu73M&md5=013211dff407addb99fe5a83baf1e57cCAS | 18047300PubMed |
[15] F. Qi, O. Sorkhabi, A. G. J. Suits, Chem. Phys. 2000, 112, 10707.
| 1:CAS:528:DC%2BD3cXktV2msrg%3D&md5=5e5cd348edc612d64de9b3bdef08ff2bCAS |
[16] S. Muthukrishnan, J. Sankaranarayanan, R. F. Klima, T. C. S. Pace, C. Bohne, A. D. Gudmundsdottir, Org. Lett. 2009, 11, 2345.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD1MXls1Glu7o%3D&md5=c3f5e933dc37838114953139a1f45e06CAS | 19432450PubMed |
[17] S. Rajam, A. V. Jadhav, Q. Li, S. K. Sarkar, P. N. D. Singh, A. Rohr, T. C. S. Pace, R. Li, J. A. Krause, C. Bohne, B. S. Ault, A. D. Gudmundsdottir, J. Org. Chem. 2014, 79, 9325.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC2cXhsVCnu7fM&md5=227274637b9947417f207e3b76041f5bCAS | 25163813PubMed |
[18] O. Stern, M. Volmer, Phys. Z. 1919, 20, 183.
| 1:CAS:528:DyaB3cXhsFCqtQ%3D%3D&md5=be664aef7525cba3b68bdc641dde85f0CAS |
[19] A. D. Becke, J. Chem. Phys. 1993, 98, 5648.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK3sXisVWgtrw%3D&md5=8d19467ad8c1702f0ea99c588855f696CAS |
[20] M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, G. Scalmani, V. Barone, B. Mennucci, G. A. Petersson, H. Nakatsuji, M. Caricato, X. Li, H. P. Hratchian, A. F. Izmaylov, J. Bloino, G. Zheng, J. L. Sonnenberg, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven, J. A. Montgomery Jr., J. E. Peralta, F. Ogliaro, M. Bearpark, J. J. Heyd, E. Brothers, K. N. Kudin, V. N. Staroverov, R. Kobayashi, J. Normand, K. Raghavachari, A. Rendell, J. C. Burant, S. S. Iyengar, J. Tomasi, M. Cossi, N. Rega, J. M. Millam, M. Klene, J. E. Knox, J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, R. L. Martin, K. Morokuma, V. G. Zakrzewski, G. A. Voth, P. Salvador, J. J. Dannenberg, S. Dapprich, A. D. Daniels, Ö. Farkas, J. B. Foresman, J. V. Ortiz, J. Cioslowski, D. J. Fox, 2009 (Gaussian Inc.: Wallingford, CT).
[21] C. Lee, W. Yang, R. G. Parr, Phys. Rev. B 1988, 37, 785.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaL1cXktFWrtbw%3D&md5=79e43ed9bf1d779a643f274495dfae91CAS |
[22] S. Muthukrishnan, S. M. Mandel, J. C. Hackett, P. N. D. Singh, C. M. Hadad, J. A. Krause, A. D. Gudmundsdottir, J. Org. Chem. 2007, 72, 2757.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD2sXjt1WitL0%3D&md5=78c40a7537443bdd64018c7af3f35b77CAS | 17373846PubMed |
[23] S. Muthukrishnan, J. Sankaranarayanan, T. C. S. Pace, A. Konosonoks, M. Demichiei, M. Meese, C. Bohne, A. D. Gudmundsdottir, J. Org. Chem. 2010, 75, 1393.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3cXht1Klsbo%3D&md5=a31828593b0dbb37d2f3159be0701458CAS | 20113004PubMed |
[24] R. A. A. Upul Ranaweera, J. Sankaranarayanan, L. Casey, B. S. Ault, A. D. Gudmundsdottir, J. Org. Chem. 2011, 76, 8177.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3MXht1Wks7rM&md5=6145886661b53241cb5b7d548666a78fCAS |
[25] D. W. Gamage, Q. Li, R. A. A. U. Ranaweera, S. K. Sarkar, G. K. Weragoda, P. L. Carr, A. D. Gudmundsdottir, J. Org. Chem. 2013, 78, 11349.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3sXhs1ejtL%2FI&md5=57ac9a0cdcb97ed033be84caca7de2d1CAS | 24127994PubMed |
[26] R. A. A. U. Ranaweera, Y. Zhao, S. Muthukrishnan, C. Keller, A. D. Gudmundsdottir, Aust. J. Chem. 2010, 63, 1645.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3cXhsFaqsbjK&md5=deb05448a14e05039d31a88f53a34388CAS |
[27] A. A. Lamola, J. P. Mittal, Science 1966, 154, 1560.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaF2sXjslWmsw%3D%3D&md5=fffd84bc55bb0e88d01de4768c2c83d7CAS | 5924924PubMed |
[28] A. Miyoshi, H. Matsui, N. Washida, J. Phys. Chem. 1990, 94, 3016.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK3cXhsFOmurc%3D&md5=5b1627931ca91daec62220e7d3d38259CAS |
[29] A. Schocker, M. Uetake, N. Kanno, M. Koshi, K. Tonokura, J. Phys. Chem. A. 2007, 111, 6622.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD2sXislent7w%3D&md5=84c1a9f25e21015715c2761cc9303b0eCAS | 17388354PubMed |
[30] H. H. Grotheer, G. Riekert, U. Meier, T. Just, Ber. Bunsenges. Phys. Chem 1985, 89, 187.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaL2MXktlKqtrY%3D&md5=70c9d5a64580a66dc6b5aefd8dc1dae2CAS |
[31] R. G. Parr, Y. Weitao, Density-Functional Theory of Atoms and Molecules 1989 (Oxford University Press: Oxford, UK).
[32] J. K. Labanowski, J. W. Andzelm, Density Functional Methods in Chemistry 1991 (Springer-Verlag: New York, NY).
[33] R. d. Bauernschmitt, Chem. Phys. Lett. 1996, 256, 454.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK28XksFWltrs%3D&md5=f1c621399117900bf751d637fc224d5fCAS |
[34] R. E. Stratmann, G. E. Scuseria, M. J. Frisch, J. Chem. Phys. 1998, 109, 8218.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK1cXmvFygsLs%3D&md5=fc9a8951eb03f6b0a2f26e9a04a1dd45CAS |
[35] J. Tomasi, B. Mennucci, R. Cammi, Chem. Rev. 2005, 105, 2999.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD2MXmsVynurc%3D&md5=51f7fd6b14bb904336cb9a41013270e1CAS | 16092826PubMed |
[36] B. Mennucci, E. Cances, J. Tomasi, J. Phys. Chem. B. 1997, 101, 10506.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK2sXnt1Smsbo%3D&md5=9ee6e98193383121167c32eae7c20851CAS |
[37] E. Cancès, B. Mennucci, J. Chem. Phys. 2001, 114, 4744.
| Crossref | GoogleScholarGoogle Scholar |
[38] J. Tomasi, M. Persico, Chem. Rev. 1994, 94, 2027.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK2cXmtlymsbg%3D&md5=74a9fe6462385b3b3f79d6efd2910963CAS |
[39] T. Imai, S. Nishida, Synthesis 1993, 1993, 395.
| Crossref | GoogleScholarGoogle Scholar |
[40] T. J. Donohoe, J. A. Basutto, J. F. Bower, A. Rathi, Org. Lett. 2011, 13, 1036.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3MXhtFKmsb0%3D&md5=fdf48f286c20c167585839c3d23d93b0CAS | 21268598PubMed |
