Journal of the American Chemical Society
Communication
this discrepancy worsens when using the UM06-2X functional (instead
Notes
of UB3LYP), with the corresponding values of ΔEST ≈ 2.1, 0.7, and 3.7
The authors declare no competing financial interest.
kcal mol−1 (Table S7): Maneru, D. R.; Pal, A. K.; Moreira, I. P. R.; Datta,
̃
S. N.; Illas, F. J. Chem. Theory Comput. 2014, 10, 335−345.
ACKNOWLEDGMENTS
■
́
(30) (a) Bodzioch, A.; Zheng, M.; Kaszynski, P.; Utecht, G. J. Org.
We thank the NSF Chemistry Division for support of this
research under Grant No. CHE-1362454.
Chem. 2014, 79, 7294−7310. (b) Constantinides, C. P.; Obijalska, E.;
Kaszyn
́
ski, P. P. Org. Lett. 2016, 18, 916−919.
(31) Constantinides, C. P.; Koutentis, P. A. Adv. Heterocycl. Chem.
2016, 119, 173−207.
REFERENCES
(1) Rajca, A. Chem. Rev. 1994, 94, 871−893.
■
(32) Enders, D.; Breuer, K.; Kallfass, U.; Balensiefer, T. Synthesis 2003,
8, 1292−1295.
(2) Gallagher, N. M.; Olankitwanit, A.; Rajca, A. J. Org. Chem. 2015, 80,
1291−1298.
(33) Koutentis, P. A.; Re, D. L. Synthesis 2010, 12, 2075−2079.
(34) Berezin, A. A.; Zissimou, G. A.; Constantinides, C. P.; Beldjoudi,
Y.; Rawson, J. M.; Koutentis, P. A. J. Org. Chem. 2014, 79, 314−327.
(35) Rajca, A.; Pink, M.; Mukherjee, S.; Rajca, S.; Das, K. Tetrahedron
2007, 63, 10731−10742.
(3) Ratera, L.; Veciana, J. Chem. Soc. Rev. 2012, 41, 303−349.
(4) Abe, M. Chem. Rev. 2013, 113, 7011−7088.
(5) Rajca, A.; Wongsriratanakul, J.; Rajca, S. Science 2001, 294, 1503−
1505.
(36) Pearson, G. R.; Walter, R. I. J. Am. Chem. Soc. 1977, 99, 5262−
5268.
(6) Rajca, A. Adv. Phys. Org. Chem. 2005, 40, 153−159.
(7) Wingate, A. J.; Boudouris, B. W. J. Polym. Sci., Part A: Polym. Chem.
2016, 54, 1875−1894.
(8) Sanvito, S. Chem. Soc. Rev. 2011, 40, 3336−3355.
(9) Shil, S.; Bhattacharya, D.; Misra, A.; Klein, D. J. Phys. Chem. Chem.
Phys. 2015, 17, 23378−23383.
(10) Tsuji, Y.; Hoffmann, R.; Strange, M.; Solomon, G. C. Proc. Natl.
Acad. Sci. U. S. A. 2016, 113, E413−E419.
(11) Gaudenzi, R.; Burzuri, E.; Reta, D.; Moreira, I. de P. R.; Bromley,
S. T.; Rovira, C.; Veciana, J.; van der Zant, H. S. J. Nano Lett. 2016, 16,
2066−2071.
(12) Herrmann, C.; Solomon, G. C.; Ratner, M. A. J. Am. Chem. Soc.
2010, 132, 3682−3684.
(13) Jahn, B. O.; Ottosson, H.; Galperin, M.; Fransson, J. ACS Nano
2013, 7, 1064−1071.
(37) Olankitwanit, A.; Kathirvelu, V.; Rajca, S.; Eaton, G. R.; Eaton, S.
S.; Rajca, A. Chem. Commun. 2011, 47, 6443−6445.
(38) Neese, F. ORCAAn Ab Initio, Density Functional and
Semiempirical Program Package, version 3.0.1; University of Bonn,
Germany, 2008.
(39) Rajca, A.; Olankitwanit, A.; Rajca, S. J. Am. Chem. Soc. 2011, 133,
4750−4753.
(40) Olankitwanit, A.; Pink, M.; Rajca, S.; Rajca, A. J. Am. Chem. Soc.
2014, 136, 14277−14288.
(41) Olankitwanit, A.; Rajca, S.; Rajca, A. J. Org. Chem. 2015, 80,
5035−5044.
(42) Sinnecker, S.; Neese, F. J. Phys. Chem. A 2006, 110, 12267−12275.
(43) Rajca, A.; Olankitwanit, A.; Wang, Y.; Boratynski, P. J.; Pink, M.;
Rajca, S. J. Am. Chem. Soc. 2013, 135, 18205−18215.
(14) Hiraoka, S.; Okamoto, T.; Kozaki, M.; Shiomi, D.; Sato, K.; Takui,
T.; Okada, K. J. Am. Chem. Soc. 2004, 126, 58−59.
(15) Suzuki, S.; Furui, T.; Kuratsu, M.; Kozaki, M.; Shiomi, D.; Sato, K.;
Takui, T.; Okada, K. J. Am. Chem. Soc. 2010, 132, 15908−15910.
(16) Inoue, K.; Iwamura, H. Angew. Chem., Int. Ed. Engl. 1995, 34,
927−928.
(17) Rajca, A.; Shiraishi, K.; Rajca, S. Chem. Commun. 2009, 4372−
4374.
(18) (a) Rajca, A.; Takahashi, M.; Pink, M.; Spagnol, G.; Rajca, S. J. Am.
Chem. Soc. 2007, 129, 10159−10170. (b) Rassat, A.; Sieveking, U.
Angew. Chem., Int. Ed. Engl. 1972, 11, 303−304.
(19) Boratynski, P. J.; Pink, M.; Rajca, S.; Rajca, A. Angew. Chem., Int.
Ed. 2010, 49, 5459−5462.
(20) Shultz, D. A.; Fico, R. M.; Lee, H.; Kampf, J. W.; Kirschbaum, K.;
Pinkerton, A. A.; Boyle, P. D. J. Am. Chem. Soc. 2003, 125, 15426−
15432.
(21) Fukuzaki, E.; Nishide, H. J. Am. Chem. Soc. 2006, 128, 996−1001.
(22) (a) Veciana, J.; Rovira, C.; Crespo, M. I.; Armet, O.; Domingo, V.
M.; Palacio, F. J. Am. Chem. Soc. 1991, 113, 2552−2561. (b) Rajca, A.;
Utamapanya, S. J. Org. Chem. 1992, 57, 1760−1767.
(23) Forrest, S. R. Chem. Rev. 1997, 97, 1793−1896.
(24) Ciccullo, F.; Gallagher, N. M.; Geladari, O.; Chasse, T.; Rajca, A.;
Casu, M. B. ACS Appl. Mater. Interfaces 2016, 8, 1805−1812.
(25) Constantinides, C. P.; Koutentis, P. A.; Krassos, H.; Rawson, J.
M.; Tasiopoulos, A. J. J. Org. Chem. 2011, 76, 2798−2806.
(26) (a) Hutchison, K.; Srdanov, G.; Hicks, R.; Yu, H.; Wudl, F.; et al. J.
Am. Chem. Soc. 1998, 120, 2989−2990. (b) Constantinides, C. P.;
Zissimou, G. A.; Berezin, A. A.; Ioannou, T. A.; Manoli, M.; Tsokkou, D.;
Theodorou, E.; Hayes, S. C.; Koutentis, P. A. Org. Lett. 2015, 17, 4026−
4029.
(27) Zheng, Y.; Miao, M.; Dantelle, G.; Eisenmenger, N. D.; Wu, G.;
Yavuz, I.; Chabinyc, M. L.; Houk, K. N.; Wudl, F. Adv. Mater. 2015, 27,
1718−1723.
(28) Frisch, M. J.; et al.. Gaussian 09, revision A.01; Gaussian, Inc.:
Wallingford, CT, 2009.
(29) For diradicals 1, 2, and 5, BS-DFT-computed ΔEST ≈ 1.4, 0.6, and
3.5 kcal mol−1 at the UB3LYP/6-31G(d,p) level, respectively. While this
level of theory overestimates the ΔEST for ground-state triplet diradicals,
D
J. Am. Chem. Soc. XXXX, XXX, XXX−XXX