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1 Electronic Supplementary Material (ESI) for Chemical Science. This journal is The Royal Society of Chemistry 2014 Electronic Supplementary Information (ESI) for A Kinetically Blocked 1,14:11,12- Dibenzopentacene: A Persistent Triplet Diradical of Non-Kekulé Polycyclic Benzenoid Hydrocarbons Yuan Li, a Kuo-Wei Huang, b Zhe Sun, a Richard D. Webster, c Zebing Zeng, a Wangdong Zeng, a Chunyan Chi, a Ko Furukawa,*,d Jishan Wu*,a,e a Department of Chemistry, National University of Singapore, 3 Science Drive 3, , Singapore; Fax: (+65) ; chmwuj@nus.edu.sg b King Abdullah University of Science and Technology (KAUST), Division of Physical Science and Engineering and KAUST Catalysis Center, Thuwal , Kingdom of Saudi Arabia c Division of Chemistry & Biological Chemistry, School of Physical & Mathematical Sciences, Nanyang Technological University, 21 Nanyang Link, , Singapore d Center for Instrumental Analysis, Institute for Research Promotion, Niigata University, 8050 ikarashi 2-no-cho, nishi-ku, Niigata , Japan; kou-f@chem.sc.niigata-u.ac.jp \ e Institute of Materials Research and Engineering, A*STAR, 3 Research Link, Singapore, Table of Contents 1. IT-T curve of the monoradical generated by the oxidation of 9 by p-chloranil S2 2. Absorption spectrum of dianion 9 2- S2 3. Concentration dependent IT-T curves for DP-Mes S3 4. DFT calculation details S4 5. Mass spectrum of the DP-Mes solution at room temperature S13 6. References S13 7. Appendix: NMR spectra and HR mass spectra of new compounds S15 S1

2 Absorbance 1. IT-T curve of the monoradical generated by the oxidation of 9 by p-chloranil The ESR signal intensity I was estimated by using the pulsed-esr technique. Fig. S1 shows the temperature dependence of IT values at 4-40 K, where T denotes the temperature. I is proportional to the magnetic susceptibility χ. Namely, IT means χt value. It was found that the IT value decrease as the temperature is lowered. This behavior indicates an intermolecular antiferromgnetic spin coupling via dimerization process at low temperature. The exchange interaction J/k B was estimated to be 12.0 ±0.8 K based on the singlet-triplet model. IT / arb. unit Obs. Calc. J / k 0 B = -12 K T / K Fig. S1. Temperature dependence of IT value for the oxidation product of 9 with p-chloranil in toluene. The blue line denotes the calculated IT value based on singlet-triplet model using BB equation. 2. Absorption spectrum of dianion Wavelength (nm) Fig. S2. Absorption spectrum of 9 2- after treatment of 9 with lithium diisopropylamide (LDA) in 2-methyl tetrahydrofuran (2-Me-THF) at -78 o C for 30 min. S2

3 IT / arb. unit 3. Concentration dependent IT-T curves for DP-Mes The concentration dependent ESR measurements were done by a dilution method. The in situ generated triplet diradical solution at -78 o C starting from 8 mm of precursor 9 (denoted as 1 conc. ) was carefully diluted by 1/2 (denoted as 1/2 conc. ) and 1/3 (denoted as 1/3 conc. ) by adding chilled anhydrous 2-Me-THF (-78 o C) in an ESR tube under nitrogen protection. Then the solutions with different concentrations were subjected to VT ESR measurements at low temperature. Upon the dilution, there was no obvious change of the ESR spectrum, indicating that there was no significant decomposition of the triplet diradical during the operation. The temperature dependent IT values were shown in Fig. S3. The comparison of the absolute signal intensity is difficult, because the measurements error includes amount of sample and signal-to-noise ratio. Therefore, we compared the normalized signal intensity at 70 K on each concentrations conc. 1/2 conc. 1/3 conc T / K Fig. S3. Temperature dependence of observed IT value for the DP-Mes at different concentrations. The in situ generated diradicals solution was carefully diluted by 1/2 (1/2 conc.) and 1/3 (1/3 conc.) of the original concentration (1 conc.) in an ESR tube at -78 o C. S3

4 4. DFT calculations details Density functional theory calculations for DP-Mes were employed with Gaussian 09 package, 1 utilizing the UCAM-B3LYP level of theory with Pople basis set 6-31G* in the gas phase. Triplet diradical: Mulliken atomic spin densities: 1 C C C C C C C H C H C C C C C C C H C S4

5 20 C H C H C H C C H C H C C H C C C H C C H H H C H H H C C C C C C H H C C C C C C H H C H H H C H H S5

6 70 H C H H H C H H H C H H H C H H H H H Sum of Mulliken atomic spin densities = <S**2>= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= C C C C C C C H C H C C C C C C C H C C H C S6

7 H C H C C H C H C C H C C C H C C H H H C H H H C C C C C C H H C C C C C C H H C H H H C H H H C H S7

8 H H C H H H C H H H C H H H H H Singlet diradical Mulliken atomic spin densities: 1 1 C C C C C C C H S8

9 9 C H C C C C C C C H C C H C H C H C C H C H C C H C C C H C C H H H C H H H C C C C C C H H C C C C S9

10 59 C C H H C H H H C H H H C H H H C H H H C H H H C H H H H H Sum of Mulliken atomic spin densities = <S**2>= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= C C C C C C C H C H C C S10

11 C C C C C H C C H C H C H C C H C H C C H C C C H C C H H H C H H H C C C C C C H H C C C C C C H H S11

12 C H H H C H H H C H H H C H H H C H H H C H H H H H S12

13 5. Mass spectrum of DP-Mes solution at room temperature Fig. S4. MALDI-TOF mass spectrum of the products when the solution of DP-Mes was briefly warmed up to room temperature. 6. References (1) Gaussian 09; Revision A.2; Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Mennucci, B.; Petersson, G. A.; Nakatsuji, H.; Caricato, M.; Li, X.; Hratchian, H. P.; Izmaylov, A. F.; Bloino, J.; Zheng, G.; Sonnenberg, J. L.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Vreven, T.; Montgomery, J., J. A.; Peralta, J. E.; Ogliaro, F.; S13

14 Bearpark, M.; Heyd, J. J.; Brothers, E.; Kudin, K. N.; Staroverov, V. N.; Kobayashi, R.; Normand, J.; Raghavachari, K.; Rendell, A.; Burant, J. C.; Iyengar, S. S.; Tomasi, J.; Cossi, M.; Rega, N.; Millam, N. J.; Klene, M.; Knox, J. E.; Cross, J. B.; Bakken, V.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Martin, R. L.; Morokuma, K.; Zakrzewski, V. G.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Dapprich, S.; Daniels, A. D.; Farkas, Ö.; Foresman, J. B.; Ortiz, J. V.; Cioslowski, J.; Fox, D. J.; Gaussian, Inc., Wallingford CT, S14

15 7. Appendix: NMR spectra and HR mass spectra of new compounds Fig. S5. 1 H NMR spectrum of 3 (300MHz, CDCl 3, rt) S15

16 Fig. S6. 13 C NMR spectrum of 3 (125MHz, CDCl 3, rt) S16

17 Fig. S7. 1 H NMR spectrum of 4 (500 MHz, CDCl 3, rt) S17

18 Fig. S8. 13 C NMR spectrum of 4 (125 MHz, CDCl 3, rt) S18

19 Fig. S9. 1 H NMR spectrum of 6 (500MHz, CDCl 3, rt) S19

20 Fig. S C NMR spectrum of 6 (125 MHz, CDCl 3, rt) S20

21 Fig. S11. 1 H NMR spectrum of 7 (500MHz, CDCl 3, rt) S21

22 Fig. S C NMR spectrum of 7 (125 MHz, CDCl 3, rt) S22

23 Fig. S13. 1 H NMR spectrum of 8 (500MHz, CDCl 3, rt) S23

24 Fig. S CNMR spectrum of 8 (125 MHz, CDCl 3, rt) S24

25 Fig. S15. 1 H NMR spectrum of 9 (500MHz, CDCl 3, rt) S25

26 Fig. S C NMR spectrum of 9 (125 MHz, CDCl 3, rt) S26

27 Fig. S17. HR-MS (EI) of compound 3 S27

28 Fig. S18. HR-MS (EI) of compound 4 S28

29 Fig. S19. HR-MS (EI) of compound 6 S29

30 Fig. S20. HR-MS (EI) of compound 7 S30

31 Fig. S21. HR-MS (EI) of compound 8 S31

32 Fig. S22. HR-MS (EI) of compound 9 S32