Macrocyclic Oligofurans: A Computational Study

Size: px

Start display at page:

Download "Macrocyclic Oligofurans: A Computational Study"

Agatha Stevenson
5 years ago
Views:

1 Supporting Information Macrocyclic Oligofurans: A Computational Study Or Dishi and Ori Gidron* Institute of Chemistry, The Hebrew University of Jerusalem, Edmond J. Safra Campus, Givat Ram, Jerusalem, Israel. ori.gidron@mail.huji.ac.il S1

2 Table of Contents S1. Average interring dihedral angles of DM-nCX... 4 Table S1. Average dihedral angle between the units for 6CF, DM-6CF, 10CT, DM-10CT, 12CT and DM-12CT S2. Energies of syn and anti conformers of ncx... 4 Table S2. Difference in energies between of syn and anti conformations of ncf and nct. ΔE = Esyn-Eanti. When attempts were made to optimize 6CF and 8CF in their anti conformations, the structures reorganized to their syn conformation S3. Raman frequencies and intensity values for the ECC mode... 5 Table S3. Normalized intensity values of the ECC modes... 5 S4. Interring dihedral angles for neutral and charged ncx... 6 Table S4: Average dihedral angles and standard deviation for ncx, ncx + and ncx S5. Optimized structures of selected macrocycles... 7 Figure S1: Optimized structures of (a,b) 8CF, (c,d) 8CF + and (e,f) 8CF 2+. Hydrogens are omitted for clarity Figure S2: Optimized structures of (a,b) 12CT and (c,d) 12CT +. Hydrogens are omitted for clarity S6. Absolute Energies for Neutral Structures... 9 Table S5: Absolute energies for all uncharged structures presented in this work S7. Reorganization energies and absolute energies for charged molecules Table S6. Absolute energies for all charged structures presented in this work S8. Calculation of the imaginary bisecting point S9. Frontier molecular orbitals for selected macrocycles Figure S4. (a) HOMO and (b) LUMO of 6CF Figure S5. (a) SOMO (α spin), (b) LUMO (α spin), (c) HOMO (β spin) and (d) SOMO (β spin) of 6CF Figure S6. (a) SOMO (α spin), (b) LUMO (α spin), (c) HOMO (β spin) and (d) SOMO (β spin) of 6CF Figure S7. (a) HOMO and (b) LUMO of 8CF Figure S8. (a) SOMO (α spin), (b) LUMO (α spin), (c) HOMO (β spin) and (d) SOMO (β spin) of 8CF S2

3 Figure S9. (a) SOMO (α spin), (b) LUMO (α spin), (c) HOMO (β spin) and (d) SOMO (β spin) of 8CF Figure S10. (a) HOMO and (b) LUMO of 12CF Figure S11. (a) SOMO (α spin), (b) LUMO (α spin), (c) HOMO (β spin) and (d) SOMO (β spin) of 12CF Figure S12. (a) HOMO and (b) LUMO of 12CF Figure S13. (a) SOMO (α spin), (b) LUMO (α spin), (c) HOMO (β spin) and (d) SOMO (β spin) of 12CT S10. Orbital energy gaps for charged macrocycles Figure S14. Orbital energy gaps for ncf + and nct Figure S15. Orbital energy gaps for ncf 2+ and nct S11. Bond length alternations S12. Comparison with M062X/6-311G(d) and B3LYP/6-31++G** Levels Table S7. Absolute energies of neutral structures calculated at different levels of theory Figure S26. Optimized structures of 6CF optimized at (a) M062X/6-311g(d), (b) B3LYP/6-311G(d), and (c) B3LYP/6-31++G** levels Figure S27. Optimized structures of 6CT optimized at (a) M062X/6-311g(d), (b) B3LYP/6-311G(d), and (c) B3LYP/6-31++G** levels Figure S28. Optimized structures of 8CF optimized at (a) M062X/6-311g(d), (b) B3LYP/6-311G(d), and (c) B3LYP/6-31++G** levels Figure S29. Optimized structures of 8CT optimized at (a) M062X/6-311g(d), (b) B3LYP/6-311G(d), and (c) B3LYP/6-31++G** levels Figure S30. Optimized structures of 10CF optimized at (a) M062X/6-311G(d) and (b) B3LYP/6-311G(d) levels Figure S31. Optimized structures of 10CT optimized at (a) M062X/6-311G(d) and (b) B3LYP/6-311G(d) levels Figure S32. Optimized structures of 12CT optimized at (a) M062X/6-311G(d) and (b) B3LYP/6-311G(d) levels References S3

4 S1. Average interring dihedral angles of DM-nCX Table S1. Average dihedral angle between the units for 6CF, DM-6CF, 10CT, DM-10CT, 12CT and DM-12CT. Average interring dihedral angle 6CF 0 DM-6CF CT DM-10CT CT DM-12CT S2. Energies of syn and anti conformers of ncx Table S2. Difference in energies between of syn and anti conformations of ncf and nct. ΔE = Esyn-Eanti. When attempts were made to optimize 6CF and 8CF in their anti conformations, the structures reorganized to their syn conformation. n ΔEnCF (kcal/mol) ΔEnCT (kcal/mol) S4

5 S3. Raman frequencies and intensity values for the ECC mode The ECC modes are the strongest vibrations in the Raman spectrum, and increase in intensity with the increase in electron delocalization. 1,2 The maximal normalized intensity for ncf is observed for 8CF and is more than twice the value obtained for 6CF, whereas for nct the trend is less pronounced, but the normalized intensity of the ECC mode generally increases with increasing size. Table S3. Normalized intensity values of the ECC modes n ncf nct ν[ecc] (cm -1 ) Normalized ν[ecc] (cm -1 ) Normalized Intensity Intensity S5

6 S4. Interring dihedral angles for neutral and charged ncx Table S4: Average dihedral angles and standard deviation for ncx, ncx + and ncx 2+. ncf ncf + ncf 2+ Average Average Average n Standard Standard Standard Dihedral Dihedral Dihedral Deviation Deviation Deviation Angle Angle Angle nct nct + nct 2+ Average Average Average n Standard Standard Standard Dihedral Dihedral Dihedral Deviation Deviation Deviation Angle Angle Angle S6

7 S5. Optimized structures of selected macrocycles a) b) c) d) e) f) Figure S1: Optimized structures of (a,b) 8CF, (c,d) 8CF + and (e,f) 8CF 2+. Hydrogens are omitted for clarity. S7

8 a) b) c) d) Figure S2: Optimized structures of (a,b) 12CT and (c,d) 12CT +. Hydrogens are omitted for clarity. S8

9 S6. Absolute Energies for Neutral Structures Table S5: Absolute energies for all uncharged structures presented in this work. Name Energy (Hartree) Name Energy (Hartree) 5F CF F CT F CT F CT F CT F CT F CT F CT F CT F CT F CT T CF-Anti T CF-Anti T CF-Anti T CF-Anti T CF-Anti T CF-Anti T CT-Anti T CT-Anti T CT-Anti T CT-Anti T CT-Anti CF CT-Anti CF CT-Anti CF Furan-PBC CF Thiophene-PBC CF DM-1F CF DM-1T CF DM-6CF CF DM-10CT CF DM-12CT S9

S7. Reorganization energies and absolute energies for charged molecules The reorganization energies for the first and second oxidation were calculated as λa + λb for the neutral cation radical states

For the dications the letters R and U are used to represent optimizations done in restricted and unrestricted calculations, respectively.

10 S7. Reorganization energies and absolute energies for charged molecules The reorganization energies for the first and second oxidation were calculated as λa + λb for the neutral cation radical states and λc + λd for cation radical dication as depicted in Figure S3. The energies for each structure are detailed in Table S5 and Table S6. For the dications the letters R and U are used to represent optimizations done in restricted and unrestricted calculations, respectively. Note that for all the energies for the optimized dications, the energy difference between the restricted and unrestricted calculations is negligible. Figure S3. Internal reorganization energies for ncx species. The first reorganization energy is calculated as the sum of the internal reorganization components λa and λb, and the second reorganization energie as the sum of the internal reorganization components λc + λd. S10

11 Table S6. Absolute energies for all charged structures presented in this work File Name Energy (Hartree) File Name Energy (Hartree) 5CF CF22R CF CF22U CF CT CF CT CF CT CF CT CF22R CT CF22U CT CT CT22U CT CF CT CF CT CF CT CF CT CF CT22R CF CT22U CF22R CF CF22U CF CT CF CT CF CT CF CT CF CT CF22R CT CF22U CT22R CT CT22U CT CF CT CF CT CF S11

12 6CT CF CT CF CT22R CF CT22U CF22R CF CF22U CF CT CF CT CF CT CF CT CF CT CF22R CT CF22U CT22R CT CT22U CT CF CT CF CT CF CT CF CT CT CT22R CF CT22U CF CF CF CF CF CF CT CF CT CF CT CF CT S12

S8. Calculation of the imaginary bisecting point The angle at the imaginary bisecting point (IBP) of two interring bonds can be calculated directly

13 S8. Calculation of the imaginary bisecting point The angle at the imaginary bisecting point (IBP) of two interring bonds can be calculated directly from the optimized structure (Chart S1). Chart S1. Calculating the angle at the IBP from structural data available from the optimized structure data. S13

14 S9. Frontier molecular orbitals for selected macrocycles a) b) Figure S4. (a) HOMO and (b) LUMO of 6CF. S14

15 a) b) c) d) Figure S5. (a) SOMO (α spin), (b) LUMO (α spin), (c) HOMO (β spin) and (d) SOMO (β spin) of 6CF +. S15

16 a) b) c) d) Figure S6. (a) SOMO (α spin), (b) LUMO (α spin), (c) HOMO (β spin) and (d) SOMO (β spin) of 6CF 2+. S16

17 a) b) Figure S7. (a) HOMO and (b) LUMO of 8CF. S17

18 a) b) c) d) Figure S8. (a) SOMO (α spin), (b) LUMO (α spin), (c) HOMO (β spin) and (d) SOMO (β spin) of 8CF +. S18

19 a) b) c) d) Figure S9. (a) SOMO (α spin), (b) LUMO (α spin), (c) HOMO (β spin) and (d) SOMO (β spin) of 8CF 2+. S19

20 a) b) Figure S10. (a) HOMO and (b) LUMO of 12CF. S20

21 a) b) c) d) Figure S11. (a) SOMO (α spin), (b) LUMO (α spin), (c) HOMO (β spin) and (d) SOMO (β spin) of 12CF +. S21

22 a) b) Figure S12. (a) HOMO and (b) LUMO of 12CF. a) b) c) d) Figure S13. (a) SOMO (α spin), (b) LUMO (α spin), (c) HOMO (β spin) and (d) SOMO (β spin) of 12CT +. S22

23 S10. Orbital energy gaps for charged macrocycles 3.0 ncf + SOMO-LUMO gap (a spin) ncf + HOMO-SOMO gap (b spin) nct + SOMO-LUMO gap (a spin) nct + HOMO-SOMO gap (b spin) 2.5 Orbital eregy gap (ev) n Figure S14. Orbital energy gaps for ncf + and nct +. Orbital eregy gap (ev) 2.6 ncf 2+ SOMO-LUMO gap (a spin) ncf 2+ HOMO-SOMO gap (b spin) 2.4 nct 2+ SOMO-LUMO gap (a spin) nct 2+ HOMO-SOMO gap (b spin) n Figure S15. Orbital energy gaps for ncf 2+ and nct 2+. S23

24 C C bond length (Å) S11. Bond length alternations Bond length alternation (BLA) is an important criterion for aromaticity for conjugated systems. 3,4 We depict here the BLA of selected ncx discussed in this work. The interring bond length (numbered (4n + 4) where n = 0,1,2,3, Chart S2) is depicted separately from the intraring bonds ((4n +1) to (4n +3) where n = 0,1,2,3, Chart S2). Unless specified otherwise, all BLA figures display the syn-conformers. Chart S2. Bond distances displayed for ncx in the BLA Figures below. n = 0,1, CF 5CT Bond number Figure S16. BLA pattern of 5CF and 5CT. S24

25 C C bond length (Å) C C bond length (Å) Bond number 6CF 6CT Figure S17. BLA pattern of 6CF and 6CT Bond number 7CF 7CT Figure S18. BLA pattern of 7CF and 7CT. S25

26 C C bond length (Å) C C bond length (Å) Bond number 8CF 8CT Figure S19. BLA pattern of 8CF and 8CT Bond number 9CF 9CT Figure S20. BLA pattern of 9CF and 9CT. S26

27 C C bond length (Å) C C bond length (Å) CF (Syn) 10CT (Syn) 10CF (Anti) 10CT (Anti) Bond number Figure S21. BLA pattern of 10CF and 10CT (syn and anti conformations) CF 11CT Bond number Figure S22. BLA pattern of 11CF and 11CT. S27

28 C C bond length (Å) C C bond length (Å) CF (Syn) 12CT (Syn) 12CF (Anti) 12CT (Anti) Bond number Figure S23. BLA pattern of 12CF and 12CT (syn and anti conformations) Bond number 14CF (Syn) 14CT (Syn) 14CF (Anti) 14CT (Anti) Figure S24. BLA pattern of 14CF and 14CT (syn and anti conformations). S28

29 C C bond length (Å) Bond number 16CF (Syn) 16CT (Syn) 16CF (Anti) 16CT (Anti) Figure S25. BLA pattern of 16CF and 16CT (syn and anti conformations). S29

30 S12. Comparison with M062X/6-311G(d) and B3LYP/6-31++G** Levels Table S7. Absolute energies of neutral structures calculated at different levels of theory M062X/6-311G(d) B3LYP/6-31++G** B3LYP/6-311G(d) Name Energy (Hartree) Name Energy (Hartree) Name Energy (Hartree) 6CF CF CF CF CF CF CF CT CF CT CT CT CT CT CT CT CT CT S30

B3LYP/6-311G(d), and (c) B3LYP/6-31++G** levels. a) b) c) Figure S28.

31 a) b) c) Figure S26. Optimized structures of 6CF optimized at (a) M062X/6-311g(d), (b) B3LYP/6-311G(d), and (c) B3LYP/6-31++G** levels. a) b) c) Figure S27. Optimized structures of 6CT optimized at (a) M062X/6-311g(d), (b) B3LYP/6-311G(d), and (c) B3LYP/6-31++G** levels. a) b) c) Figure S28. Optimized structures of 8CF optimized at (a) M062X/6-311g(d), (b) B3LYP/6-311G(d), and (c) B3LYP/6-31++G** levels. S31

32 a) b) c) Figure S29. Optimized structures of 8CT optimized at (a) M062X/6-311g(d), (b) B3LYP/6-311G(d), and (c) B3LYP/6-31++G** levels. a) b) Figure S30. Optimized structures of 10CF optimized at (a) M062X/6-311G(d) and (b) B3LYP/6-311G(d) levels. S32

References (1) Casado, J.; Hernández, V.; López Navarrete, J. T.

33 a) b) Figure S31. Optimized structures of 10CT optimized at (a) M062X/6-311G(d) and (b) B3LYP/6-311G(d) levels. a) b) Figure S32. Optimized structures of 12CT optimized at (a) M062X/6-311G(d) and (b) B3LYP/6-311G(d) levels. References (1) Casado, J.; Hernández, V.; López Navarrete, J. T. The Chemical Record 2015, 15, (2) Hernandez, V.; Castiglioni, C.; Del Zoppo, M.; Zerbi, G. Phys. Rev. B 1994, 50, (3) Bredas, J. L. J. Chem. Phys. 1985, 82, (4) Geskin, V. M.; Dkhissi, A.; Brédas, J. L. Int. J. Quantum Chem. 2003, 91, S33

CHEM 344 Molecular Modeling

CHEM 344 Molecular Modeling The Use of Computational Chemistry to Support Experimental Organic Chemistry Part 1: Molecular Orbital Theory, Hybridization, & Formal Charge * all calculation data obtained