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1 Supporting Information Tuning of Excited-State Intramolecular Proton Transfer (ESIPT) Fluorescence of Imidazo[1,2-a]pyridine in Rigid Matrices by Substitution Effect Toshiki Mutai,* irotaka Sawatani, Toshihide Shida, ideaki Shono, and Koji Araki* Department of Materials and Environmental Science, Institute of Industrial Science, the University of Tokyo, 4-6-1, Komaba, Meguro-ku, Tokyo , Japan. Contents: Table S1. Calculated energy level of M IPT and LUM IPT, and the lowest transition energy (ΔE) obtained using the CIS-method in the intramolecular hydrogen-transferred (IPT) state of Page S1 Gaussian job files for geometry optimization and energy calculation of the ESIPT state of Figure S1 S26. 1 MR (400 Mz) and 13 C MR (100 Mz) spectra of 2 14 in CDCl S2 S15... S16 S41

2 Table S1. Calculated energy level of M IPT and LUM IPT, and the lowest transition energy (ΔE) obtained using the CIS-method in the intramolecular hydrogen-transferred (IPT) state of M IPT /ev LUM IPT /ev ΔE /ev S1

3 Gaussian job file of PIP (1) %chk=1_ipt_ex_pt.chk # opt cis/6-31g(d) nosymm fchk Density=All FChk=All Pop=Regular 1_ESIPT_ptimization C C C C C C C C C C C C C Link1-- %chk=1_ipt_ex_pt.chk # cis=direct/6-31+g(d) nosymm geom=check Density=CI FChk=All Pop=Regular 1_ESIPT_ptimized_SinglePoint S2

4 Gaussian job file of 5 -methoxy PIP (2) %chk=2_ipt_ex_pt.chk # opt cis/6-31g(d) nosymm fchk Density=All FChk=All Pop=Regular 2_ESIPT_ptimization C C C C C C C C C C C C C C Link1-- %chk=2_ipt_ex_pt.chk # cis=direct/6-31+g(d) nosymm geom=check Density=CI FChk=All Pop=Regular 2_ESIPT_ptimized_SinglePoint S3

5 Gaussian job file of 5 -methyl PIP (3) %chk=3_ipt_ex_pt.chk # opt cis/6-31g(d) nosymm fchk Density=All FChk=All Pop=Regular 3_ESIPT_ptimization C C C C C C C C C C C C C C Link1-- %chk=3_ipt_ex_pt.chk # cis=direct/6-31+g(d) nosymm geom=check Density=CI FChk=All Pop=Regular 3_ESIPT_ptimized_SinglePoint S4

6 Gaussian job file of 5 -chloro PIP (4) %chk=4_ipt_ex_pt.chk # opt cis/6-31g(d) nosymm fchk Density=All FChk=All Pop=Regular 4_ESIPT_ptimization C C C C C C C C C C C C C Cl Link1-- %chk=4_ipt_ex_pt.chk # cis=direct/6-31+g(d) nosymm geom=check Density=CI FChk=All Pop=Regular 4_ESIPT_ptimized_SinglePoint S5

7 Gaussian job file of 5 -bromo PIP (5) %chk=5_ipt_ex_pt.chk # opt cis/6-31g(d) nosymm fchk Density=All FChk=All Pop=Regular 5_ESIPT_ptimization C C C C C C C C C C C C C Br Link1-- %chk=5_ipt_ex_pt.chk # cis=direct/6-31+g(d) nosymm geom=check Density=CI FChk=All Pop=Regular 5_ESIPT_ptimized_SinglePoint S6

8 Gaussian job file of 5 -fluoro PIP (6) %chk=6_ipt_ex_pt.chk # opt cis/6-31g(d) nosymm fchk Density=All FChk=All Pop=Regular 6_ESIPT_ptimization C C C C C C C C C C C C C F Link1-- %chk=6_ipt_ex_pt.chk # cis=direct/6-31+g(d) nosymm geom=check Density=CI FChk=All Pop=Regular 6_ESIPT_ptimized_SinglePoint S7

9 Gaussian job file of 6-methyl PIP (7) %chk=7_ipt_ex_pt.chk # opt cis/6-31g(d) nosymm fchk Density=All FChk=All Pop=Regular 7_ESIPT_ptimization C C C C C C C C C C C C C C Link1-- %chk=7_ipt_ex_pt.chk # cis=direct/6-31+g(d) nosymm geom=check Density=CI FChk=All Pop=Regular 7_ESIPT_ptimized_SinglePoint S8

10 Gaussian job file of 6-chloro PIP (8) %chk=8_ipt_ex_pt.chk # opt cis/6-31g(d) nosymm fchk Density=All FChk=All Pop=Regular 8_ESIPT_ptimization C C C C C C C C C C C C C Cl Link1-- %chk=8_ipt_ex_pt.chk # cis=direct/6-31+g(d) nosymm geom=check Density=CI FChk=All Pop=Regular 8_ESIPT_ptimized_SinglePoint S9

11 Gaussian job file of 6-bromo PIP (9) %chk=9_ipt_ex_pt.chk # opt cis/6-31g(d) nosymm fchk Density=All FChk=All Pop=Regular 9_ESIPT_ptimization C C C C C C C C C C C C C Br Link1-- %chk=9_ipt_ex_pt.chk # cis=direct/6-31+g(d) nosymm geom=check Density=CI FChk=All Pop=Regular 9_ESIPT_ptimized_SinglePoint S10

12 Gaussian job file of 6-trifluoromethyl PIP (10) %chk=10_ipt_ex_pt.chk # opt cis/6-31g(d) nosymm fchk Density=All FChk=All Pop=Regular 10_ESIPT_ptimization C C C C C C C C C C C C C C F F F Link1-- %chk=10_ipt_ex_pt.chk # cis=direct/6-31+g(d) nosymm geom=check Density=CI FChk=All Pop=Regular 10_ESIPT_ptimized_SinglePoint S11

13 Gaussian job file of 6-cyano PIP (11) %chk=11_ipt_ex_pt.chk # opt cis/6-31g(d) nosymm fchk Density=All FChk=All Pop=Regular 11_ESIPT_ptimization C C C C C C C C C C C C C C Link1-- %chk=11_ipt_ex_pt.chk # cis=direct/6-31+g(d) nosymm geom=check Density=CI FChk=All Pop=Regular 11_ESIPT_ptimized_SinglePoint S12

14 Gaussian job file of 4 -methoxy PIP (12) %chk=12_ipt_ex_pt.chk # opt cis/6-31g(d) nosymm fchk Density=All FChk=All Pop=Regular 12_ESIPT_ptimization C C C C C C C C C C C C C C Link1-- %chk=12_ipt_ex_pt.chk # cis=direct/6-31+g(d) nosymm geom=check Density=CI FChk=All Pop=Regular 12_ESIPT_ptimized_SinglePoint S13

15 Gaussian job file of 6-chloro-5 -methyl PIP (13) %chk=13_ipt_ex_pt.chk # opt cis/6-31g(d) nosymm fchk Density=All FChk=All Pop=Regular 13_ESIPT_ptimization C C C C C C C C C C C C C Cl C Link1-- %chk=13_ipt_ex_pt.chk # cis=direct/6-31+g(d) nosymm geom=check Density=CI FChk=All Pop=Regular 13_ESIPT_ptimized_SinglePoint S14

16 Gaussian job file of 5 -methyl-6-trifluoromethyl PIP (14) %chk=14_ipt_ex_pt.chk # opt cis/6-31g(d) nosymm fchk Density=All FChk=All Pop=Regular 14_ESIPT_ptimization C C C C C C C C C C C C C F C F C F Link1-- %chk=14_ipt_ex_pt.chk # cis=direct/6-31+g(d) nosymm geom=check Density=CI FChk=All Pop=Regular 14_ESIPT_ptimized_SinglePoint S15

17 2 C 3 5 -Methoxy PIP (2) Figure S1. 1 MR spectrum (CDCl 3, 400 Mz) of 2.

18 C 3 5 -Methoxy PIP (2) Figure S2. 13 C MR spectrum (CDCl 3, 100 Mz) of 2.

19 C 3 5 -Methyl PIP (3) Figure S3. 1 MR spectrum (CDCl 3, 400 Mz) of 3.

20 C 3 5 -Methyl PIP (3) Figure S4. 13 C MR spectrum (CDCl 3, 100 Mz) of 3.

21 2 Cl 5 -Chloro PIP (4) Figure S5. 1 MR spectrum (CDCl 3, 400 Mz) of 4.

22 Cl 5 -Chloro PIP (4) Figure S6. 13 C MR spectrum (CDCl 3, 100 Mz) of 4.

23 Br 5 -Bromo PIP (5) Figure S7. 1 MR spectrum (CDCl 3, 400 Mz) of 5.

24 Br 5 -Bromo PIP (5) Figure S8. 13 C MR spectrum (CDCl 3, 100 Mz) of 5.

25 2 F 5 -Fluoro PIP (6) Figure S9. 1 MR spectrum (CDCl 3, 400 Mz) of 6.

26 F 5 -Fluoro PIP (6) Figure S C MR spectrum (CDCl 3, 100 Mz) of 6.

27 2 C 3 6-Methyl PIP (7) Figure S11. 1 MR spectrum (CDCl 3, 400 Mz) of 7.

28 C 3 6-Methyl PIP (7) Figure S C MR spectrum (CDCl 3, 100 Mz) of 7.

29 2 Cl 6-Chloro PIP (8) Figure S13. 1 MR spectrum (CDCl 3, 400 Mz) of 8.

30 Cl 6-Chloro PIP (8) Figure S C MR spectrum (CDCl 3, 100 Mz) of 8.

31 2 Br 6-Bromo PIP (9) Figure S15. 1 MR spectrum (CDCl 3, 400 Mz) of 9.

32 Br 6-Bromo PIP (9) Figure S C MR spectrum (CDCl 3, 100 Mz) of 9.

33 2 CF 3 6-Trifluoromethyl PIP (10) Figure S17. 1 MR spectrum (CDCl 3, 400 Mz) of 10.

34 CF 3 6-Trifluoromethyl PIP (10) Figure S C MR spectrum (CDCl 3, 100 Mz) of 10.

35 2 C 6-Cyano PIP (11) Figure S19. 1 MR spectrum (CDCl 3, 400 Mz) of 11.

36 C 6-Cyano PIP (11) Figure S C MR spectrum (CDCl 3, 100 Mz) of 11.

37 2 C 3 4 -Methoxy PIP (12) Figure S21. 1 MR spectrum (CDCl 3, 400 Mz) of 12.

38 C 3 4 -Methoxy PIP (12) Figure S C MR spectrum (CDCl 3, 100 Mz) of 12.

39 2 Cl C 3 5 -Methyl-6-chloro PIP (13) Figure S23. 1 MR spectrum (CDCl 3, 400 Mz) of 13.

40 Cl C 3 5 -Methyl-6-chloro PIP (13) Figure S C MR spectrum (CDCl 3, 100 Mz) of 13.

41 2 CF 3 C 3 5 -Methyl-6-trifluoromethyl PIP (14) Figure S25. 1 MR spectrum (CDCl 3, 400 Mz) of 14.

42 CF 3 C 3 5 -Methyl-6-trifluoromethyl PIP (14) Figure S C MR spectrum (CDCl 3, 100 Mz) of 14.

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