Dual facet of gold(iii) in the reactions of gold(iii) and porphyrins

Article abstract of DOI:10.1039/c2dt12280d

We have firstly demonstrated the dual facet of gold(iii) in the reaction between gold(iii) and porphyrins, which could be tuned through changing the counter ions, ligands and the electronic effect of the substituents of the porphyrins. The Royal Society o

Full text of DOI:10.1039/c2dt12280d

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Supporting Information
Dual facet of gold(III) in the reactions of gold(III) and
porphyrins
Hongbin Lv,a Boyan Yang,a Jing Jing,a Yi Yu,a Jing Zhang *b,Jun-Long Zhang*a
a Beijing National Laboratory for Molecular Sciences,
State Key Laboratory of Rare Earth Materials Chemistry and Applications,
College of Chemistry and Molecular Engineering,
Peking University, Beijing 100871, P.R. China,
Fax: +86-10-62767034,
E-mail: zhangjunlong@pku.edu.cn
b College of Materials Science and Opto-Electronic Technology,
Graduate University of Chinese Academy of Sciences,
Beijing 100049, P.R. China
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Table of Contents ：
1. Experimental Section ................................................................................................................4
1.1 General Experimental Information .....................................................................................4
1.2 Synthesis of Gold Porphyrins..............................................................................................4
1.2.1 Gold(III) 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin.....................................4
1.2. 2 Gold(III) 5,10,15,20-tetrakis(2,6-dichlorophenyl)porphyrin ..................................4
1.2.3 Gold(III) 5,10,15,20-tetrakis(phenyl)porphyrin (11b) .............................................5
1.2.4 Gold(III) 5,10,15,20-tetrakis(3,5-ditertbutylphenyl)porphyrin................................5
1.2.5 Gold(III) 5,10,15,20-tetrakis(2,6-dimethoxylphenyl)porphyrin ..............................5
1.3 Synthesis of porpholactones........................................................................................5
1.3.1 Synthesis and Characterization of [Au(Pic.)Cl2]......................................................5
1.3.2 Synthesis and Characterization of [Au(bpy)Cl2]Cl..................................................5
1.3.3 Synthesis and Characterization of [Au(Salen)Cl] ....................................................6
1.3.4 Synthesis and Characterization of [Au(Phen)Cl2]Cl................................................6
1.3.5 Synthesis and Characterization of [Au(DiPic)Cl]....................................................6
1.3.6 Synthesis of Silver Porphyrins.................................................................................6
1.3.7 Synthesis and Characterization of Prophyrins..................................................................6
1.3.8 5,10,15,20-Tetrakis(pentafluorophenyl)porphyrin...................................................6
1.3.9 5,10,15,20-Tetrakis(2,3,5,6-tetrafluorophenyl) porphyrin (4)..................................6
1.3.10 5,10,15,20-Tetrakis(2,3,4,5-tetrafluorophenyl) porphyrin (5)................................7
1.3.11 5,10,15,20-Tetrakis(2,4,6-trifluorophenyl) porphyrin (6) ......................................7
1.3.11 5,10,15,20-Tetrakis(2,6-difluorophenyl) porphyrin (7)..........................................7
1.3.12 5,10,15,20-Tetrakis(3,5-difluorophenyl) porphyrin (8)..........................................7
1.3.13 5,10,15,20-Tetrakis(4-fluorophenyl) porphyrin (9)................................................7
1.3.14 Gold(III) 5,10,15,20-tetrakis(2,3,5,6-tetrafluorophenyl)porphyrin (4b)................7
1.3.15 Gold(III) 5,10,15,20-tetrakis(2,3,4,5-tetrafluorophenyl)porphyrin (5b)................7
1.3.16 Gold(III) 5,10,15,20-tetrakis(2,4,6-trifluorophenyl)porphyrin (6b).......................7
1.3.17 Gold(III) 5,10,15,20-tetrakis(2,6-difluorophenyl)porphyrin (7b)..........................8
1.3.18 Gold(III) 5,10,15,20-tetrakis(3,5-difluorophenyl)porphyrin (8b)..........................8
1.3.19 Gold(III) 5,10,15,20-tetrakis(4-fluorophenyl)porphyrin (9b)................................8
1.3.20 Gold(III) 5,10,15,20-tetrakis(4-chlorophenyl)porphyrin (10b)..............................8
1.5 Spectra for β-Monochloroporphyrins..................................................................................9
1.5.1 β-Monochloro tetra(pentafluorophenyl)porphyrins (β-Cl-F20TPP) (2)....................9
2. Spectra data for porpholactones............................................................................................9
2.1 Tetra(pentafluorophenyl)porpholactone (3) ................................................................9
Figure S1. 1H NMR spectrum of 3 (CDCl3)....................................................................10
Figure S2. 19F NMR spectrum of 3 (CDCl3)...................................................................10
Figure S3. UV-vis (Black trace) and fluorescence (Red trace) spectra of 3 (CH2Cl2) ....11
Figure S4. FT-IR of 3......................................................................................................11
Figure S5. MS of 3..........................................................................................................12
2.2 Tetra(2,3,5,6-tetrafluorophenyl)porpholactone (4a)
Figure S6. 1H NMR spectrum of 4a (CDCl3)..................................................................13
Figure S8. UV-vis (Black trace) and fluorescence (Red trace) spectra of 4a (CH2Cl2) ..14
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Figure S9. FT-IR of 4a....................................................................................................14
Figure S10. MS of 4a......................................................................................................15
2.3 Tetra(2,3,4,5-tetrafluorophenyl)porpholactone (5a)..................................................16
Figure S11. 1H NMR spectrum of 5a (CDCl3)................................................................16
Figure S13. UV-vis (Black trace) and fluorescence (Red trace) spectra of 5a (CH2Cl2) 17
Figure S14. FT-IR of 5a..................................................................................................17
Figure S15. MS of 5a......................................................................................................18
2.4 Tetra(2,4,6-tetrafluorophenyl)porpholactone (6a).
Figure S16. 1H NMR spectrum of 6a (CDCl3)................................................................19
Figure S17. 19F NMR spectrum of 6a (CDCl3)...............................................................19
Figure S18. UV-vis (Black trace) and fluorescence (Red trace) spectra of 6a (CH2Cl2) 20
Figure S19. FT-IR of 6a..................................................................................................20
Figure S20. MS of 6a......................................................................................................21
2.5 Tetra(2,6-difluorophenyl)porpholactone (7a)............................................................22
Figure S21. 1H NMR spectrum of 7a (CDCl3)................................................................22
Figure S22. 19F NMR spectrum of 7a (CDCl3)...............................................................23
Figure S23. UV-vis (Black trace) and fluorescence (Red trace) spectra of 7a (CH2Cl2) 23
Figure S24. FT-IR of 7a..................................................................................................24
Figure S25. MS of 7a......................................................................................................24
2.6 Tetra(3,5-difluorophenyl)porpholactone (8a)............................................................25
Figure S26. 1H NMR spectrum of 8a (CDCl3)................................................................25
Figure S27. 19F NMR spectrum of 8a (CDCl3)...............................................................26
Figure S28. UV-vis (Black trace) and fluorescence (Red trace) spectra of 8a (CH2Cl2) 26
Figure S29. FT-IR of 8a..................................................................................................27
Figure S30. MS of 8a......................................................................................................27
2.7 Tetra(4-fluorophenyl)porpholatcone (9a)..................................................................28
Figure S31. 1H NMR spectrum of 9a (CDCl3)................................................................28
Figure S32. 19F NMR spectrum of 9a (CDCl3)...............................................................29
Figure S33. UV-vis (Black trace) and fluorescence (Red trace) spectra of 9a (CH2Cl2) 29
Figure S34. FT-IR of 9a..................................................................................................30
Figure S35. MS of 9a......................................................................................................30
2.8 Tetra(4-chlorophenyl)porpholatcone (10a) ...............................................................31
Figure S36. 1H NMR spectrum of 10a (CDCl3)..............................................................31
Figure S37. UV-vis (Black trace) and fluorescence (Red trace) spectra of 10a (CH2Cl2)
.........................................................................................................................................32
Figure S38. FT-IR of 10a................................................................................................32
Figure S39. MS of 10a....................................................................................................33
2.9 Tetraphenylporpholactone (11a)................................................................................34
Figure S40. 1H NMR spectrum of 11a (CDCl3)..............................................................34
Figure S41. UV-vis (Black trace) and fluorescence (Red trace) spectra of 11a (CH2Cl2)
.........................................................................................................................................35
Figure S42. FT-IR of 11a ................................................................................................35
Figure S43. MS of 11a ....................................................................................................36
3. References...............................................................................................................................36
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1. Experimental Section
1.1 General Experimental Information
Unless otherwise stated, all reactions were performed under an inert atmosphere of nitrogen in
either standard Schlenk techniques or flame-dried flasks. UV-vis spectra were recorded on an
Agilent 8453 UV-vis spectrometer equipped with an Agilent 89090A thermostat (±0.1 ℃). All
NMR spectra were recorded on a Varian Mercury Plus 300 MHz spectrophotometer (300M for 1H,
1
and 282M for 19F) or Bruker Avance 600 MHz spectrophotometer (600M for H, and 564M for
19F). All chemical shifts were reported in ppm and all coupling constants were in Hz. For 19F
NMR spectra，hexafluorobenzene in CDCl3 was used as the internal reference at 0 ppm. Mass
spectra were recorded on Bruker APEX IV FT-ICR Mass Spectrometer. GC/MS spectra we
collected on Agilent 5975C/7890A. IR spectra were recorded on Nicolet Magna IR 750. X-ray
Crystallography data was collected on a Rigaku Saturn 724 diffractometer at 173K.
1.2 Synthesis of Gold Porphyrins
General procedure: A mixture of HAuCl4·4H2O (30.9mg, 0.075mmol) and AgOTf (77.1mg,
0.3mmol) in 4mL THF wasadded to the solution of porphyrin (0.05mmol) and NaOAc (26.7mg,
0.325mmol) in CH2Cl2. The reaction mixture was stirred at room temperature for 1-2h. After the
solvent was evaporated in vacuum, the residue was chromatographyed on silica column (using
CH2Cl2 to remove free porphyrin and CH2Cl2/CH3OH=50:1 to collect the product). After solvent
evaporation, the solid was dissolved in 3mL acetone. 20mg LiCl dissolved in 5mL water was then
added to the acetone solution and reddish-brown precipitation was obtained after acetone was
removed. The resulted solid was filtrated and recrystallized from CH2Cl2/petroleum ether to afford
corresponding product.
1.2.1 Gold(III) 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin
1HNMR (CDCl3, 300 MHz): δ 9.51 (s, 8H) 19FNMR (CDCl3, 282 MHz): δ 25.33-25.25 (m, 8F),
14.704 (t, 4F, J = 23.1 Hz), 3.06-2.88 (m, 8F); ESI-MS (M+) m/z = 1169.0; HRMS-ESI (M+):
calc’d for C44H8AuF20N4 : 1169.0095, found: 1169.0017.
1.2. 2 Gold(III) 5,10,15,20-tetrakis(2,6-dichlorophenyl)porphyrin
1HNMR (CDCl3, 300 MHz): 9.23(s, 8H, Por-H), 7.95(s, 12H, Ar-H); HRMS-ESI (M-Cl+): calc’d
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for C44H20AuCl8N4: 1084.8803, found: 1084.8766.
1.2.3 Gold(III) 5,10,15,20-tetrakis(phenyl)porphyrin (11b)
1HNMR (CDCl3, 300 MHz): δ 9.25 (s, 8H) 8.30(dd, 8H, ortho-Ar-H, J=7.5Hz, 1.5Hz), 7.83-7.86(m,
12H, Ar-H); HRMS-ESI (M-Cl+): calc’d for C44H28AuN4: 809.1974, found: 809.1968.
1.2.4 Gold(III) 5,10,15,20-tetrakis(3,5-ditertbutylphenyl)porphyrin
1HNMR (CDCl3, 300 MHz): δ 9.33 (s, 8H, Por-H), 8.09(d, 8H, ortho-Ar-H, J=1.5Hz), 7.91(t, 4H,
para-Ar-H, J=1.5Hz), 1.53 (s, 72H, -C(CH3)3); HRMS-ESI (M-Cl+): calc’d for C76H92AuN4:
1257.6982, found: 1257.6952.
1.2.5 Gold(III) 5,10,15,20-tetrakis(2,6-dimethoxylphenyl)porphyrin
1HNMR (CDCl3, 300 MHz): 9.15 (s, 8H, Por-H), 7.85 (t, 4H, para-Ar-H, J=8.5Hz), 7.08 (d, 8H,
meta-Ar-H, J=8.5Hz), 3.58 (s, 24H, -OCH3); HRMS-ESI (M-Cl+): calc’d for C52H44AuN4O8:
1049.2819, found: 1049.2826.
1.3 Synthesis of porpholactones
General Procedure: Porphyrins (for 3-8) or silver porphyrins (for 9a-11) (0.025 mmol), gold
complex (0.05 mmol), AgOTf (0.1 mmol, 26.0 mg) and NaOAc (0.125 mmol, 10.5 mg) were added
to a Schlenk tube, 2 mL acetic acid was added via syringe in succession. The resulting reaction
mixture was refluxed for 12 h at 120ºC. The solvent was then removed under vacuum and the
residue was then purified by flash column chromatography to give the products.
1.3.1 Synthesis and Characterization of [Au(Pic.)Cl2]
[Au(Pic.)Cl2] was synthesized according to the literature.1 1H NMR (d6-acetone, 300 MHz):
δ 9.31(d, 1H, J = 6.0 Hz), 8.69 (t, 1H, J = 7.6 Hz), 8.26 (m, 1H), 8.20 (d, 1H, J = 7.6 Hz).
1.3.2 Synthesis and Characterization of [Au(bpy)Cl2]Cl
[Au(bpy)Cl2]Cl was synthesized according to the literature.2 1H NMR (d3-acetonitrile, 300 MHz):
8.45 (d, 2H, J = 6.9 Hz), 8.01-7.93 (m, 4H), 7.44 (dt, 2H, J1 = 2.4 Hz, J2 = 6.3 Hz).
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1.3.3 Synthesis and Characterization of [Au(Salen)Cl]
[Au(Salen)Cl] was synthesized according to the literature.3
1.3.4 Synthesis and Characterization of [Au(Phen)Cl2]Cl
[Au(Phen)Cl2]Cl was synthesized according to the literature.2
1.3.5 Synthesis and Characterization of [Au(DiPic)Cl]
Au(DiPic)Cl was synthesized according to the literature.1
1.3.6 Synthesis of Silver Porphyrins
General procedure: Porphyrins (0.1 mmol), AgOTf (0.2 mmol) and NaOAc (0.5 mmol) were
dissolved in CH2Cl2/THF = 1:1(v/v), the mixture was refluxed for 12h, then the solvent was
removed and the residue was purified by flash column chromatography to give the products
(yields >80%).
1.3.7 Synthesis and Characterization of Prophyrins
Fn
Fn
Fn
BF3 (cat.)
CH2Cl2
NH
N
N
DDQ
+
N2, reflux, 4h CH2Cl2
N
HN
H
Fn
CHO
Fn
All porphyrins were synthesized according to the literature.5
1.3.8 5,10,15,20-Tetrakis(pentafluorophenyl)porphyrin
1H NMR (CDCl3, 300 MHz): δ 8.92 (s, 8H), -2.92 (s, 2H); 19F NMR (CDCl3, 282 MHz): δ 25.45 (m,
8F), 10.62 (m, 4F), 0.505 (m, 8F); ESI-MS: m/z = 975.1 (MH+).
1.3.9 5,10,15,20-Tetrakis(2,3,5,6-tetrafluorophenyl) porphyrin (4)
1H NMR (CDCl3, 300 MHz): δ 8.93 (s, 8H), 7.65 (m, 4H), -2.78 (s, 2H); 19F NMR (CDCl3, 282
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MHz): δ 25.11 (s, 8F), 24.39 (s, 8F); ESI-MS: m/z = 903.1 (MH+).
1.3.10 5,10,15,20-Tetrakis(2,3,4,5-tetrafluorophenyl) porphyrin (5)
1H NMR (CDCl3, 300 MHz): δ 8.86 (s, 8H), 7.79 (m, 4H), -2.99 (s, 2H); 19F NMR (CDCl3, 282
MHz): δ 25.47 (m, 4F), 21.85 (m, 4F), 8.13 (m, 4F), 6.70 (m, 4F); ESI-MS: m/z = 903.1 (MH+).
1.3.11 5,10,15,20-Tetrakis(2,4,6-trifluorophenyl) porphyrin (6)
1H NMR (CDCl3, 600 MHz): δ 8.89 (s, 8H), 7.17 (t, 8H, J = 6.6 Hz), -2.84 (s, 2H);19F NMR (CDCl3,
282 MHz): δ 59.61, (t, 8F, J = 6.8 Hz), 55.77 (m, 4F); ESI-MS : m/z = 831.1 (MH+).
1.3.11 5,10,15,20-Tetrakis(2,6-difluorophenyl) porphyrin (7)
1H NMR (CDCl3, 300 MHz): δ 8.88 (s, 8H), 7.81 (m, 4H), 7.39 (q, 8H, J1 = 6.6 Hz, J2 = 1.8 Hz),
-2.78 (s, 2H); 19F NMR (CDCl3, 282 MHz): δ 53.49 (s, 8F); ESI-MS: m/z = 759.2 (MH+).
1.3.12 5,10,15,20-Tetrakis(3,5-difluorophenyl) porphyrin (8)
1H NMR (CDCl3, 300 MHz): δ 8.90 (s, 8H), 7.75 (s, 8H), 7.33 (s, 4H), -2.98 (s, 2H); 19F NMR
(CDCl3, 282 MHz): δ 50.5 (s, 8F); ESI-MS: m/z = 759.2 (MH+).
1.3.13 5,10,15,20-Tetrakis(4-fluorophenyl) porphyrin (9)
1H NMR (CDCl3, 600 MHz): δ 8.83 (s, 8H), 8.16 (dd, 8H, J1= 5.4 Hz, J2 = 2.4 Hz), 7.46 (m, 12H),
-2.83 (s, 2H); 19F NMR (CDCl3, 564 MHz): δ 47.27 (s, 4F); ESI-MS: m/z = 687.2 (MH+).
1.3.14 Gold(III) 5,10,15,20-tetrakis(2,3,5,6-tetrafluorophenyl)porphyrin (4b)
1H NMR (CDCl3, 300 MHz): δ 9.49 (s, 8H,), 7.70-7.60 (m, 4H), 19F NMR (CDCl3, 282 MHz): δ
24.52-24.27 (m, 8F), 23.32-23.05(m, 8F). ESI-MS: m/z = 1097.1 (M+).
1.3.15 Gold(III) 5,10,15,20-tetrakis(2,3,4,5-tetrafluorophenyl)porphyrin (5b)
1H NMR (CDCl3, 300 MHz): δ 9.51 (s, 8H), 7.90-7.70 (m, 4H), 19F NMR (CDCl3, 282 MHz): δ
25.23-25.20 (m, 4F), 21.54-21.40-23.05(m, 4F), 7.70 (m, 4F), 6.30-5.80 (m, 4F). ESI-MS: m/z =
1097.1 (M+).
1.3.16 Gold(III) 5,10,15,20-tetrakis(2,4,6-trifluorophenyl)porphyrin (6b)
1H NMR (CDCl3, 300 MHz): δ 9.48 (s, 8H), 7.18 (t, 4H, J = 4.8 Hz), 19F NMR (CDCl3, 282 MHz):
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δ 56.67 (t, 4F, J = 3.6 Hz), 55.24(s, 8F). ESI-MS: m/z = 1025.1 (M+).
1.3.17 Gold(III) 5,10,15,20-tetrakis(2,6-difluorophenyl)porphyrin (7b)
1H NMR (CDCl3, 300 MHz): δ 9.50 (s, 8H), 7.55-7.52 (m, 4H), 7.23 (m, 8H) 19F NMR (CDCl3, 282
MHz): δ 83.33 (m, 8F). ESI-MS: m/z = 953.1 (M+).
1.3.18 Gold(III) 5,10,15,20-tetrakis(3,5-difluorophenyl)porphyrin (8b)
1H NMR (CDCl3, 300 MHz): δ 9.46 (s, 8H), 7.80-7.0 (d, 4H, J = 5.7 Hz), 7.34-7.29 (m, 8H), 19F
NMR (CDCl3, 282 MHz): δ 50.03 (s, 8F). ESI-MS: m/z = 953.1 (M+).
1.3.19 Gold(III) 5,10,15,20-tetrakis(4-fluorophenyl)porphyrin (9b)
1H NMR (CDCl3, 300 MHz): δ 9.25 (s, 8H), 8.24-8.20 (m, 8H), 7.74-7.69 (m, 8H). 19F NMR
(CDCl3, 282 MHz): δ 50.08 (m, 4F). ESI-MS: m/z = 881.0 (M+).
1.3.20 Gold(III) 5,10,15,20-tetrakis(4-chlorophenyl)porphyrin (10b)
1HNMR (CDCl3, 300 MHz): δ=9.23 (s, 8H, Por-H), 8.20 (d, 8H, Ar-H, J=8.1Hz), 7.84 (d, 8H, Ar-H,
J=8.1Hz); (d6-acetone, 300MHz): δ=9.46 (s, 8H, Por-H), 8.35 (d, 8H, Ar-H, J=8.1Hz), 7.97 (d, 8H,
Ar-H, J=8.1Hz); HRMS-ESI (M-Cl+): calc’d for C44H24AuCl4N4: 947.0391, found: 947.0372.
1.4 Mechanistic Studies
Porphyrin H2F20TPP (0.025 mmol), gold complex (0.05 mmol), AgOTf (0.1 mmol, 26.0 mg) and
NaOAc (0.125 mmol, 10.5 mg) were added to a Schlenk tube, 2 mL acetic acid was added via
syringe in succession. The resulting reaction mixture was refluxed for 12 h at 120ºC. The solvent
was then removed under vacuum and the residue was then purified by flash column chromatography
to give the products.
1.4.1 Spectra Data for β-Acetylated H2F20TPP
1H NMR (CDCl3, 300 MHz): δ 8.98-8.84 (m, 7H), 2.25 (s, 3H), -3.02 (s, 1H). 19FNMR: δ
25.79-25.69 (m, 4F), 24.36-24.01 (m, 4F), 13.43-13.23 (m, 2F), 12.56-12.77 (m, 2F), 2.80-2.60 (m,
4F), 2.05-1.88 (m, 4F). IR (cm-1): 1774.3 (C=O); ESI-MS (MH+) m/z = 1011.0; HRESI-MS
(MH+): calc’d for C42H7F20N4O4: 1011.0143, found: 1011.0148.
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1.5 Spectra for β-Monochloroporphyrins
1.5.1 β-Monochloro tetra(pentafluorophenyl)porphyrins (β-Cl-F20TPP) (2)
1H NMR (CDCl3, 300 MHz): δ 9.00 (d, 4H, J = 5.1 Hz), 8.83 (s, 2H), 8.78 (s, 1H), -3.014 (s, 2H);
19F NMR (CDCl3, 282 MHz): δ 25.39-25.15(m, 6F), 25.61 (dd, 2F, J1 = 7.8 Hz, J2 = 24.3 Hz),
11.09-10.77 (m, 3F), 10.18 (t, 1F, J = 22.8 Hz), 0.85-0.50 (m, 6F), -0.24 - -0.42 (m, 2F);
HRMS-ESI (MH+): calc’d for C44H10ClF20N4: 1009.0269, found:1009.0269.
2. Spectra data for porpholactones
2.1 Tetra(pentafluorophenyl)porpholactone (3)
1H NMR (CDCl3, 300 MHz): δ 8.92 (d, 1H, J = 5.4 Hz), 8.89 (d, 1H, J = 4.8 Hz), 8.86 (d, 1H, J = 3.6
Hz), 8.82 (d, 1H, J = 4.2 Hz), 8.65 (dd, 2H, J1 = 4.8 Hz, J2 = 42.0 Hz), -1.80 (s, 1H), -2.10 (s, 1H);
19F NMR (CDCl3, 282 MHz): δ 25.12-24.93 (m, 4F), 24.73 (dd, 2F, J1 = 7.2 Hz , J2 = 16.8 Hz ),
11.33 (quad, 3F, J = 22.5 Hz)，10.60 (t, 1F, J = 22.2 Hz), 1.14-0.87 (m, 6F), 0.46-0.29 (m, 2F);
ESI-MS (MH+) m/z =993.0; HRESI-MS (MH+): calc’d for C43H9F20N4O2: 993.0405, found
993.0402; IR (cm-1): 1774 (C=O), 1793 (C=O); UV-vis (CH2Cl2), λmax (logε) : 409 (5.18), 510
(3.95), 545 (3.81), 589 (3.60), 642 (4.03).
F
F
F
F
F
O
O
F
F
F
F
F
F
F
F
NH
N
N
F
F
HN
F
F
F
F
F
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Figure S1. 1H NMR spectrum of 3 (CDCl3)
F
F
F
F
F
O
O
F
F
F
F
F
F
F
F
NH
N
N
F
F
HN
F
F
F
F
F
Figure S2. 19F NMR spectrum of 3 (CDCl3)
F
F
F
F
F
O
O
F
F
F
F
F
F
F
F
NH
N
N
F
F
HN
F
F
F
F
F
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Figure S3. UV-vis (Black trace) and fluorescence (Red trace) spectra of 3 (CH2Cl2)
F
F
F
F
F
O
O
F
F
F
F
F
F
F
F
NH
N
N
F
F
HN
F
F
F
F
F
C=O: 1774cm-1, 1793cm-1
Figure S4. FT-IR of 3
Experimental Result
Simulating Result
MH+ 993.0
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Figure S5. MS of 3
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2.2 Tetra(2,3,5,6-tetrafluorophenyl)porpholactone (4a)
1H NMR (CDCl3, 300 MHz): δ 8.90 (s, 1H, J = 4.8 Hz), 8.86 (s, 1H, J = 4.2 Hz), 8.83 (s, 1H, J = 4.2
Hz), 8.79 (s, 1H, J = 3.0 Hz), 8.66 (dd, 2H, J1 = 4.8 Hz, J2 = 42.0 Hz), 7.65-7.53 (m, 4H), -1.76 (s,
1H), -2.06 (s, 1H); 19F NMR (CDCl3, 564 MHz): δ 24.46 (broad), 24.11 (broad), 23.83 (broad),
23.21 (broad), 22.76 (broad); ESI-MS (MH+) m/z = 921.1; HRESI-MS (MH+): calc’d for
C43H13F16N4O2: 921.0872, found: 921.0767; IR (cm-1): 1768 (C=O), 1795 (C=O); UV-vis (CH2Cl2),
λ
max (logε) : 413 (5.25), 510 (3.96), 544 (3.33), 588 (3.52), 642 (3.68).
Figure S6. 1H NMR spectrum of 4a (CDCl3)
Figure S7. 19F NMR spectrum of 4a (CDCl3)
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Figure S8. UV-vis (Black trace) and fluorescence (Red trace) spectra of 4a (CH2Cl2)
C=O: 1768cm-1, 1795cm-1
Figure S9. FT-IR of 4a
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921.0767
921.0782
922.0807
923.0847
922.0814
923.0845
MH+ 922.1
Experimental Result
Simulating Result
Figure S10. MS of 4a
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2.3 Tetra(2,3,4,5-tetrafluorophenyl)porpholactone (5a).
1H NMR (CDCl3, 300 MHz): δ 8.87 (s, 1H, J = 4.8 Hz,), 8.84 (s, 1H, J = 4.2 Hz), 8.80 (s, 1H, J = 4.2
Hz), 8.74 (s, 1H, J = 4.2 Hz), 8.62 (dd, 2H, J1 = 4.8 Hz, J2 = 39.0 Hz), 7.65-7.48 (broad, 4H, ), -1.86
(s, 1H), -2.18 (s,1H); 19F NMR (CDCl3, 282 MHz): δ 25.25 (broad), 22.33 (broad), 8.92(m), 8.32 (t),
7.40 (m), 6.73 (m); ESI-MS (MH+) m/z = 921.1; HRESI-MS (MH+): calc’d for C43H13F16N4O2:
921.0782, found: 921.0770; IR (cm-1): 1790 (C=O); UV-vis (CH2Cl2), λmax (logε) : 413 (5.24), 510
(3.98), 547 (3.47), 586 (3.54), 642 (3.42).
Figure S11. 1H NMR spectrum of 5a (CDCl3)
Figure S12. 19F NMR spectrum of 5a (CDCl3)
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Figure S13. UV-vis (Black trace) and fluorescence (Red trace) spectra of 5a (CH2Cl2)
F
F
F
F
O
O
F
F
F
F
F
NH
N
N
F
F
HN
F
F
F
F
F
C=O: 1790cm-1
Figure S14. FT-IR of 5a
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921.0770
921.0782
922.0804
923.0859
922.0814
923.0845
MH+ 921.1
Experimental Result
Simulating Result
Figure S15. MS of 5a
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2.4 Tetra(2,4,6-trifluorophenyl)porpholactone (6a)
1H NMR (CDCl3, 300 MHz): δ 8.90 (s, 1H, J = 4.8 Hz), 8.87 (s, 1H, J = 4.2 Hz), 8.83 (s, 1H, J = 4.2
Hz), 8.79 (s, 1H, J = 4.2 Hz), 8.64 (dd, 2H, J1 = 4.8 Hz, J2 = 42.0 Hz ), 7.79 (m, 8H), -1.84 (s, 1H),
-2.10 (s, 1H); 19F NMR (CDCl3, 282 MHz): δ 48.24-47.80 (m, 8F), 47.51 (m, 1H), 47.20 (t, 2H, J =
7.05Hz), 45.75 (t, 2H, J = 7.05Hz); ESI-MS(MH+) m/z = 849.1; HRESI-MS (MH+): calc’d for
C43H17F12N4O2: 849.1159, found:849.1163; IR (cm-1): 1790 (C=O); UV-vis (CH2Cl2), λmax (logε) :
412 (5.02), 511 (3.73), 547 (3.44), 587(3.36), 642 (3.50).
Figure S16. 1H NMR spectrum of 6a (CDCl3)
Figure S17. 19F NMR spectrum of 6a (CDCl3)
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Figure S18. UV-vis (Black trace) and fluorescence (Red trace) spectra of 6a (CH2Cl2)
F
F
F
F
O
O
F
F
F
F
NH
N
N
F
F
HN
F
F
C=O: 1790cm-1
Figure S19. FT-IR of 6a
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849.1159
849.1163
850.1191
850.1196
851.1243
851.1222
Experimental Result
Simulating Result
MH+ 849.1
Figure S20. MS of 6a
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2.5 Tetra(2,6-difluorophenyl)porpholactone (7a)
1H NMR (CDCl3, 300 MHz): δ 8.85-8.70 (m, 4H), 8.66 (d, 1H, J = 4.8Hz), 8.64 (d, 1H, J = 4.8Hz),
8.56 (d, 1H, J = 4.5Hz), 7.73-7.77 (m, 4H), 7.40-7.33 (m, 8H), -1.69 (s, 1H), -2.02 (s, 1H); 19F NMR
(CDCl3, 282 MHz): δ 40.47-39.82 (m, 6F), 39.24 (m, 1F), 37.94 (m, 1F); ESI-MS (MH+) m/z =
777.2; HRESI-MS (MH+): calc’d for C43H21F8N4O2: 777.1536, found: 777.1544; IR (cm-1): 1780
(C=O); UV-vis (CH2Cl2), λmax (logε) : 412 (4.97), 512 (3.72), 548 (3.58), 588(3.48), 641 (3.56).
Figure S21. 1H NMR spectrum of 7a (CDCl3)
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Figure S22. 19F NMR spectrum of 7a (CDCl3)
Figure S23. UV-vis (Black trace) and fluorescence (Red trace) spectra of 7a (CH2Cl2)
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C=O: 1780cm-1
Figure S24. FT-IR of 7a
777.1536
777.1543
778.1584
779.1604
778.1584
779.1599
Experimental Result
Simulating Result
MH+ 777.2
Figure S25. MS of 7a
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2.6 Tetra(3,5-difluorophenyl)porpholactone (8a)
1H NMR (CDCl3, 300 MHz): δ 8.87 (dd, 2H, J1 = 4.8 Hz, J2 = 11.4 Hz), 8.77 (d, 1H, J = 4.8 Hz),
8.66 (d, 1H, J = 4.8Hz), 8.63 (d, 1H, J = 4.8Hz), 8.56 (d, 1H, J = 4.8Hz), 7.76-7.62(m, 8H),
7.54-7.48 (m, 4H), -1.85 (s, 1H), -2.20 (s, 1H); 19F NMR (CDCl3, 564 MHz): δ 51.69 (s, 2F), 51.32
(s, 2F), 51.18 (s, 2F), 50.61 (s, 2F); ESI-MS (MH+) m/z = 777.2; HRESI-MS (MH+): calc’d for
C43H21F8N4O2: 777.1536, found: 777.1529; IR (cm-1): 1780 (C=O); UV-vis (CH2Cl2), λmax (logε) :
415 (4.84), 514 (3.48), 552 (3.20), 567 (3.09), 641 (2.95).
Figure S26. 1H NMR spectrum of 8a (CDCl3)
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Figure S27. 19F NMR spectrum of 8a (CDCl3)
Figure S28. UV-vis (Black trace) and fluorescence (Red trace) spectra of 8a (CH2Cl2)
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C=O: 1780cm-1
Figure S29. FT-IR of 8a
777.1536
777.1529
778.1566
778.1568
779.1594
779.1599
Experimental Result
Simulating Result
MH+ 777.2
Figure S30. MS of 8a
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2.7 Tetra(4-fluorophenyl)porpholatcone (9a)
1H NMR (CDCl3, 300 MHz): δ 8.85-8.80 (m, 4H), 8.68 (dd, 2H, J1 = 2.4 Hz, J2 = 5.1 Hz),
8.57-8.50 (m, 4H), 8.01-7.98 (m, 8H), 7.85-7.80 (m, 4H), -1.76 (s, 1H), -2.07 (s, 1H); 19F NMR
(CDCl3, 564 MHz): δ 11.31 (q, 3F, J = 40.0Hz), 10.60 (t, 1F, J = 40.7Hz); ESI-MS (MH+) m/z
705.2; HRESI-MS (MH+): calc’d for C43H25F4N4O2: 705.1913, found: 705.1908; IR (cm-1): 1790
(C=O); UV-vis (CH2Cl2), λmax (logε) : 418 (4.41), 516 (2.80), 548 (2.79), 588 (2.37), 644 (1.89).
Figure S31. 1H NMR spectrum of 9a (CDCl3)
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Figure S32. 19F NMR spectrum of 9a (CDCl3)
Figure S33. UV-vis (Black trace) and fluorescence (Red trace) spectra of 9a (CH2Cl2)
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C=O: 1790cm-1
Figure S34. FT-IR of 9a
705.1911
705.1913
706.1949
707.2011
706.1945
707.1976
MH+ 705.2
Experimental Result
Simulating Result
Figure S35. MS of 9a
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