Synthesis of New Porphyrin Trimers via Buchwald-Hartwig Amination Reaction

Vladimir S. Tyurin, Elena A. Mikhalitsyna, Alexandr S. Semeikin, and Irina P. Beletskaya

Supporting Information

Figure 1. Synthesis of aminophenylporphyrins ZnPMes3PhNH2 и ZnPMes2(PhNH2)2.

+

NH

CH3H3C

OHC

MeOH, HBrN HN

NNH

H3C

H3C

H3C

C5H11 C5H11

CH3

CH3

CH3

Br

H+

NH+ HN

+HNNH

H3C

H3C

H3C

C5H11 C5H11

CH3

CH3

CH3

2Br-ArCHO

Ar = -C6H4Br-4

57%

NH

NH

H3C

C5H11

C5H11

H3C

H2PPhBr

HN

CH3H3C

OHC

Figure 2. Synthesis of 5-(4-bromophenyl)-β-octaalkylporphyrin.

Figure 3. The structure of the porphyrin trimer ZnPMes2(PhNH)2-(ZnPPh)2 . Table 1. 1Н NMR data of the b-unsubstituted porphyrin substrates and coupling productsa.

β-Н,

δ(Δδ), ppm

meso-H δ(Δδ), ppm

HAr δ(Δδ), ppm Compound

1 2 Ha Hb a b c d

HArmes CH3

mes CH’3mes

ZnPPhBr - 9.90 9.52 7.90 - - - - - ZnPMes2(PhNH2)2 8.85 8.65 - - - - 7.98 7.05 7.41 2.61 1.86 ZnPMes3PhNH2 8.79 8.71 - - - - 7.69 6.03 7.28 2.69 1.84

ZnPMes2(PhNH)2-(ZnPPh)2

9.15 (0.3)

8.89 (0.24)

10.04 (0.14)

9.76 (0.24)

8.05 (0.15)

7.78 (-0.12)

8.30 (0.32)

7.74 (0.69)

7.34 (-0.07)

1.93 (-0.68)

1.54 (-0.32)

(ZnPMes3Ph)2 8.72 (-0.07)

8.55 (-0.16)

8.49 (-0.22) - - - - 8.12

(0.43) 7.58

(1.55)

7.27 (-0.01)

7.26 (-0.02)

2.54 (-0.15)

1,76 (-0,08)

(ZnPMes3Ph)2NH 8.85 (0.06)

8.78 (0.07) - - - - 8.22

(0.24) 7.49

(0.44) 7.27

(-0.01) 2.63

(-0.06) 1.84 (0)

aIn CDCl3 Table 2. 1Н NMR data of the b-substituted porphyrin substrates and coupling productsa.

aIn CDCl3, bIn DMSO-d6

meso-H δ(Δδ), ppm

HAr δ(Δδ), ppm

CH2 of diaza-18-Cr-6 δ, ppm Compound

Ha Hb a b

NCH2 N’CH2

1, 1’ 2, 2’ 3, 3’ 4, 4’ ZnP(PhPip)2

b 10.00 8.11 7.28 3.55 3.31 - - - -

ZnP(PhDiaza18C6)2 10.03 7.81 7.07 3.78 3.68 3.64 3.57 3.52 3.45

ZnP(PhPip)2-(ZnPPh)2 10.19 10.11 7.95 7.28 3.04 2.84 - - - - ZnP(PhDiaza18C6)2-(ZnPPh)2

10.13-9.91 7.79 6.91 3.86 3.86 3.86 3.73 3.73 3.73

ZnP(PhDiaza18C6)2-ZnPPh 10.16-10.05 7.63 7.47 3.98 3.98 3.98 3.98 3.98 3.98

Figure 4. UV-Vis spectra of the porphyrin trimer ZnPMes2(PhNH)2-(ZnPPh)2 .

10.1 10.0 9.9 9.8 9.7 9.6 9.5 9.4 9.3 9.2 9.1 9.0 8.9 8.8 8.7 8.6 8.5 8.4 8.3 8.2 8.1 8.0 7.9 7.8 7.7 7.6 7.5 7.4 7.3Chemical Shift (ppm)

7.29

7.34

7.73

7.747.77

7.78

8.04

8.05

8.29

8.30

8.88

8.899.14

9.15

9.76

10.0

4

3.9 3.8 3.7 3.6 3.5 3.4 3.3 3.2 3.1 3.0 2.9 2.8 2.7 2.6 2.5 2.4 2.3 2.2 2.1 2.0 1.9 1.8 1.7 1.6 1.5 1.4 1.3 1.2 1.1 1.0Chemical Shift (ppm)

3.93

3.92

3.90

3.57

3.56

2.71

2.67

1.93

1.79

1.78

1.77

1.75

1.74

1.60

1.59 1.58

1.57

1.03

1.02

1.01

H-meso

H'-mesoH'

b Hb Hb

Hd Hc Ha

Hames

CDCl3

H4

H1

H2

H3

N

N N

N

CH2

HN

H2C

HNZn

N

N N

N

C5H11

H3C

C5H11

Zn

N

NN

N

C5H11

H2C

H2C

CH2

CH

Zn

HCCH

HC

H2C

H'b

HaHb

Hb

H-meso

Hc

12

3

45

69

10

1112

13

14

23

2425

2627

28

2930

3133

34

35

Hbmes

Hames

H'-meso

H1

H2

H4

H3

H5

H6

H7

H8

Hd

Hemes

36

38

4

3

8 7

14

15

15

16

17

1618 20

21

22

2425

3237

35

Hames

H5

Hbmes

H6

H7

H8

Figure 5. NMR spectra of the porphyrin trimer ZnPMes2(PhNH)2-(ZnPPh)2 .

2132 2134 2136 2138 2140 2142 2144 m/z0

2

4

6

8x10Intens.

21372136

2135

2134

2133

2132

2138

2139

2140

2141

Figure 6. MALDI ToF spectra of the porphyrin trimer ZnPMes2(PhNH)2-(ZnPPh)2.