Supplementary information
First structural characterization of core modified 10,15-meso aryl
azuliporphyrins: observation of C-H---π interaction between pyrrole
β−CH and mesityl ring
Sundararaman Venkatramana, Venkataramanarao G. Ananda, Viswanathan
PrabhuRajaa,
Harapriya
Ratha,
Jeyaraman
Sankara,
Tavarekere
Chandrashekar*a, Weijie Tengb and Karin Ruhlandt Sengeb
a
Department of Chemistry, Indian Institute of Technology, Kanpur 208 016, India.
E-mail: [email protected]
b
Department of Chemistry, Syracuse University, Syracuse, New York 13244
K.
FAB mass m/z (%): 673 [M+1]
S 1: FAB Mass spectra for 9
8
[8.2H]
Absorbance
Soret
1
Q-bands
X5
0
400
500
Wavelength
600
700
Free base [8]: (CH2Cl2): λmax nm (log ε) = 395 (4.99), 477 (sh) (4.7), 494 (4.95), 670
(4.20)
Protonated [8.2H]+ :(5% TFA/ CH2Cl2): λmax nm (log ε) = 364 (4.6), 502 (5.2), 612
(4.0)
S2: Electronic absorption spectra for 8
+
9
[9.2H]
2+
Absorbance
1
Soret
Q-bands
X3
0
400
500
600
700
Wavelength (nm)
Free base [9]: (CH2Cl2): λmax nm (log ε) = 397 (4.8), 465 (sh) (4.7), 492 (4.9), 664
(4.2)
Protonated [9.2H]+:(5% TFA/ CH2Cl2): λmax nm (log ε) = 375 (4.5), 523 (4.11), 642
(3.7)
S3: Electronic absorption spectra for 9
L+
J
&
&+
G
M
J
+&
M J
+&
M G
&+
6
F
L
&+
1
F
1
J
M
I
I
K
E
E
j
D
D
H
H
H
i
h
2.8
2.6
2.4
2.2
2.0
1.8
*
g
d
b
c
e
a
9.5
9.0
8.5
ppm
8.0
f
7.5
7.0
S4: 1H NMR spectra of 8 in CDCl3. The assignments are marked
g
g
hH C
3
CH3
c
h
H C
i 3
c
i
CH3
g
g
i
CH3
Se
H3C
f
i
f
N
N
e
e
g
b
b
a
i
a
d
d
d
h
g
3.0
2.8
2.6
2.4
2.2
2.0
c,f
1.8
*
g
b
e
a
9.5
d
9.0
8.5
ppm
8.0
7.5
7.0
S5: 1H NMR spectra of 9 in CDCl3. The assignments are marked
L+
J
&
&+
G
M
+&
G
J
J
J
M
+&
L
&+
M
&+
6
F
F
1
1
I
M
I
K
E
E
D
D
H
H
H
S6: 2D COSY NMR spectra of 8: observed correlations are marked
g
g
hH C
3
CH3
c
H C
i 3
c
i
g
g
i
h
CH3
CH3
Se
H3C
f
i
f
N
N
e
e
g
b
b
a
a
d
d
d
S7: 2D COSY NMR spectra of 9: observed correlations are marked
C H
CD2Cl2/TFA
Temperature
N H
1 2 5
µ L
2 4 8
K
1 2 5
µ L
2 6 3
K
1 2 5
µ L
1 2 5
µ L
7 5
µ L
7 5
µ L
7 5
µ L
5 0
µ L
2 5
2 9 8
2 7 3
K
2 7 3
K
2 8 8
2 9 8
2 9 8
µ L
2 9 8
- 0 .4
- 0 .8
- 1 .2
- 1 .6
- 2 .0
- 2 .4
K
K
K
K
K
- 2 .8
p p m
S8: Dependence of chemical shift of azulene inner CH proton on the
concentration of TFA and the temperature. From a stock solution of 10%
v/v TFA in CD2Cl2, the titrations were carried out using indicated amount
of this solution. The protonated pyrrole proton (NH) is also shown.