Electronic Supplementary Information for :
Zinc (II) complex of meso-tetraphenylporphyrin with 4-methoxyaniline : Crystal structure
and antimicrobial activities of 4-methoxyaniline-5, 10, 15, 20-tetraphenyl-porphyrinatozinc
(II)
Joshua A. Obaleye1* ; Adedibu C. Tella1;Gabriel K. Obiyenwa1; Nzikahyel Simon1,2 ; Margaret
D.Olawale1
1
2
Department of Chemistry, P.M.B.1515, University of Ilorin, Nigeria
Department of Chemistry, University of Uyo, Nigeria.
*corresponding author :jobaleye@yahoo.com; jobaleye@unilorin.edu.ng
Tel.:+2348033582048
Table of contents
Experimental section ---------------------------------------------------------------------- S2
Synthesis of 5, 10, 15, 20-Tetraphenylporphyrin (TPPH2).-----------------------------------S2
5, 10, 15, 20-Tetraphenylporphyrinatozinc(II) (ZnTPP).--------------------------------------- S3
NMR spectra data discussionSpectra of TPPH2 and ZnTPP---------------------------
S4
Additional figures and Tables,
Fig.S1. Various views of ZnTPP(MOAN) molecule------------------------------------- S4
Table S1.Proton NMR spectral data for TPPH2 and ZnTPP------------------------------------S5
S1
1
Experimental section
Synthesis of 5, 10, 15, 20-Tetraphenylporphyrin (TPPH2).
The synthesis was carried out using Adler-Longo method*(Scheme 1) and The compound was purified by
column chromatography. on silica gel and dichloromethane/petroleum ether (3:1) as eluting
solvent.Melting point > 360 °C. Molecular weight = 614.752; Anal. Calcd.for C44H30N4 (%): C, 85.97; H,
4.92; N, 9.11. Found (%): C, 85.45; H, 5.40; N, 9.00. UV-vis (CH2Cl2): 425 nm, 515 nm, 545 nm, 590
nm, and 655 nm. IR (KBr, cm-1): 3317, 3053, 1595, 1473, 1350, 799, 746, 723, and 698. 1H NMR
(CDCl3, 200 MHz): δ (ppm) 13.20, 8.85, 8.30, 7.75, and 7.25. 13C NMR δ (ppm): 142.19, 134.58, 132.00,
127.73, 126.70, and 120.66.
CHO
NH
4
N
H
pyrrole
+
N
4
+
N
4H2O
+
3H2
HN
benzaldehyde
meso-5,10,15,20-tetraphenylporphyrin
Scheme 1. Synthesis of TPPH2
5, 10, 15, 20-Tetraphenylporphyrinatozinc(II)(ZnTPP).
The methods reported by Terazono, et al* and Sapien and Grazynski* with some modifications was were
adopted for the synthesis (Scheme 2). Solution of ZnCl2 (0.2217 g, 1.627 mmol) was dissolved in
methanol (20 ml) and mixed with a solution of TPPH2 (0.1020 g, 0.1627 mmol) in chloroform (25 ml).
*Ref. 14, 15,16 and 17 in the text.
S2
2
The mixture was heated under reflux ,1 ml of triethylamine was added after 2 minutes and refluxing
continued for 30 minutes with stirring. Then, the resulting solution was evaporated to dryness. The
residue was dissolved in CH2Cl2 to give reddish viscous mixture which was washed with 3 x50ml of
distilled water. Bright red liquid obtained was dried with anhydrous MgSO4 . The solution was
evaporated to dryness. The resulting product was recrystallized with toluene to obtain fine purple-red
crystals. Yield = 0.028g (72.54 %). Melting point, 240 °C. Molecular weight = 678.126; Anal. Calcd.for
ZnC44H28N4 (%): C, 77.93; H, 4.16; N, 8.26. Found: C, 76.98; H, 4.26; N, 8.07. UV-vis (CH2Cl2): λmax
(nm) 430, 550, and 585. IR (KBr, cm-1): 3435, 3051, 1595, 1485, 1339,995, 799, 750, 700, and 718. 1H
N1MR (CDCl3, 200 MHz): δ (ppm) 8.85, 8.30, 7.80, and 7.20.
C NMR δ (ppm): 150.22, 142.81,
13
134.43, 131.66, 127.49, 126.55, and 121.14.
NH
N
+
N
ZnCl2
HN
meso-tetraphenylporphyrin
N
N
+
Zn
N
2HCl
N
Scheme 2. Synthesis of ZnTPP
S3
3
NMR Spectra of TPPH2 and ZnTPP
Table S1.Proton NMR spectral data for TPPH2 and ZnTPP
TPPH2
Chemical
ZnTPP
Multiplicity
Assignment
shift(ppm)
8.85
Chemical
Multiplicity
Assignment
Singlet
H2 β-pyrrole
shift(ppm)
Singlet
H
β-pyrrole 8.88
(8H)
8.25,7.82,7.20
Triplet
H
(8H)
phenyl 8.25,7.80,7.20
Triplet
(20H)
1.5
Singlet
Water
H1
phenyl
(20H)
1.5
Singlet
Water
Proton NMR spectral data for TPPH2 and ZnTPPare shown in Table S1. The singlet signal at 8.85 ppm
attributed to β-pyrrole of TPPH2 was observed at 8.88 ppm in the zinc (II) complex. These insignificant
changes were in agreement with the findings of previous workers *. The signals observed in the ligand
and zinc complex at 1.5 ppm are due to water molecules present in the aprotic solvent CDCl 3 used while
the solvent itself was observed at 7.20 ppm and overlapped with phenyl protons. Adler et al * , reported a
signal of N-H protons of porphyrins 13 ppm upfield than the N-H proton resonance in pyrrole. The signal
at 13.25 ppm found in the spectra of TPPH2 completely disappeared in ZnTPP spectra as previously
observed and reported by Terazono, et al* . This could be attributed to coordination of the metal through
the nitrogen atoms.
Ref. 16, 32 and 25 cited in the text.
S4
4
Figure S1. Various views of ZnTPP(ANSD) molecule
S5
5
6