Synthesis and characterization of novel unsymmetrical porphyrin and its complexes

Article abstract of DOI:10.1080/15533170802255294

A novel unsymmetrical porphyrin meso-5-(p-octanoyloxyphenyl)-10,15,20- triPhenylporphyrin (OPTPPH2) and relative transition metal complexes (DPTPPM, M = Zn, Fe, Co, Ni, Cu, Mn) were synthesized and characterized by elemental analysis, UV-Vis spectra, mass spectra, 1H NMR, infrared spectra, Raman spectra, and cyclic voltammetry. In dimethylformamide (DMF), 0.1 mol·L-1 tetrabutylammonium perchlorate (TBAP), these compounds exhibit two or three one-electron reversible redox reactions. Quantum yields of the S1?S0 fluorescence are measured at room temperature. These studies will contribute to further choice and application of the liquid crystals. Copyright Taylor & Francis Group, LLC.

Full text of DOI:10.1080/15533170802255294

This article was downloaded by: [University of California Santa Cruz]
On: 13 October 2014, At: 16:18
Publisher: Taylor & Francis
Informa Ltd Registered in England and Wales Registered Number: 1072954 Registered office: Mortimer
House, 37-41 Mortimer Street, London W1T 3JH, UK
Synthesis and Reactivity in Inorganic, Metal-Organic,
and Nano-Metal Chemistry
Publication details, including instructions for authors and subscription information:
http://www.tandfonline.com/loi/lsrt20
Synthesis and Characterization of Novel
Unsymmetrical Porphyrin and its Complexes
Yuhua Shi a , Xuexin Tang a , Erjun Sun a , Xiuli Cheng a , Dong Wang a , Shuangjiang Yu a
& Tongshun Shi a
a College of Chemistry, Jilin University , Changchun, P.R. China
Published online: 24 Sep 2008.
To cite this article: Yuhua Shi , Xuexin Tang , Erjun Sun , Xiuli Cheng , Dong Wang , Shuangjiang Yu & Tongshun Shi
(2008) Synthesis and Characterization of Novel Unsymmetrical Porphyrin and its Complexes, Synthesis and Reactivity in
Inorganic, Metal-Organic, and Nano-Metal Chemistry, 38:5, 431-438
To link to this article: http://dx.doi.org/10.1080/15533170802255294
PLEASE SCROLL DOWN FOR ARTICLE
Taylor & Francis makes every effort to ensure the accuracy of all the information (the “Content”) contained
in the publications on our platform. However, Taylor & Francis, our agents, and our licensors make no
representations or warranties whatsoever as to the accuracy, completeness, or suitability for any purpose of
the Content. Any opinions and views expressed in this publication are the opinions and views of the authors,
and are not the views of or endorsed by Taylor & Francis. The accuracy of the Content should not be relied
upon and should be independently verified with primary sources of information. Taylor and Francis shall
not be liable for any losses, actions, claims, proceedings, demands, costs, expenses, damages, and other
liabilities whatsoever or howsoever caused arising directly or indirectly in connection with, in relation to or
arising out of the use of the Content.
This article may be used for research, teaching, and private study purposes. Any substantial or systematic
reproduction, redistribution, reselling, loan, sub-licensing, systematic supply, or distribution in any
form to anyone is expressly forbidden. Terms & Conditions of access and use can be found at http://
www.tandfonline.com/page/terms-and-conditions

Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 38:431–438, 2008
Copyright © Taylor & Francis Group, LLC
ISSN: 1553-3174 print / 1553-3182 online
DOI: 10.1080/15533170802255294
Synthesis and Characterization of Novel Unsymmetrical
Porphyrin and its Complexes
Yuhua Shi, Xuexin Tang, Erjun Sun, Xiuli Cheng, Dong Wang, Shuangjiang Yu,
and Tongshun Shi
College of Chemistry, Jilin University, Changchun, P.R. China
˚
except DMF was predried over activated 4A molecular sieve
and vacuum distilled from calcium hydride (CaH2) prior to use.
Pyrrole was distilled under reduced pressure and stored in sealed
ampoules
A
novel unsymmetrical porphyrin meso-5-(p-octanoy-
loxyphenyl)-10,15,20-triPhenylporphyrin (OPTPPH2) and rela-
tive transition metal complexes (DPTPPM, M=Zn, Fe, Co, Ni, Cu,
Mn) were synthesized and characterized by elemental analysis,
UV-Vis spectra, mass spectra, 1H NMR, infrared spectra, Raman
spectra, and cyclic voltammetry. In dimethylformamide (DMF),
0.1 mol·L−1 tetrabutylammonium perchlorate (TBAP), these
compounds exhibit two or three one-electron reversible redox
Instrumentation
Elemental analyses were obtained by a Perkin-Elmer 240 C
reactions. Quantum yields of the S1•S0 fluorescence are measured auto elementary analyzer. UV-vis spectra were recorded on a
at room temperature. These studies will contribute to further
choice and application of the liquid crystals.
Shimadzu UV-365 spectrometer using chloroform as solvent.
IR spectra were recorded on a Nicolet 5PC-FT-IR spectrometer
in the region 400–4000 cm-1 using KBr pellets. 1HNMR spectra
were obtained in CDCl3 employing tetramethylsilane, (CH3)4Si
as an internal reference on Varian Unity-500 (500 MHz) spec-
trometer, mass spectra (FBA) were obtained on a JEOL AX-505
spectrometer.
Keywords cyclic voltammetry, fluorescence spectra, luminescence
spectra, Raman spectra, unsymmetrical porphyrin
INTRODUCTION
Flucrescence spectra were recorded with a Shimadzu
RF5301PC spectrofluorometer. Ramn spectra were recorded
with a Renishawinvia resonance raman spectroscopy.
Redox potentials of the porphyrin and its complexes (10−3
mol·L−1) in dried DMF containing 0.1 M TBAP as a support-
ing electrolyte using a glassy carbon working electrode, plat-
inum counter electrode, and Ag+/Ag (0.01 mol·L−1 AgNO3 in
CH3CN)pseudo-reference electrode under deaerated conditions
and a CHI 660A electrochemical analyzer were determined at
room temperature by cyclic voltammetry.
The study of porphyrins has received increased interest in
recent years. Porphyrins have been utilized for the development
of artificial receptors for molecular recognition and new chi-
ral catalysts for asymmetric synthesis,[1−3] for the exploration
of the mechanisms of biologically important reactions such as
photosynthesis and P450-catalyzed redox reactions, and for the
study of stereochemistry.
Metalloporohyrin chemistry is one of the most important
areas of modern chemistry, the unique structure and novel reac-
tivity promise metalloporphyrin complexes for expansive appli-
cations in biology, medicine, chemistry, material science fields,
such as catalysis, new material, etc. In this paper, we report for
the first time, the synthesis and characterization of a series of
novel unsymmetrical porphyrin and complexes (Scheme 1).
Synthesis
Octanoyl chloride was prepared and purified in our labora-
tory.
Meso-5-(p-hydroxy)phenyl-10,15,20-triphenylporphyrin
(HTPP) was prepared and purified by known procedures.[4]
Synthesis of ligand (OPTPPH2 ). The HTPP(1.5 g) and
Triethylamine were added to benzene (400 ml, distilled from
CaCl2) in a 250 ml round bottom flask. Octanoyloxychlorin (di-
luted by 10 ml benzene) was trickled between 0.5h. The solution
mixture was refluxed and stirred for 8h under the protection of
a dry nitrogen stream. Then benzene was evaporated, triethy-
lamine and overplus octanoyloxychlorin were was evaporated
out under vacuum. The crude dry product was chromatographed
MATERIALS AND METHODS
All reagents and solvent were commercial reagent grade and
were used without further purification unless otherwise noted,
Received 12 July 2007; accepted 1 December 2007.
Address correspondence to Xuexin Tang, College of Chemistry,
Jilin University, Changchun 130023, P.R. China. E-mail: xuexintang@
email.jlu.edu.cn
431

432
Y. SHI ET AL.
SCHEME 1. The structure of the unsymmetrical porphyrin and its complexes.
on neutral aluminum oxid using CHCl3 as the eluent. The first C 76.28, H 5.13, N 6.85; found(%): C 76.14, H 5.20,
band (purple red) was collected and evaporated to dryness to give N 6.79
a purple red solid which was further recrystallized from CHCl3
(83.4% yield). Elemental ana1. calc. (%) for C52H44O2N4: Ni)were similar to above-mentioned method.
The synthetic methods of the other complexes(M = Cu,
C 82.54,H 5.82,N 7.41; found (%): C 82.49, H 5.94, N 7.36.
Synthesis of OPTPPCo. OPTPPH2 were added to DMF (20
Synthesis of OPTPPZn. OPTPPH2 and ZnCl2 were added ml) and CH2Cl2 (20 ml), then the solution mixture was purged
to DMF (20 ml) and CH2Cl2 (20 ml), then the solution was with dry nitrogen for about 30 min. CoCl2•H2O were added
refluxed for about 20 min. The extent of the reaction was mon- to mixture and refluxed for 30 min. The extent of the reaction
itored by measuring the UV-visible spectrum of the reaction was monitored by measuring the UV-visible spectrum of the
solution per 5 min. The CH2Cl2 was evaporated out, then the reaction solution per 5 min. Then DMF and CH2Cl2 were evap-
solution was added to distilled water (500 ml), was suction- orated out under vacuum. The red-black was collected and the
filtered, and the crude product was purified by column chro- crude product was purified by column chromatography on neu-
matography on silica gel using a solvent of CHCl3 as the eluent. tral aluminum oxid using a solvent of CHCl3 as the eluent. The
The second band was collected and evaporated to dryness to give second band was collected and evaporated to dryness to give a
a purple red solid. Elemental ana1. calc.(%) for C52H42O2N4Zn: purple red solid. Elemental ana1. calc.(%) for C52H42O2N4Co:
TABLE 1
The UV-visible spectra and data of the ligand and the complexes in chloroform (1.00 ×10−6 mol/L)
Compounds
Solvent
Soret band
Q band
Ligand
CHCl3 420 (3.10×105) 515 (1.91×104) 550 (8.20×103) 590 (6.47×103) 645 (6.01×103)
CHCl3 420 (2.90×105) 545 (2.26×104) 585 (4.35×103)
CHCl3 415 (2.90×105) 540 (2.13×104)
OPTPPZn
OPTPPCu
OPTPPNi
OPTPPCo
OPTPPFeCl
CHCl3 415 (2.50×105) 525 (1.78×104)
CHCl3 410 (2.60×105) 525 (1.61×104)
CHCl3 415 (8.30×104) 505 (9.27×103) 570 (6.15×103)
OPTPPMnCl CHCl3 480 (1.00×105) 580 (1.07×104) 615 (1.15×104)
*Molar extinction coefficients are in parentheses.

NOVEL UNSYMMETRICAL PORPHYRIN
433
TABLE 2
Fluorescence Spectroscopy
Fluorescence spectral data of the ligand and the complexes in
The fluorescence emission spectra of the porphyrin com-
pounds at room temperature are shown in Figure 1. Table 2
gives the excitation spectral maxima and the quantum yields of
the fluorescent emission of the ligand and its complexes.
The porphyrin was disolved in dry chloroform and deaerated
by Ar carefully. The compounds exhibit two emission bands in
the regions 650, 592, 653 and 711, 640, 710 nm correspond-
ing to Q (0,0) and Q (0,1) transition, respectively. To deter-
mine fluorescence quantum yield, fluorescence intensity makes
chloroform (1.00 × 10−6 mol/L)
Compounds
λemmax/nm
Quantum yields (f)
Ligand
OPTPPZn
OPTPPNi
650
592
653
711
640
710
0.066
0.040
0.033
C 76.85, H 5.17, N 6.90; found(%): C 76.93, H 5.24, the yield of S1 fluorescence of meso-tetraphenylporphyrin zinc
N 6.82.
(TPPZn) in CHCl3 (f = 0.033, ex = 420 nm) as a standard.
The synthetic methods of the other complexes (M = Mn,Fe) There are fluorescences of the S2 (B band) and the S1 (Q band)
were similar to above-mentioned method.
in the porphyrin. The fluorescence of the B (Soret) band is at-
tributed to the transition from the second excited singlet state
S2 to the ground state S0, S2 → S0. The Soret fluorescence is
about two orders of magnitude weaker than the S 1 → S0 of Q
band emission. Its quantum yield is so low that the fluorescence
becomes unobservable sometimes. This fluorescence emission
was not observed at room temperature and the experimental ex-
cited wavelength of 420 nm. The fluorescence quantum yields
of our complexes are less than 0.07. Thus, the excited state S1
is primarily deactivated by radiationless decay. This indicates
RESULTS AND DISCUSSION
UV-vis Spectra
The data of UV-visible spectra of the ligand and compounds
were recorded in chloroform (see Table 1).
The UV-visible absorption bands of the porphyrin are due to
the electronic transitions from the ground state(S0) to the two
lowest singlet excited states S1 (Q state ) and S2 (B state). The
S0–S1 transition gives rise to the weak Q bands in visible region
(550–650 nm), while S0–S2 transition produces the strong B
band in near UV region (380–450 nm).
fairly certainly that the spin forbidden process S ∼ • Tn is
1
predominant for radiationless deactivation of S1 in porphyrin
complexes.
From Table 1, we know that OPTPPH2 have one Soret band
(420 nm) and four Q bands (515, 550, 590, 645 nm). The Soret
band of OPTPPM occurs to different degree shift and number
of Q band reduced.
After the metal ion has entered the body of porphyrin because
of the increasing of molecular symmetry from D2h to D4h, the
number of Q band decreases, and the absorption frequencies
shift.[5]
Infrared Spectra
The important band frequencies and assignments of the lig-
and and complexes as presented in Table 3.
From Table 3, We can see that 3317 cm−1and 966 cm−1 in the
free porphyrin are due to N-H sretching vibration and winding
vibration of porphyrin core, respectively. But the two bands in
the complexes disappear since the two hydrogen atoms in the
N−H bonding are replaced by a metal ion. The band in the range
3052–3056 cm−1 in the ligand and complexes are found that are
assigned to the C−H stretching vibration of aromaticity. The
band in the range 1590–1598 cm−1 in the ligand and complexes
are found that are assigned to the C=C stretching vibration
of benzene ring. The bands at 698–703 cm−1 are assigned to
the methylene in-plane rocking vibration of straight alkyl chain
including over four carbons. Assignment of other absorption
bands are also presented in Table 3.
Raman Spectra
The importa band frequencies and assignments of the lig-
and and complexes as presented in Table 4 according to
literature.[6−9]
Figure 2 displays the Raman spectra of ligand and complexes
excited at 514.5 nm. The Cβ-Cβ and Cα Cm stretching frequen-
cies are usually in 1450–1600 cm−1 region due to the relatively
large force constants of these bonds. The stretching motions
of Cα-Cβ and Cα-N bonds are known to interact with each
FIG. 1. Fluorescence spectra of ligand and complexes at room temperature in
CHCI3.

434
Y. SHI ET AL.
TABLE 3
Infrared photoacoustic spectra of ligand and complexes (cm−1
)
Ligand OPTPPZn OPTPPCu OPTPPCo OPTPPNi OPTPPFeCl OPTPPMnCl
Assignment
3317.1
υ(N-H)
υ(C-H)(Ar)
υ(C-H)
3056.7 3052.9
2927.6 2925.6
2856.2 2852.3
1758.8 1722.2
1596.8 1596.8
1471.5 1485.0
1440.6 1440.6
1351.9 1338.4
1199.6 1200.1
1132.1 1166.8
1072.3 1068.4
995.1
3054.8
2923.7
2852.3
1758.8
1598.8
1490.8
1440.6
1346.1
1201.4
1162.9
1072.4
1002.9
3052.9
2925.6
2854.3
1756.9
1598.8
1490.8
1440.6
1348.1
1205.4
1164.9
1070.4
1004.8
3056.7
2919.8
2850.4
1756.9
1596.8
1490.8
1440.6
1346.1
1201.4
1162.9
1068.4
1002.9
3054.8
2923.7
2852.3
1758.8
1596.8
1488.9
1440.6
1338.4
1201.5
1164.8
1072.3
1002.9
3054.8
2923.7
2854.3
1758.8
1598.8
1488.9
1440.6
1342.3
1203.4
1166.7
1072.3
1010.6
υ(C-H)
υ(C=O)
υ(C=C)
C=C(benzene)
υ(C-C)
υ(C-O)
β(C-H)
υ(Cα-N) δ(CCN) υ(Cα-Cm)
P
966.2
δ(N-H)
798.4
698.1
796.5
702.0
798.4
700.1
798.4
698.1
794.6
700.1
798.4
702.0
802.2
703.9
-(CH2)n-
FIG. 2. Raman spectra of OPTPPH2 and OPTPPM (M=Ni, Cu, Mn).
FIG. 3. 1HNMR spectra of OPTPPH2.

NOVEL UNSYMMETRICAL PORPHYRIN
435
FIG. 4. 1HNMR spectra of OPTPPZn.
other substantially. Raman bands in 1300–1450 cm−1 region -2.790(2H,pyrrole N-H). The 1H-NMR chemical shift values in
are due to the out-of-phase coupled (Cα-Cβ)/(Cα-N) stretching CDCl3 (δ, ppm) for OPTPPZn are at 8.948–8.969(8H, pyrrole
modes. In the 1008–995 cm−1 region spectrum are due to the ring), 7.476–8.227 (19H, benzene ring), 2.732–2.762 (2H,
in-phase coupled (Cα-Cβ)/(Cα-N) stretching mode, while the OOCH2), 1.254–1.912 (10H, alkyl CH2), 0.930–0.943 (3H,
917 cm−1 band of ligand can be assigned to the Pyr. breathing alkyl CH3).
stretching modes. In the 363–390 cm−1 region spectrum of com-
plexes can be assigned to δ(CαCmCα) and (M - N) stretching for the metalloporphyrins complexes than for the free base. In
From Figures 3 and 4, we can see that there are fewer peaks
modes.
the complex OPTPPZn, the signal peak at −2.790 (2H, pyrrole
N-H) disappears, since the hydrogen atom in the N-H bond is
replaced by Zinc ion. Other peaks of the complex are similar as
compared with those of the ligand.
1H-NMR Spectra
The 1HNMR spectra of the ligand and the complex
OPTPPZn (shown in Figures 3 and 4) were obtained in
CDCl3. The 1H-NMR chemical shift values in CDCl3 (δ, ppm)
for ligand OPTPPH2 are at 8.843–8.864(8H, pyrrole ring),
Mass Spectra (FBA)
In the mass spectra (Figures 5 and 6), the molecular ion peak
7.481–8.224(19H, benzene ring), 2.733–2.763(2H, OOCH2), of the ligand OPTPPH2 is 757.8 (100%), and the molecular ion
1.373–1.911(10H, alkyl CH2), 0.929–0.956(3H, alkyl CH3), peak of the OPTPPZn is 820.3(100%).
TABLE 4
Characteristic Raman bands of ligand and complexes (cm−1
)
Ligand OPTPPZn OPTPPCu OPTPPCo OPTPPNi OPTPPFeCl OPTPPMnCl
Assignment
1550.4vs 1545.9m
1560.9s
1502.4m
1364.0vs
1541.5s
1502.4m
1373.2s
1553.4vs
1494.8w
1373.2s
1550.4vs
1511.4m
1357.9s
1578.9m
1499.3m
1373.2m
(Cβ-Cβ)
(Cβ-Cβ)
1493.3s
1361.0m
1327.2m
1238.9s
1134.1m
999.1m
917.1w
714.3m
542.2m
1490.3w
1350.2s
(Cα-N) + (Cβ-Cβ)
δ(C-H)
1229.6w
1173.4vm 1181.2s
1002.3w
1234.3s
1231.2w
1185.9m
995.9m
1237.4m
1130.9w
1002.3m
1228.1m
1181.2m
1000.7m
1215.6w
1130.9w
1008.7vm
(Cα-N)
δ(Cβ- H)
1002.3s
(Cα-N) + (Cα-Cβ)
Pyr.breathing
724.3vw
570.9w
729.2vw
564.2vw
387.4vs
715.9w
557.4w
390.8vs
730.9w
547.3w
389.1m
722.6w
560.8w
387.4s
755.6m
532.1w
363.3s
389.1vw
δ(CαCmCα) + (M- N )
334.0m
vs. very strong; s. strong; m. medium; w. weak; vw. very weak

436
Y. SHI ET AL.
FIG. 5. Mass spectra of OPTPPH2.
FIG. 6. Mass spectra of OPTPPZn.

NOVEL UNSYMMETRICAL PORPHYRIN
437
FIG. 7. Cyclic voltammograms of OPTPPH2 and OPTPPM (M=Zn,Co,Ni,Cu,Mn) dissolved in DMF containing 0.1M TBAP. Scan rate=0.1V/S.
Electrochemistry
7, we can know two reductive reactions of cyclic voltammo-
grams of OPTPPMnCl were obtained , the first at −0.59V
corresponds to the reaction Mn(III) [ Mn(II), and the second
occurs at −1.73V, and can be assigned as formation of the anion
radical.
In the DMF, OPTPPCo undergoes three redox reactions. The
second reaction peak occurs to Ep= −0.12, corresponds to the
reaction Co(III) [ Co(II); The second reaction peak occurs to
Ep= −0.12, corresponds to the reaction Co(II) [ Co(I). Com-
pared with the redox reaction of TPPCo [TPPCo(III)/TPPCo(II),
Ep=−0.1 V; TPPCo(II)/TPPCo(I), Ep= −1.154 V], those of
DPTPP are more negative. This behavior may be explained
that octanoyloxy increases the electron density of the π-ring
system and the energy of both the HOMO and the LUMO,
The redox potentials of OPTPPH2 and OPTPPM (M=Zn,
Co,Ni,Cu,Mn) were measured by cyclic voltammetry.
Cyclic voltammograms of OPTPPH2 and OPTPPM(M=Zn,
Co, Ni, Cu, Mn) dissolved in DMF are shown in Figure 7 and
Table 5. From Figure 7 and Table 5, we can see that in the pres-
ence of 0.1 M TBAP of DPTPPH2 undergoes one irreversible
oxidation reaction at Ep = 0.63 V (P+/P0) and one reversible
reductive reaction at Ep = −1.46 V (P−/P2−) for a scan rate of
0.1 V/S. The difference in E1/2 was 2.10 V, which are in good
ox
1/2
red
1/2
agreement with E (1)- E (1) = 2.25 0.15.
All voltammograms of OPTPPNi, OPTPPCu, OPTPPZn
were similar in shape. Each compound undergoes two irre-
versible oxidation reactions and a single one reversible reductive
reaction with the potential range of the solvent. From Figure
TABLE 5
Summary of redox potentials for the ligand and the complexes
Ligand oxidation
E1/2(1) E1/2(2)
Metal
E1/2
Ligand reduction
E1/2(1)
OPTPPH2
OPTPPMnCl
OPTPPCo
OPTPPNi
OPTPPCu
OPTPPZn
0.63
−1.46
−1.73
−0.59(•–•)
0.73
−0.12(•–•),−1.21(•–•)
0.56
0.79
0.67
0.39
0.37
−1.58
−1.58

438
Y. SHI ET AL.
which makes them easier to oxidize and harder to reduce than
TPPCo10.
2. J. P. Collman, X. Zhang, V. J. Lee, E. S. Uffelman, J. I. Brauman. SRegios-
elective and enantioselective epoxidation catalyzed by metalloporphyrins,
Science, 1993, 261, 1404–1411.
3. D. Mansuy. Activation of alkanes: The biomimetic approach. Coord. Chem.
Rev., 1993, 125, 129–142.
CONCLUSIONS
4. Ji Liangnian, Qin Xia, Huang Yinwan, The Synthesis and Characterization
of a New Tailed Metalloporphyrin Coordination Compound. Acta Scien-
tiarum Naturalium Universitatis Sunyatseni, 1993, 32, 1–7.
5. W. D. Horrocks, Jr., C. P. Wong. Lanthanide Porphyrin Complexes. Eval-
uation of Nuclear Magnetic Resonance Dipolar Probe and Shift Reagent
Capabilities. J. Am. Chem. Soc., 1976, 98, 7157.
From the above results of UV-vis spectra, infrared spectra,
1H-NMR spectra, mass Spectra, we can propose the structure
of the OPTPPH2 and relative transition metal complexes is as
we expected.
A
series of meso-5-(p-octanoyloxyphenyl)-10,15,20-
6. G. S. S. Saini, Resonance Raman study of free-base tetraphenylporphine
and its dication. Spectrochimica Acta Part A., 2006, 64, 981–986.
7. Ingar Halvorsen, Erik Steene, Abhik Ghosh. Resonance Raman marker
bands of β-octahalogeno-meso-tetraarylmetalloporphyrins. J. Porphyrins
Phthalocyanines, 2001, 5, 721–730.
8. Florian Paulat, V. K. K. Praneeth, Christian Nalther, and Nicolai Lehnert.
Quantum Chemistry-Based Analysis of the Vibrational Spectra of 5-
Coordinate Metalloporphyrins [M(TPP)Cl]. Inorg. Chem., 2006, 45, 2835–
2856.
triphenylporphyrin and relative transition metal complexes
have been prepared. We have illustrated the application of
cyclic voltammetry. The cyclic voltammetry contributes to the
investigation of porphyrins.
The fluorescence intensity of OPTPPZn and OPTPPNi is
much bigger than other transition metal complexes.
9. Huiying Jia, Weiqing Xu. Spectral Study of 5, 10, 15, 20-Tetra (p-
Chlorophenyl) Porphyrin Lanthanide Complexes. Chem Icai Journal of
Chinese Universities, 2004, 2, 338–341.
REFERENCES
1. Z. Gross, S. Ini. Remarkable Effects of Metal, Solvent, and Oxidant on
Metalloporphyrin-Catalyzed Enantiselective Epoxidation of Olefins. J. Org.
Chem., 1997, 62, 5514–5521.
10. Wei Liu, Tongshun Shi, Synthesis and Characterization of Tetra-(p-
octanoyloxyphenyl) Porphyr in Cobalt complex. Acta Scientiarum Nat-
uralium Universitatis Jilinensis, 1999, 01, 94–96.