Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 40:404–409, 2010
Copyright © Taylor & Francis Group, LLC
ISSN: 1553-3174 print / 1553-3182 online
DOI: 10.1080/15533174.2010.492552
Meso-tetra[(p-alkoxyl-m-ethyloxy)phenyl]porphyrins
and their Transition Metal Complexes: Synthesis and
Characterization
Miao Yu,1,2 Yu J. Zhang,2 Jian H. Shi,2 Guo F. Liu,2 and Hong J. Zhang1
1 State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry,
Chinese Academy of Sciences, Changchun, Jilin, P. R. China
2College of Chemistry, Jilin University, Changchun, Jilin, P. R. China
can change porphyrins, electronic structure, which give them
many characteristics.
Three
meso-tetra[(p-alkoxyl-m-ethyloxy)phenyl]porphyrins
and their transition metal (Zn, Cu, Ni, Co, Mn) complexes were
synthesized. The molecular structures were confirmed by means of
1H NMR, UV-Vis, IR, elemental analyses, etc., which indicate the
valence state of Mn atom in the compound is +3 and Ni, Cu, Zn,
Co atom is +2. Optical properties were discussed by fluorescence
spectrum. The quantum yields of the complexes are much lower
than the corresponding ligands.
It is well known that chlorophyll, haem and cytochrome,
each of which plays a key role in life, are tetrapyrrole com-
pounds that contain Mg2+, Fe3+ ions, etc.[9] In recent years,
dyads and triads containing porphyrins as electron acceptor or
donor, have been proved of interest as photosynthetic model
compounds[10]; metal porphyrins have also been widely used
in photocatalysis, light-energy conversion and various medical
applications.[11−13]
Fluorescein exhibits strong absorption and fluorescence in
the UV-vis region; fluorescence is a convenient way of re-
vealing electron transfer in photosynthesis model compounds.
Fluorescein is a good candidate to form dyads with por-
phyrin in order to research the photoelectron properties.
In the past few years, Sun et al. had synthesized a se-
ries of fluoresceine porphyrin dyads, and discussed their
photoproperties.[14−15]
Keywords luminescence spectroscopy, porphyrin, transition metal
complex
INTRODUCTION
Porphyrins are tetrapyrrolic macrocycles and have special
structures with big π-orbital on the carbon-nitrogen framework.
Because of the large conjugational effect of the tetrapyrrolic
macrocycle, porphyrins have special photophysical properties
and have been used in many fields[1] such as oxygen transfer,[2]
energy and electron transfer,[3] light harvesting,[4] molecular
wires[5] and so on. Porphyrins can be synthesized flexibly by
introducing different substituents at the meso- and β-position,
and their photophysical and photochemical properties can be
applied in many fields.[6] The meso-substituted porphyrins are a
subgroup of porphyrins with interesting properties.[7−8] Meso-
tetraaryl porphyrins show attractive properties such as easy syn-
thesis and functionalization, and have been used in a wide variety
of model systems. Metal porphyrin research is the center of por-
phyrin chemistry since the metal ions in porphyrin complexes
In this study, we synthesized three meso-tetra [(p-alkoxyl-
m-ethyloxy) phenyl] porphyrins and their transition metal (Zn,
Cu, Ni, Co, Mn) complexes. Their molecular structures were
1
confirmed by H NMR, UV-Vis, IR and elemental analyses.
We also discussed the optical properties of these compounds
(Scheme 1).
EXPERIMENTAL
Materials and Instrumentation
All reagents and solvents were of commercial reagent grade
and used without further purification. All chemicals were
reagent grade and dried before use. Pyrrole was newly distilled
Received 7 September 2009; accepted 7 May 2010.
The authors are grateful to the financial support of the National before use.
Natural Science Foundation of China (No. 20801022).
The proposed molecular structures of the compounds were
Address correspondence to Mao Yu, and Hong J. Zhang, State Key
Laboratory of Rare Earth Resource Utilization, Changchun Institute
of Applied Chemistry, Chinese Academy of Sciences, Yinghua Road,
Changchun 130022, Jilin, P. R. China. E-mail: yumiao@jlu.edu.cn;
confirmed by IR and 1H NMR spectroscopy. The IR spec-
tra were recorded on a Nicolet 5PC-FT-IR spectrometer in
1
the region 200–4000 nm−1 using CsI pellets. H NMR spec-
tra were recorded on a Varian-Unity-500 NMR spectrometer
404
Yu, Miao
