Synthesis And Studies On Properties Of Dimeric Porphyrin

College of Chemistry,Jilin University,ChangChun 130023,P.R. ChinaIn this paper, I has synthesized and characterized series ofp-hyhroxylphenyporphyrin and investigated their properties of luminescence. Ialso investigated self-aggregated properties of MHTPP in chloroform solvent.Furthermore, I have attained the self-aggregated dimer of the MHTPP. Itsstructure was characterized by the element analysis, mass spectra, IR spectra,UV-Vis spectra and so on. We have investigated photoelectrochemistry ofself-aggregated dimer of MHTPP. We prepared porphyrin dimer by the bridgeof L-glutamic acid and maleic acid. These compounds were characterized bythe element analysis, mass spectra, IR spectra, UV-Vis spectra and so on.Germany chemistry J.Deisenhofer together with his co-worker R.Huberand H. Michel has firstly measured photosynthesis reaction central X-raythree-dimensional structure of bacterial Rhodopseudomonas virridis(Rp.viridis) (therefore ,J.Deisenhofer has received 1988 Nobel Chemical prize).Followed, the bacterial Rb. Sphaeroides reaction central structure has beenconfirmed, too. Study on the photosynthesis reaction system of green plantsshowed the reaction center of P680 and P700 also is porphyrin dimer.metalloporphyrin dimer as important compositions of chlorophyll reactionactive center in photosynthesis reaction courses of the green plants andbacterial plays a crucial role in charge-transfer and charge-separation andimportant biological effect. In order to search special bio-mimic porphyrin, it isimportant for us to mimic the structure and function of natural porphyrindimers.However, it is very difficult to investigate the complicated structure ofnatural porphyrin dimers directly. Up to date, the main study orientation ofporphyrin dimers is to design and synthesize dimers which can mimic thefunction of natural porphyrin aggregates. In two decades, researchers havedone a lot of studies on the porphyrin dimer and oliger.After the earliest covalent porphyrin dimer was preparated in 1972, Boxand Closs design and synthesize all kinds of chlorophyll dimer to mimicreaction active center of special Pair in 1976. N. E. Kagan synthesized a seriesof two covalent-bridged porphyrin derivative dimers which are rigidconjugated and high-block in 1977. These dimers showed remarkableaggregated properties in the solution. Then a number of porphyrin dimersincluding simple μ-OXO porphyrin dimer, linear porphyrin dimer and layerporphyrin dimer and so on were synthesized. Kojinakanishi and NinaBerovareported a special structural porphyrin dimer which is pliers-type porphyrindimer. Up to date, all kinds of covalent and non-covalent porphyrin dimershave been prepared and their structures were confirmed by the elementanalysis, Uv-vis spectra, FT-IR, mass spectra and other spectroscopics. Thephoto-and electro-chemistry was investigated by the all kinds of methods.I Synthesis of series of p-hydroxyphenylporphyrins:The p-hydroxylphenyl meso-substituted porphyrin arrays weresynthesized using two mixed aldehydes;the compounds were separated bycolumn chromatography on the aluminum oxide with different ratio ofchloroform/ ethanol eluted. And the compounds were confirmed byspectroscopic analysis. Their fluorescence spectra were studied. The resultsshowed that the fluorescence intensity at 440nm was very weak and increasedwith the hydroxyl increased, at 650nm was strong and decreased with thehydroxyl increased for p-hydroxylphenylporphyrin arrays.II Self-aggregated properties of MHTPP and synthesis ofself-aggregated dimer:The self-aggregate properties of MHTPP in the chloroform solutions havebeen investigated. The fresh solution of MHTPP strictly obeys Beer's lawwhile the deposited solution of MHTPP widely deviates from Beer's law. Thesoret band of the UV-Vis spectra was red-shifted from 420nm to 450nm in thetwo solutions. The important information suggests that the self-aggregatereaction of MHTPP occur. Furthermore, the self-aggregate process of MHTPPwas monitored using thin-layer chromatogram (TLC), UV-Vis spectra,FTIR-IR spectra, Mass spectra, and 1H NMR. The results show that theself-aggregate process of MHTPP proceeded along with the effectivecharge–separation and proton-migration in the molecule. According to themonitor's results in the process of self-aggregate reaction, we speculate theself-aggregate mechanism of MHTPP. Furthermore, I has synthesizedself-aggregated dimer and its structure was confirmed using UV-Vis spectra,FTIR-IR spectra, element ananysis, Mass spectra, and 1H NMR. Its photo-andelectron-chemistry was investigated by comparing with monomer.III Synthesis of L-glutamic acid bridged porphyrin dimerligand and transition metal porphyrin complexes:The L-glutamicacyl dichlorade was prepared by the reaction ofL-glutamic acid (NH2 was protected by using acetyl group) with SOCl2. ThenL-glutamic acid bridged diporphyrins was synthesized using theL-glutamicacyl dichlorade with 5-(4-hydroxyphenyl)-10, 15, 20-triphenylpo-rphyrin and transition metal porphyrin complexes were synthesized. The dimerwas confirmed using FT-IR spectra, 1HNMR, UV-Vis spectra, the mass spectra(FAB) and element analysis and so on. The Raman spectra, fluorescencespectra and chiral characteristics of the dimer were investigated. the CDspectra showed that there were no split cotton effect in the CD spectra of theligand, however, there were negative and positive Cotton effect in the CDspectra of the complexes, the fluorescence intensity of ligand was stronger thanthat of the copper complex in the fluorescence spectra, while in the Raman,there was great difference between the dimer ligand and the transition metalcomplexes due to changes of the symmetry of porphyrin plane and electroneffect of the d orbits of the metal ion. synthetical routes of dimer and transitionmetal porphyrin dimers was displayed:IV Synthesis of male acid bridged porphyrin dimer ligand andtransition metal porphyrin complexes:The maleilacyl dichlorade was prepared by the reaction of maleic acidwith SOCl2. Then maleic acid bridged diporphyrins was synthesized using themaleilacyl dichlorade with 5-(4-hydroxyphenyl)-10, 15, 20-triphenylporphyrinand transition metal porphyrin complexes were synthesized. The dimers wasconfirmed using UV-Vis spectra, FT-IR spectra, mass spectra (FAB), elementanalysis and so on. Synthetical routes of dimer ligand and transition metalporphyrin dimers were displayed:...