Synthesis of Novel Diporphyrins

The novel diporphyrin ligands in which the two porphyrin ring units attached via a rigid aromatic linker were prepared. Their structures have been identified by IR, UV visible, 1 H NMR spectra and elemental analysis.

Synthesis and characterization of novel chiral diporphyrins and their dimetal complexes

Reaction of chiral 2,2'-biamino-1,1'-binaphthalene (R or S) with monosubstituted porphyrin Ib and 2b-c afforded novel chiral diporphyrins 3a-c and 4a-c. Their dimetal complexes [(M)(2)DiPor] have also been prepared. Both structures have been identified by MS, IR, W-visible, H-1 NMR spectra and elemental analysis. These novel chiral compounds show very high optical activities.

Novel Substitution Reactions of 5-(4-Nitrophenyl)-10,15,20-Triphenyl- Porphyrin with Nucleophilic Reagents

Substitution reactions of 5-（4-nitrophenyl）-10, 15,20-triphenylporphyrin （NO2 TPP） and its metal complexes with different nucleophilic reagents were studied for preparing asymmetric porphyrin. The reaction products are different with the nucleophilic reagents changing, and three different products were found. The first obtaining product was diporphyrin when NO2 TPP reacted with sodium phenoxide or diphenoxide in DMF solution; The second was reduced product 5-（4-aminophenyl）-10, 15, 20-triphenylporphrin-M （Ⅱ） when the metal （Ni,Zn） complex of NO2 TPP reacted with above nucleophilic reagents, as well as NO2 TPP reacted with lithium mercaptoethanolate or lithium thiophenolate; The third product CNTPP was achieved with the substitution of nitro group by cyanic anion when NO2 TPP reacted with radium cyanide. Above results were explained with reduction and single electron transfer reaction respectively.

The Strong Cooperativity of Dioxygen Binding by Dicobalt(II) Diporphyrin Compounds in Nonaqueous Solution at Room Temperature

Thermodynamic data were determined for the reversible binding of O 2 to two compounds of dicobalt(II) di(meso tetra phenyl)porphyrin derivatives with different lengths of diamidoaliphatic bridge (abbreviated to Co 2PP 8 and Co 2PP 4) in N,N dimethylformamide at room temperature. The partial pressure of dioxygen necessary for half oxygenation ( P 1/2 ) and Hill coefficient ( n ) at 298 K were determined as follows: P 1/2 =54.2 kPa, n =2.0 for Co 2PP 8 and P 1/2 =6.8 kPa, n =1.8 for Co 2PP 4,respectively. The rate equations of reversible oxygen binding by Co 2PP 8 were determined and the reaction path was proposed. The results of thermodynamic and kinetic studies indicate that there exists strong cooperative effect during oxygenation of the compounds. The ESR observation reveals that the dioxygen complexes formed in the solutions are of superoxo (Co O - 2) type.

Kinetic studies on oxygen binding to dicobalt(Ⅱ) diporphyrin

It has been an important project in the field of biochemistry to search for a seriesof synthetic compounds which have good abilities of carrying oxygen at room temperatureand simulating the hemoglobin’s function of cooperative binding to oxygen. Uemori et al.and Tabushi et al. have reported that some dicobat(Ⅱ) diporphyrins have thecooperative effect of binding oxygn in organic solution below 0℃, the Hill coefficients areabout 1.0--1.5. We have reported the thermodynamics of a dicobalt(Ⅱ)