Experimental crystallographic structural parameters of a range of metaled meso-substituted and unsubstituted porphyrins were reviewed to show how far the meso-substitution by any functional group and the insertion of ...Experimental crystallographic structural parameters of a range of metaled meso-substituted and unsubstituted porphyrins were reviewed to show how far the meso-substitution by any functional group and the insertion of metal in the porphyrins core macrocycle may affect the geometry. The analysis of twists and angles has shown two kinds of distortions: external [T(C<sup>β</sup>-C<sup>α</sup>-C<sup>meso</sup>-X<sup>n</sup>) and T(C<sup>β</sup>-C<sup>α</sup>-C<sup>meso</sup>-C<sup>α</sup>)] and internal [T(N<sup>m</sup>-C<sup>α</sup>-C<sup>meso</sup>-X<sup>n</sup>) and T(N<sup>n</sup>-C<sup>α</sup>-C<sup>meso</sup>-C<sup>α</sup>)] with averages of [+6°and –6°] and [–5°and +5°], respectively. In the meso-substituted case, the external and internal twists C<sup>β</sup>-C<sup>α</sup>-C<sup>meso</sup>-X and N-C<sup>α</sup>-C<sup>meso</sup>-X, respectively are oppositely orientated. Similar effect is observed in meso-unsubstituted of C<sup>β</sup>-C<sup>α</sup>- C<sup>meso</sup>-H and N-C<sup>α</sup>-C<sup>meso</sup>-H. However, the external distortions are more significant than internal. Considering the same order, the limit of distortions is [97°and 132°(–48°)] for external and [91°(–89°) and 52°] for internal. In the two cases, the substituents have opposite directions of distortions. The meso-substituted porphyrins have a high limit of twisting than usubstituted one, depending of the weight of substituents. The average of the bond angular deformations is 168°, almost planar. However, the limit of angular deformation is 94°.展开更多
The electronic spectroscopic properties of several meso-substituted zinc tetrabenzoporphyrins(ZnTBP,ZnTMTBP, ZnTPTBP,ZnTTTBP and ZnTNTBP)have been investigated in toluene.The lifetimes determined showed that the fluor...The electronic spectroscopic properties of several meso-substituted zinc tetrabenzoporphyrins(ZnTBP,ZnTMTBP, ZnTPTBP,ZnTTTBP and ZnTNTBP)have been investigated in toluene.The lifetimes determined showed that the fluorescence of these compounds decay with good double exponentials.展开更多
文摘Experimental crystallographic structural parameters of a range of metaled meso-substituted and unsubstituted porphyrins were reviewed to show how far the meso-substitution by any functional group and the insertion of metal in the porphyrins core macrocycle may affect the geometry. The analysis of twists and angles has shown two kinds of distortions: external [T(C<sup>β</sup>-C<sup>α</sup>-C<sup>meso</sup>-X<sup>n</sup>) and T(C<sup>β</sup>-C<sup>α</sup>-C<sup>meso</sup>-C<sup>α</sup>)] and internal [T(N<sup>m</sup>-C<sup>α</sup>-C<sup>meso</sup>-X<sup>n</sup>) and T(N<sup>n</sup>-C<sup>α</sup>-C<sup>meso</sup>-C<sup>α</sup>)] with averages of [+6°and –6°] and [–5°and +5°], respectively. In the meso-substituted case, the external and internal twists C<sup>β</sup>-C<sup>α</sup>-C<sup>meso</sup>-X and N-C<sup>α</sup>-C<sup>meso</sup>-X, respectively are oppositely orientated. Similar effect is observed in meso-unsubstituted of C<sup>β</sup>-C<sup>α</sup>- C<sup>meso</sup>-H and N-C<sup>α</sup>-C<sup>meso</sup>-H. However, the external distortions are more significant than internal. Considering the same order, the limit of distortions is [97°and 132°(–48°)] for external and [91°(–89°) and 52°] for internal. In the two cases, the substituents have opposite directions of distortions. The meso-substituted porphyrins have a high limit of twisting than usubstituted one, depending of the weight of substituents. The average of the bond angular deformations is 168°, almost planar. However, the limit of angular deformation is 94°.
文摘The electronic spectroscopic properties of several meso-substituted zinc tetrabenzoporphyrins(ZnTBP,ZnTMTBP, ZnTPTBP,ZnTTTBP and ZnTNTBP)have been investigated in toluene.The lifetimes determined showed that the fluorescence of these compounds decay with good double exponentials.
