meso-Aryl substituted rubyrin and its higher homologues: structural characterization and chemical properties

meso-Aryl substituted rubyrin ([26]hexaphyrin(1.1.0.1.1.0)) 2 and a series of rubyrin-type large expanded porphyrins were obtained from a facile one-pot oxidative coupling reaction of meso-pentafluorophenyl substituted tripyrrane 1. The structures of two of the resulting products were determined by single-crystal X-ray diffraction analysis. Whereas [52]dodecaphyrin(1.1.0.1.1.0.1.1.0.1.1.0) 4 takes a symmetric helical conformation, the larger species, [62]pentadecaphyrin(1.1.0.1.1.0.1.1.0.1.1.0.1.1.0) 5, adopts a nonsymmetric distorted conformation in the solid state that contains an intramolecular helical structure. The ability of rubyrin 2 to act as an anion receptor in its diprotonated form (2(.)2H(+)) was demonstrated in methanolic solutions. Oxidation of 2 with MnO(2) gave [24]rubyrin 6, a species that displays antiaromatic characteristics. [26]Rubyrin 2 and [24]rubyrin 6 both underwent metallation when reacted with Zn(OAc)(2) to give the corresponding bis-zinc(II) complexes 7 and 8 quantitatively without engendering a change in the oxidation state of the ligands. As a result, complexes 7 and 8 exhibit aromatic and antiaromatic character, respectively. NICS calculation on these compounds also supported aromaticity of 2 and 7, and antiaromaticity of 6 and 8.     

40]nonaphyrin(1.1.1.1.1.1.1.1.1) and its heterometallic complexes with palladium-carbon bonds

meso-Pentafluorophenyl- substituted [40]nonaphyrin(1.1.1.1.1.1.1.1.1) 3 has been prepared by using a stepwise ring-size-selective synthesis, and has been reduced with NaBH(4) to [42]nonaphyrin(1.1.1.1.1.1.1.1.1) 5. Structurally, 3 is characterized by a figure-of-eight shape, consisting of a porphyrin-like tetrapyrrolic segment and a hexaphyrin-like hexapyrrolic segment, whereas 5 has been found to adopt a distorted nonplanar butterfly-like shape. In the mono-metal complexes 6 and 7, a Zn(II) or Cu(II) ion is bound by the porphyrin-like tetrapyrrolic segment, maintaining the overall structure of 3. Similarly to 3, complexes 6 and 7 are interconvertible with the corresponding complexes 9 and 10 through two-electron reduction with NaBH(4) and oxidation with DDQ. The metal-free hexaphyrin-like segments of 6 and 7 have been shown to serve as a suitable platform for the complexation of two palladium ions, providing hetero-trinuclear metal complexes 11 (Zn(II)-Pd(II)-Pd(II)) and 13 (Cu(II)-Pd(II)-Pd(II)) in high yields, in which the Zn or Cu ion resides at the same porphyrin-like segment, and one Pd ion is bound in an NNCC fashion through double C--H bond activation while the other is bound in an NNC fashion with single C--H bond activation. Multi-metal complexes 11, 12, and 13 exhibit small electrochemical HOMO-LUMO gaps (<0.6 eV), despite their nonplanar conformations.     

Group 12 metal complexes of [26]hexaphyrin(1.1.1.1.1.1)

Metalation of meso-hexakis(pentafluorophenyl)-substituted [26]hexaphyrin(1.1.1.1.1.1) (1) has been explored with group 12 metal ions Zn(II), Cd(II), and Hg(II). Zn(II) and Cd(II) ions afforded dinuclear gable-shaped complexes 2 and 3 in good yields, while Hg(II) ion provided bis-Hg(II) and mono-Hg(II) planar complexes (4 and 5) via C-H bond cleavage.     

Group 10 metal complexes of meso-aryl-substituted [26]hexaphyrins with a metal-carbon bond

Nickel(II), palladium(II), and platinum(II) complexes of meso-aryl-substituted [26]hexaphyrin have been prepared and structurally characterized. In mono-metalated complexes, the metal ion is commonly bound with three pyrrolic nitrogen atoms and one pyrrolic beta-carbon, whereas a bis-Pd(II) complex exhibits a unique structure involving a Pd-C(alpha) bond. These results reveal novel coordination abilities of the hexaphyrin that lead to a metal-carbon bond at either pyrrolic C(beta) or C(alpha) position.     

Core-modified phthalocyanine analogues with a seven-membered ring unit in place of a five-membered ring unit

A variety of phthalocyanine analogues with a seven-membered ring unit in place of a five-membered ring unit were synthesized from aromatic dicarbonitriles bearing cyano groups at 1,4-separate positions. Based on the spectroscopic analyses and theoretical calculations, tetraazachlorine-like electronic structures of these novel compounds stemming from severe twist of the conjugation system at the seven-membered ring unit have been revealed.     

Comparative photophysics of [26]- and [28]hexaphyrins(1.1.1.1.1.1): large two-photon absorption cross section of aromatic [26]hexaphyrins(1.1.1.1.1.1)

We have explored the electronic natures of representative expanded porphyrins, [26]- and [28]hexaphyrins, to investigate the interplay between the aromaticity and antiaromaticity that is brought by two electron oxidation/reduction processes. The excited singlet and triplet states of [26]hexaphyrin in solution exhibit lifetimes of 125 ps and 1.8 mus, respectively, as revealed by various time-resolved spectroscopic measurements. On the other hand, [28]hexaphyrin shows faster singlet and triplet lifetimes than those of [26]hexaphyrin, which is largely in accordance with the perturbation of aromaticity due to the pi electron formulation of [4n] in [28]hexaphyrins. The two-photon absorption cross-section values at 1200 nm for [26]hexaphyrins show ca. 9890 GM which is >10(2) larger than those of porphyrins. The reduced TPA values of 2600 and 810 GM of [28]hexaphyrin and perfluorinated [28]hexaphyrin, respectively, match well with their relatively short excited-state lifetimes. Overall, the enhanced excited-state lifetimes for various hexaphyrins go in line with the increased TPA cross-section values and the ring planarity.