1D Columnar stacking structures in the single crystals of 5,10-diarylporphyrin metal complexes

Abstract

ABSTRACT:A general design of a meso-aryl porphyrin for the formation of a 1D columnar stacking structure in the single crystal state is proposed. We found that 5,10-diphenyl-and 5,10-bis(pentafluorophenyl)porphyrin metal complexes (M = Zn, Ni) can stack in a complementary manner to form a 1D columnar stacking structure in the single crystals, while the corresponding freebase porphyrins displayed herringbone or dimeric orthogonal packing forms. The structural details of the obtained 1D columnar packing structures are discussed in comparison with precedented examples including 5,10-diphenylporphyrin Cu(II) and Ag(II) complexes, 5,10-diphenyl N-confused porphyrin Ag(III) complex and 5,10-bis(pentafluorophenyl)corrole.

Development of the Peripheral Functionalization Chemistry of meso‐Free Corroles

“…Interestingly, 16 formed a columnar stacking assembly as observed for various 5,10diarylporphyrins. [24] The crystal structures of the corresponding Co III and Ga III complexes were also revealed, and their dihedral angles are within the same degree (63-86°). [22] 3.…”

Rational Synthesis of 5,10-Diazaporphyrins via Nucleophilic Substitution Reactions of α,α′-Dibromotripyrrin and Dihydrogenation to Give 5,10-Diazachlorins

“…In the crystal, 2 forms a one-dimensional columnar stacking structure (Figure S3-2). The inter-porphyrin distances are 3.378 and 3.375 Å. This packing structure is formed by not only π–π interaction but also CH–N hydrogen bonding interactions between the meso -nitrogen atom and ortho -hydrogen atom of the phenyl group.…”

“…(Some signals were not observed presumably because of their broadness). UV/vis (CH 2 Cl 2 ): λ max [nm] (ε [M −1 cm −1 ]) = 401 (110,000), 535 (18,000), 597 (12,000), and 614 (11,000) 5,. 13 C{ 1 H} NMR (CDCl 3 , r.t.) δ (ppm): 176.3, 166.3, 160.7, 150.4, 149.1, 145.2, 141.9, 141.2, 140.2, 135.3, 135.2, 133.8, 133.1, 132.0, 130.9, 129.7, 129.5, 128.6, 128.5, 128.4, 128.1, 127.2, 122.7, 116.9, 36.8, and 33.8.…”