Self-Assembly of Porphyrin Arrays by Hydrogen Bonding in the Solid State: An Orthogonal Porphyrin–Bisresorcinol System

Abstract

The crystal structures of two adducts (1´2 H 2 O´2 IBB and 1´4 THF; IBB isobutyl benzoate) of an orthogonal porphyrin ± bisresorcinol derivative, the Zn II complex of 5,15-bis(3,5-dihydroxy-1-phenyl)octaethylporphyrin (1), are described. Both adducts contain an extensive hydrogen-bonding network, which forces the porphyrin rings into a columnar alignment. The resulting sheets are layered to give either a staggered arrangement (in adduct 12 H 2 O´2 IBB) or herringbone-type edge-to-face contacts (in adduct 14 THF) of the porphyrin moieties in neighboring sheets. In the large cavities left, guest molecules are incorporated by hydrogen bonding (resorcinol´´´OH 2´´Í BB) in adduct 1´2 H 2 O´2 IBB, or by a combination of hydrogen bonding (resorcinol´´´THF) and metal coordination (Zn II´´´T HF) in adduct 1´4 THF. The use of the large porphyrin spacer in the orthogonality strategy is discussed in the light of the known crystal structures of related anthracene ± bisresorcinol derivatives.

High‐Yielding Synthesis of β‐Octaalkyl‐meso‐(bromophenyl)‐Substituted Porphyrins and X‐ray Study of Axial Complexes of Their Zinc Complexes with THF and 1,4‐Dioxane

“…[30,31] In all the complexes described, the porphyrin macrocycles are virtually planar, independently of the zinc coordination number. Metal-oxygen distances were noticeably increased (2.371-2.555 Å) [43][44][45][46][47][48][49] and close to that observed in complex ZnP-1. This is apparently a consequence of strong CH-π interactions (C···C distances between bromophenyl substituents and pyrrole moieties are 3.447-3.856 Å) observed in two adjacent molecules in the unit cell of the complex (Zn···Zn 6.256 Å; Figures 12 and 13).…”

One‐Dimensional, Cofacial Porphyrin Polymers Formed by Self‐Assembly of meso‐Tetrakis(ERE Donor) Zinc(II) Porphyrins

“…[78] It was recognized that octahedrally coordinated zinc(II) porphyrins can be formed as well, [51][52][53][54][55][56][61][62][63][64][65][66][67][68][69][70][71] especially when the porphyrin ligand bears multiple electron-withdrawing groups. [78] It was recognized that octahedrally coordinated zinc(II) porphyrins can be formed as well, [51][52][53][54][55][56][61][62][63][64][65][66][67][68][69][70][71] especially when the porphyrin ligand bears multiple electron-withdrawing groups.…”

“…Within the series of reported zinc(II) porphyrins with two axial O ligands, [51,52,[60][61][62][63][64][65][66][67][68][69][70][71] this value is in the expected range for bisA C H T U N G T R E N N U N G (ether) complexes. The ZnÀO distances in bisA C H T U N G T R E N N U N G (THF) complexes of ZnTPP derivatives are between 2.371 [63] and 2.56 , [68] and in a zinc(II) porphyrin polymer the Zn À O benzylmethylether distances were found to be 2.434 . [72] In the case of [3Zn] 1 , the phenyl groups connected to the coordinating EBrE donor groups (E = OMe) are bent out of the porphyrin plane by 13.7(8)8 away from the adjacent zinc(II) porphyrin unit; this arrangement pulls two adjacent porphyrin rings closer together.…”

Crystal structure of [5-n-butyl-10-(2,5-dimethoxyphenyl)-2,3,7,8,13,12,17,18-octaethylporphyrinato]nickel(II)

“…Other highly substituted porphyrin structures include 5, 15disubstituted-2,3,7,8,12,13,17,18-octaethylporphyrins (Senge et al, 2000;Kobayashi et al, 1998;Jiang et al, 1996;Zhu et al, 1992) and 5,10,15-trisubstituted-2,3,7,8,12,13,17,18-octaethylporphyrins (Kalisch & Senge, 1998;Senge et al, 2000;Senge & Bischoff, 2001).…”