These authors contributed equally to this work.
Exploring Supramolecular Self-Assembly of Tetraarylporphyrins by Halogen Bonding: Crystal Engineering with Diversely Functionalized Six-Coordinate Tin(L)2–Porphyrin Tectons
Article first published online: 13 SEP 2013
Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chemistry - A European Journal
Volume 19, Issue 44, pages 14941–14949, October 25, 2013
How to Cite
Titi, H. M., Patra, R. and Goldberg, I. (2013), Exploring Supramolecular Self-Assembly of Tetraarylporphyrins by Halogen Bonding: Crystal Engineering with Diversely Functionalized Six-Coordinate Tin(L)2–Porphyrin Tectons. Chem. Eur. J., 19: 14941–14949. doi: 10.1002/chem.201301857
- Issue published online: 16 OCT 2013
- Article first published online: 13 SEP 2013
- Manuscript Revised: 24 JUL 2013
- Manuscript Received: 14 MAY 2013
- The Israel Science Foundation. Grant Number: 108/12
- supramolecular chemistry;
This study targets the construction of porphyrin assemblies directed by halogen bonds, by utilizing a series of purposely synthesized Sn(axial ligand)2–(5,10,15,20-tetraarylporphyrin) [Sn(L)2-TArP] complexes as building units. The porphyrin moiety and the axial ligands in these compounds contain different combinations of complimentary molecular recognition functions. The former bears p-iodophenyl, p-bromophenyl, 4′-pyridyl, or 3′-pyridyl substituents at the meso positions of the porphyrin ring. The latter comprises either a carboxylate or hydroxy anchor for attachment to the porphyrin-inserted tin ion and a pyridyl-, benzotriazole-, or halophenyl-type aromatic residue as the potential binding site. The various complexes were structurally analyzed by single-crystal X-ray diffraction, accompanied by computational modeling evaluations. Halogen-bonding interactions between the lateral aryl substituents of one unit of the porphyrin complex and the axial ligands of neighboring moieties was successfully expressed in several of the resulting samples. Their occurrence is affected by structural (for example, specific geometry of the six-coordinate complexes) and electronic effects (for example, charge densities and electrostatic potentials). The shortest intermolecular I⋅⋅⋅N halogen-bonding distance of 2.991 Å was observed between iodophenyl (porphyrin) and benzotriazole (axial ligand) moieties. Manifestation of halogen bonds in these relatively bulky compounds without further activation of the halophenyl donor groups by electron-withdrawing substituents is particularly remarkable.