Intermolecular interactions of tetrabenzoporphyrin- and phthalocyanine-based charge-transfer complexes

The effect of molecular modification on the intermolecular interactions in tetrabenzoporphyrin-based charge transfer complexes is reported. TPP[Fe III (tbp)Cl 2 ] 2 , TPP[Co III (tbp)Cl 2 ] 2 and TPP[Co III (tbp)Br 2 ] 2 (TPP = tetraphenylphosphonium and tbp = tetrabenzoporphyrin) were synthesized a...

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Bibliographic Details
Published in:Dalton transactions : an international journal of inorganic chemistry 2019-12, Vol.48 (48), p.17723-17728
Main Authors: Nishi, Miki, Hayata, Yuki, Hoshino, Norihisa, Hanasaki, Noriaki, Akutagawa, Tomoyuki, Matsuda, Masaki
Format: Article
Language:English
Subjects:
Charge transfer
Charge transport
Chemical bonds
Crystal structure
Crystallography
Ligands
Personal computers
Transport properties
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Summary:The effect of molecular modification on the intermolecular interactions in tetrabenzoporphyrin-based charge transfer complexes is reported. TPP[Fe III (tbp)Cl 2 ] 2 , TPP[Co III (tbp)Cl 2 ] 2 and TPP[Co III (tbp)Br 2 ] 2 (TPP = tetraphenylphosphonium and tbp = tetrabenzoporphyrin) were synthesized and their crystal structures were compared to those of the reported TPP[M III (tbp)(CN) 2 ] 2 , TPP[Fe III (tbp)Br 2 ] 2 and TPP[M III (Pc)L 2 ] 2 complexes (Pc = phthalocyanine; and L = CN, Cl or Br). The prepared CT complexes were isostructural to reported systems. However, their intermolecular interactions were found to depend on the combination of the macrocyclic (Mc) and axial ligands (L). In Pc-based systems, the overlap integral between HOMOs of Pc decreased with the increase in the size of the axial ligand, which indicated that the intermolecular interactions in Pc-based systems were dominated by repulsive interactions. On the other hand, in tbp-based systems, attractive and repulsive interactions competed with each other. Furthermore, charge transport properties were found to depend on the central metal ion as well as the combination of Mc and L, which suggested that minor molecular modifications to porphyrin complexes will cause drastic changes in both inter- and intramolecular interactions. The effect of molecular modification on the intermolecular interactions in tetrabenzoporphyrin-based charge transfer complexes is reported.
ISSN:1477-9226
1477-9234
DOI:10.1039/c9dt03653a