Structural changes in non-planar octaaryl substituted phthalocyanine phosphorus complexes

Taniyuki Furuyama, Ryosuke Harako, Nagao Kobayashi

Research output: Contribution to journalArticlepeer-review

8 Citations (Scopus)

Abstract

Phosphorus complexes of non-planar α-octaaryl phthalocyanine derivatives ((α-Ar)8Pc), 3a and 3b have been synthesized by introduction of phosphorus(V) ions into free-base Pcs 2a and 2b. 3a and 3b were characterized by MS, 1H and 31P NMR spectra. The solid state structure of 3a indicated a ruffled Pc structure due to the small atomic radius of phosphorus, although the corresponding free-base Pc 2a has a saddled Pc structure. The phosphorus complexes showed intense absorption bands (Q-bands) in the near-IR region, while the introduction of electron-donating groups at the peripheral phenyl groups was efficient for additional red-shifting of the Q-band. Electrochemical data revealed that the red-shift of the Q-band is attributable to a decrease in the HOMO-LUMO gap due to significant and moderate stabilization of the LUMO and HOMO, respectively. MO calculations suggested that the phosphorus(V) ion intensified the electronic interaction between the peripheral aryl moieties and the Pc macrocyclic core.

Original languageEnglish
Pages (from-to)500-509
Number of pages10
JournalJournal of Porphyrins and Phthalocyanines
Volume19
Issue number1-3
DOIs
Publication statusPublished - 2015 Jan 1

Keywords

  • electronic structure
  • near-infrared absorption
  • phosphorus phthalocyanine
  • ruffled structure

ASJC Scopus subject areas

  • Chemistry(all)

Fingerprint Dive into the research topics of 'Structural changes in non-planar octaaryl substituted phthalocyanine phosphorus complexes'. Together they form a unique fingerprint.

Cite this