Electronic property of Group IV phthalocyanine dimers: SiPcMPc

Gwanghoon Kwag, Cheolbeom Bae, Sunghyun Kim, Jae Joon Lee, Malcome E. Kenney

Research output: Contribution to journalArticlepeer-review

3 Scopus citations

Abstract

A series of Group IV phthalocyanine (Pc) dimers, (n-C6H13)3SiOSiPcOSiPcOSi(n-C6H13)3 (SiPcSiPc), (n-C6H13)3SiOSiPcOGePcOSi(n-C6H13)3 (SiPcGePc), and (n-C6H13)3SiOSiPcOSnPcOH (SiPcSnPc), was characterized by cyclic voltammetry and DFT calculation. Two oxidations and two reductions were observed for (n-C6H13)3SiOSiPcOSiPcOSi(n-C6H13)3 and (n-C6H13)3SiOSiPcOGePcOSi(n-C6H13)3, while there were two oxidations and three reductions for (n-C6H13)3SiOSiPcOSnPcOH. The Pc with a bigger size of the central metal in one part of the dimeric compound is more difficult to be oxidized but it is easier to be reduced at the same time: i.e., both oxidation and reduction potentials showed a positive shift with the increase of the size of the central metal atom. Density functional theory was used to optimize the structures of the Pc dimers and to understand the electrochemical properties. The optimized structures of HOSiPcOSiPcOH, HOSiPcOGePcOH and HOSiPcOSnPcOH as model compounds for SiPcSnPc, SiPcGePc, SiPcSiPc, respectively, show that all the Pc dimers are staggered, the plane-to-plane distances are 3.394, 3.538 and 3.722 Å, respectively. Tin generates a saddle-type structure of phthalocyanine, but silicon or germanium does not greatly distort the ring structure, and yields a planar ring structure. A large plane-to-plane distance and a high degree of plane distortion yield a red-shift of Q-band, a low ring current, high oxidation and low reduction potentials and high ionization energies.

Original languageEnglish
Pages (from-to)2027-2032
Number of pages6
JournalInorganica Chimica Acta
Volume362
Issue number6
DOIs
StatePublished - 20 Apr 2009

Keywords

  • Cyclic voltammetry
  • DFT calculation
  • Group IV phthalocyanine dimers

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