Halide-anion binding by singly and doubly N-confused porphyrins

Hiromitsu Maeda, Tatsuki Morimoto, Atsuhiro Osuka, Hiroyuki Furuta

Research output: Contribution to journalArticle

53 Citations (Scopus)

Abstract

The halide-binding properties of N-confused porphyrin (NCP, 1) and doubly N-confused porphyrins (trans-N 2 CP (2), cis-N 2 CP (3)) were examined in CH 2 Cl 2 . In the free-base forms, cis-N 2 CP (3) showed the highest affinity to each anion (Cl - , Br - , I - ) with association constants K a = 7.8 × 10 3 , 1.9 × 10 3 , and 5.8 × 10 2 M -1 , respectively. As metal complexes, on the other hand, trans-N 2 CP 2-Cu exhibited the highest affinity to Cl - , Br - , and I - with K a = 9.0 × 10 4 , 2.7 × 10 4 , and 1.9 × 10 3 M -1 , respectively. The corresponding K a values for cis-N 2 CP 3-Cu and NCP 1-Cu were about 1/10 and 1/2, respectively, of those of 2-Cu. With the help of density functional theory (DFT) calculations and complementary affinity measurements of a series of trisubstituted N-confused porphyrins, the efficient anion binding of NCPs was attributed to strong hydrogen bonding at the highly polarized NH moieties owing to the electron-deficient C 6 F 5 groups at meso positions as well as the ideally oriented dipole moments and large molecular polarizability. The orientation and magnitude of the dipole moments in NCPs were suggested to be important factors in the differentiation of the affinity for anions.

Original languageEnglish
Pages (from-to)832-844
Number of pages13
JournalChemistry - An Asian Journal
Volume1
Issue number6
DOIs
Publication statusPublished - Dec 1 2006

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Porphyrins
Anions
Dipole moment
Coordination Complexes
Hydrogen Bonding
Density functional theory
Hydrogen bonds
Association reactions
Electrons

All Science Journal Classification (ASJC) codes

  • Biochemistry
  • Organic Chemistry

Cite this

Halide-anion binding by singly and doubly N-confused porphyrins. / Maeda, Hiromitsu; Morimoto, Tatsuki; Osuka, Atsuhiro; Furuta, Hiroyuki.

In: Chemistry - An Asian Journal, Vol. 1, No. 6, 01.12.2006, p. 832-844.

Research output: Contribution to journalArticle

Maeda, Hiromitsu ; Morimoto, Tatsuki ; Osuka, Atsuhiro ; Furuta, Hiroyuki. / Halide-anion binding by singly and doubly N-confused porphyrins. In: Chemistry - An Asian Journal. 2006 ; Vol. 1, No. 6. pp. 832-844.
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