Unusual interchromophoric interactions in β,β' directly and doubly linked corrole dimers: Prohibited electronic communication and abnormal singlet ground states

Sung Cho, Jong Min Lim, Satoru Hiroto, Pyosang Kim, Hiroshi Shinokubo*, Atsuhiro Osuka, Dongho Kim

*Corresponding author for this work

Research output: Contribution to journalArticle

58 Citations (Scopus)

Abstract

Directly and doubly β,β'-linked corrole dimers (DH3CD, DH2CD, and DZnCD) are excellent platforms for the investigation of intercorrole interactions because of their enforced coplanar geometries and short edge-to-edge distances. Through the use of these molecules along with the reference monomer H3CM and the singly β,β'-linked corrole dimer SH3CD, the intercorrole interactions have been systematically studied by density functional theory calculations, ultrafast photophysical measurements, and two-photon absorption measurements. A particular focus was placed on revealing factors that are important for the induced photophysical properties of the doubly linked corrole dimers compared with corrole monomer. In the doubly linked corrole dimers, strong molecular orbital interactions caused by the coplanar geometry and the short interchromophoric distance give rise to perturbations of the electronic states that are responsible for the red-shifted and intensified Q-like band in DH3CD and the broad NIR absorption bands and fast excitation-energy relaxation processes in DH2CD and DZnCD. On the other hand, electronic communication between corrole units is prohibited by the structurally constrained octagonal core in the center, so each constituent corrole unit in the doubly linked corrole dimers maintains an intrinsic π-conjugation system. Consequently, the overall aromaticity of the directly linked corrole dimers can be explained in terms of a linear sum of two constituent corrole monomers, and the singlet biradical character of DH 2CD and DZnCD can be understood in terms of two unpaired electrons (one from each constituent oxidized corrole monomer) and their appropriate interaction. In addition, the nonlinear optical properties of DH2CD and DZnCD with singlet biradical character have been confirmed to be significantly enhanced compared with those of closed-shell DH3CD. Collectively, double β,β'-linkages of corroles provide the coplanar geometry with a short interchromophoric distance and the strained octagonal core that play key roles in allowing the strong molecular orbital interactions and restricting the electronic communication between the two corroles, respectively.

Original languageEnglish (US)
Pages (from-to)6412-6420
Number of pages9
JournalJournal of the American Chemical Society
Volume131
Issue number18
DOIs
StatePublished - May 13 2009

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Dimers
Ground state
Communication
Monomers
Molecular orbitals
Geometry
Excitation energy
Electronic states
Relaxation processes
Density functional theory
Haemophilus influenzae type b-polysaccharide vaccine-diphtheria toxoid conjugate
corrole
Absorption spectra
Photons
Optical properties
Molecules
Electrons

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Cho, Sung ; Lim, Jong Min ; Hiroto, Satoru ; Kim, Pyosang ; Shinokubo, Hiroshi ; Osuka, Atsuhiro ; Kim, Dongho. / Unusual interchromophoric interactions in β,β' directly and doubly linked corrole dimers : Prohibited electronic communication and abnormal singlet ground states. In: Journal of the American Chemical Society. 2009 ; Vol. 131, No. 18. pp. 6412-6420.
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abstract = "Directly and doubly β,β'-linked corrole dimers (DH3CD, DH2CD, and DZnCD) are excellent platforms for the investigation of intercorrole interactions because of their enforced coplanar geometries and short edge-to-edge distances. Through the use of these molecules along with the reference monomer H3CM and the singly β,β'-linked corrole dimer SH3CD, the intercorrole interactions have been systematically studied by density functional theory calculations, ultrafast photophysical measurements, and two-photon absorption measurements. A particular focus was placed on revealing factors that are important for the induced photophysical properties of the doubly linked corrole dimers compared with corrole monomer. In the doubly linked corrole dimers, strong molecular orbital interactions caused by the coplanar geometry and the short interchromophoric distance give rise to perturbations of the electronic states that are responsible for the red-shifted and intensified Q-like band in DH3CD and the broad NIR absorption bands and fast excitation-energy relaxation processes in DH2CD and DZnCD. On the other hand, electronic communication between corrole units is prohibited by the structurally constrained octagonal core in the center, so each constituent corrole unit in the doubly linked corrole dimers maintains an intrinsic π-conjugation system. Consequently, the overall aromaticity of the directly linked corrole dimers can be explained in terms of a linear sum of two constituent corrole monomers, and the singlet biradical character of DH 2CD and DZnCD can be understood in terms of two unpaired electrons (one from each constituent oxidized corrole monomer) and their appropriate interaction. In addition, the nonlinear optical properties of DH2CD and DZnCD with singlet biradical character have been confirmed to be significantly enhanced compared with those of closed-shell DH3CD. Collectively, double β,β'-linkages of corroles provide the coplanar geometry with a short interchromophoric distance and the strained octagonal core that play key roles in allowing the strong molecular orbital interactions and restricting the electronic communication between the two corroles, respectively.",
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Unusual interchromophoric interactions in β,β' directly and doubly linked corrole dimers : Prohibited electronic communication and abnormal singlet ground states. / Cho, Sung; Lim, Jong Min; Hiroto, Satoru; Kim, Pyosang; Shinokubo, Hiroshi; Osuka, Atsuhiro; Kim, Dongho.

In: Journal of the American Chemical Society, Vol. 131, No. 18, 13.05.2009, p. 6412-6420.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Unusual interchromophoric interactions in β,β' directly and doubly linked corrole dimers

T2 - Prohibited electronic communication and abnormal singlet ground states

AU - Cho, Sung

AU - Lim, Jong Min

AU - Hiroto, Satoru

AU - Kim, Pyosang

AU - Shinokubo, Hiroshi

AU - Osuka, Atsuhiro

AU - Kim, Dongho

PY - 2009/5/13

Y1 - 2009/5/13

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AB - Directly and doubly β,β'-linked corrole dimers (DH3CD, DH2CD, and DZnCD) are excellent platforms for the investigation of intercorrole interactions because of their enforced coplanar geometries and short edge-to-edge distances. Through the use of these molecules along with the reference monomer H3CM and the singly β,β'-linked corrole dimer SH3CD, the intercorrole interactions have been systematically studied by density functional theory calculations, ultrafast photophysical measurements, and two-photon absorption measurements. A particular focus was placed on revealing factors that are important for the induced photophysical properties of the doubly linked corrole dimers compared with corrole monomer. In the doubly linked corrole dimers, strong molecular orbital interactions caused by the coplanar geometry and the short interchromophoric distance give rise to perturbations of the electronic states that are responsible for the red-shifted and intensified Q-like band in DH3CD and the broad NIR absorption bands and fast excitation-energy relaxation processes in DH2CD and DZnCD. On the other hand, electronic communication between corrole units is prohibited by the structurally constrained octagonal core in the center, so each constituent corrole unit in the doubly linked corrole dimers maintains an intrinsic π-conjugation system. Consequently, the overall aromaticity of the directly linked corrole dimers can be explained in terms of a linear sum of two constituent corrole monomers, and the singlet biradical character of DH 2CD and DZnCD can be understood in terms of two unpaired electrons (one from each constituent oxidized corrole monomer) and their appropriate interaction. In addition, the nonlinear optical properties of DH2CD and DZnCD with singlet biradical character have been confirmed to be significantly enhanced compared with those of closed-shell DH3CD. Collectively, double β,β'-linkages of corroles provide the coplanar geometry with a short interchromophoric distance and the strained octagonal core that play key roles in allowing the strong molecular orbital interactions and restricting the electronic communication between the two corroles, respectively.

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