Structure-property relationship for two-photon absorbing multiporphyrins

Supramolecular assembly of highly-conjugated multiporphyrinic ladders and prisms

Shanmugam Easwaramoorthi, So Young Jang, Zin Seok Yoon, Jong Min Lim, Cheng Wei Lee, Chi Lun Mai, Yen Chun Liu, Chen Yu Yeh, Josh Vura-Weis, Michael R Wasielewski, Dongho Kim

Research output: Contribution to journalArticle

28 Citations (Scopus)

Abstract

Two-photon absorption (TPA) phenomena of a series of single-strand as well as supramolecular self-assembled ladders and prisms of highly conjugated ethyne bridged multiporphyrin dimer, trimer, and star shaped pentamer have been investigated. The ligand mediated self-assembled supramolecular structures were characterized by UV-visible spectroscopy and small- and wide-angle X-ray scattering (SAXS/WAXS) analysis. The TPA cross section values of multiporphyrins increase nonlinearly from ∼100 to ∼18000 GM with an increased number of porphyrin units and elongated π-conjugation length by virtue of charge transfer and excited-state cumulenic configurations. The observed opposite TPA behavior between their supramolecular ladder and prism configurations necessitates the importance of interstrand interactions between the multiporphyrinic units and the overall shape of the assembly. Furthermore, the diminished TPA cross section of the pentamer, despite the increased π-conjugation resulting from duplex formation suggests that destabilizing the essential functional configurations at the cost of elongation of π-delocalization pathway must cause unfavorable effects. We have also shown that one- and two-photon allowed energy-levels of linear multiporphyrins are nearly isoenergetic and the latter transition originates exclusively from the extent of π-delocalization within the molecule. The identical TPA maximum position of the trimer and pentamer indicates that the TPA of the pentamer arises only from its basic trimer unit in spite of its extended two-dimensional π-conjugation pathway involving five porphyrinic units.

Original languageEnglish
Pages (from-to)6563-6570
Number of pages8
JournalJournal of Physical Chemistry A
Volume112
Issue number29
DOIs
Publication statusPublished - Jul 24 2008

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Ladders
Prisms
ladders
prisms
Photons
assembly
photons
trimers
conjugation
absorption cross sections
configurations
Acetylene
Porphyrins
X ray scattering
Excited states
porphyrins
Dimers
strands
Electron energy levels
elongation

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Structure-property relationship for two-photon absorbing multiporphyrins : Supramolecular assembly of highly-conjugated multiporphyrinic ladders and prisms. / Easwaramoorthi, Shanmugam; Jang, So Young; Yoon, Zin Seok; Lim, Jong Min; Lee, Cheng Wei; Mai, Chi Lun; Liu, Yen Chun; Yeh, Chen Yu; Vura-Weis, Josh; Wasielewski, Michael R; Kim, Dongho.

In: Journal of Physical Chemistry A, Vol. 112, No. 29, 24.07.2008, p. 6563-6570.

Research output: Contribution to journalArticle

Easwaramoorthi, Shanmugam ; Jang, So Young ; Yoon, Zin Seok ; Lim, Jong Min ; Lee, Cheng Wei ; Mai, Chi Lun ; Liu, Yen Chun ; Yeh, Chen Yu ; Vura-Weis, Josh ; Wasielewski, Michael R ; Kim, Dongho. / Structure-property relationship for two-photon absorbing multiporphyrins : Supramolecular assembly of highly-conjugated multiporphyrinic ladders and prisms. In: Journal of Physical Chemistry A. 2008 ; Vol. 112, No. 29. pp. 6563-6570.
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AU - Jang, So Young

AU - Yoon, Zin Seok

AU - Lim, Jong Min

AU - Lee, Cheng Wei

AU - Mai, Chi Lun

AU - Liu, Yen Chun

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AU - Vura-Weis, Josh

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AU - Kim, Dongho

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AB - Two-photon absorption (TPA) phenomena of a series of single-strand as well as supramolecular self-assembled ladders and prisms of highly conjugated ethyne bridged multiporphyrin dimer, trimer, and star shaped pentamer have been investigated. The ligand mediated self-assembled supramolecular structures were characterized by UV-visible spectroscopy and small- and wide-angle X-ray scattering (SAXS/WAXS) analysis. The TPA cross section values of multiporphyrins increase nonlinearly from ∼100 to ∼18000 GM with an increased number of porphyrin units and elongated π-conjugation length by virtue of charge transfer and excited-state cumulenic configurations. The observed opposite TPA behavior between their supramolecular ladder and prism configurations necessitates the importance of interstrand interactions between the multiporphyrinic units and the overall shape of the assembly. Furthermore, the diminished TPA cross section of the pentamer, despite the increased π-conjugation resulting from duplex formation suggests that destabilizing the essential functional configurations at the cost of elongation of π-delocalization pathway must cause unfavorable effects. We have also shown that one- and two-photon allowed energy-levels of linear multiporphyrins are nearly isoenergetic and the latter transition originates exclusively from the extent of π-delocalization within the molecule. The identical TPA maximum position of the trimer and pentamer indicates that the TPA of the pentamer arises only from its basic trimer unit in spite of its extended two-dimensional π-conjugation pathway involving five porphyrinic units.

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