Water-soluble [2.2]paracyclophane chromophores with large two-photon action cross sections

Han Young Woo, Janice W. Hong, Bin Liu, Alexander Mikhailovsky, Dmitry Korystov, Guillermo C. Bazan

Research output: Contribution to journalArticle

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Abstract

A series of α,ω-donor-substituted distyrylbenzene dimers held together by the [2.2]paracyclophane core were designed, synthesized, and characterized. Different substituents were chosen to modulate the strength of the donor nitrogen groups and to allow the molecules to be either neutral and soluble in nonpolar organic solvents or charged and water-soluble. The specific neutral structures are (in order of decreasing donor strength) 4,7,12,15-tetra[N,N-bis(6′′-chlorohexyl)-4′-aminostyryl]-[2.2]paracyclophane (1N), 4,7,12,15-tetra[(N-(6′′-chlorohexyl)carbazol-3′-yl)vinyl]-[2.2]paracyclophane (2N), and 4,7,12,15-tetra[N,N-bis(4′′-(6′″-chlorohexyl)phenyl)-4′-aminostyryl]-[2.2]paracyclophane (3N). The charged species are 4,7,12,15-tetra[N,N-bis(6′′-(N,N,N-trimethylammonium)hexyl)-4′-aminostyryl]-[2.2]paracyclophane octaiodide (1C), 4,7,12,15-tetra[(N-(6′′-(N,N,N-trimethylammonium)hexyl)carbazol-3′-yl)vinyl]-[2.2]paracyclophane octaiodide (2C), and 4,7,12,15-tetra[N,N-bis(4′′-(6′″-(N,N,N-trimethylammonium)hexyl)phenyl)-4′-aminostyryl]-[2.2]paracyclophane octaiodide (3C). Two-photon excitation spectra, measured using the two-photon induced fluorescence technique, show in toluene the following trend for the two-photon cross sections (δ): 3N > 2N > 1N. In water the δ values follow the same order, 3C ≈ 2C > 1C, but are smaller (approximately one-third). Significantly, the fluorescence quantum yield (η) in water decreases much more for 1, relative to 2 and 3. The two-photon action cross sections (δη) of 2C and 3C are 294 GM and 359 GM, respectively. These values are among the highest reported thus far. These results show that, to maximize the δη in this class of chromophores, one needs to fine-tune the magnitude of the charge transfer character of the excited state, to minimize fluorescence quenching in polar media.

Original languageEnglish
Pages (from-to)820-821
Number of pages2
JournalJournal of the American Chemical Society
Volume127
Issue number3
DOIs
Publication statusPublished - 2005 Jan 26
Externally publishedYes

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Chromophores
Photons
Water
Fluorescence
Quantum yield
Excited states
Dimers
Organic solvents
Toluene
Charge transfer
Quenching
Nitrogen
Molecules
(2.2)paracyclophane

ASJC Scopus subject areas

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

Cite this

Water-soluble [2.2]paracyclophane chromophores with large two-photon action cross sections. / Woo, Han Young; Hong, Janice W.; Liu, Bin; Mikhailovsky, Alexander; Korystov, Dmitry; Bazan, Guillermo C.

In: Journal of the American Chemical Society, Vol. 127, No. 3, 26.01.2005, p. 820-821.

Research output: Contribution to journalArticle

Woo, Han Young ; Hong, Janice W. ; Liu, Bin ; Mikhailovsky, Alexander ; Korystov, Dmitry ; Bazan, Guillermo C. / Water-soluble [2.2]paracyclophane chromophores with large two-photon action cross sections. In: Journal of the American Chemical Society. 2005 ; Vol. 127, No. 3. pp. 820-821.
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abstract = "A series of α,ω-donor-substituted distyrylbenzene dimers held together by the [2.2]paracyclophane core were designed, synthesized, and characterized. Different substituents were chosen to modulate the strength of the donor nitrogen groups and to allow the molecules to be either neutral and soluble in nonpolar organic solvents or charged and water-soluble. The specific neutral structures are (in order of decreasing donor strength) 4,7,12,15-tetra[N,N-bis(6′′-chlorohexyl)-4′-aminostyryl]-[2.2]paracyclophane (1N), 4,7,12,15-tetra[(N-(6′′-chlorohexyl)carbazol-3′-yl)vinyl]-[2.2]paracyclophane (2N), and 4,7,12,15-tetra[N,N-bis(4′′-(6′″-chlorohexyl)phenyl)-4′-aminostyryl]-[2.2]paracyclophane (3N). The charged species are 4,7,12,15-tetra[N,N-bis(6′′-(N,N,N-trimethylammonium)hexyl)-4′-aminostyryl]-[2.2]paracyclophane octaiodide (1C), 4,7,12,15-tetra[(N-(6′′-(N,N,N-trimethylammonium)hexyl)carbazol-3′-yl)vinyl]-[2.2]paracyclophane octaiodide (2C), and 4,7,12,15-tetra[N,N-bis(4′′-(6′″-(N,N,N-trimethylammonium)hexyl)phenyl)-4′-aminostyryl]-[2.2]paracyclophane octaiodide (3C). Two-photon excitation spectra, measured using the two-photon induced fluorescence technique, show in toluene the following trend for the two-photon cross sections (δ): 3N > 2N > 1N. In water the δ values follow the same order, 3C ≈ 2C > 1C, but are smaller (approximately one-third). Significantly, the fluorescence quantum yield (η) in water decreases much more for 1, relative to 2 and 3. The two-photon action cross sections (δη) of 2C and 3C are 294 GM and 359 GM, respectively. These values are among the highest reported thus far. These results show that, to maximize the δη in this class of chromophores, one needs to fine-tune the magnitude of the charge transfer character of the excited state, to minimize fluorescence quenching in polar media.",
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T1 - Water-soluble [2.2]paracyclophane chromophores with large two-photon action cross sections

AU - Woo, Han Young

AU - Hong, Janice W.

AU - Liu, Bin

AU - Mikhailovsky, Alexander

AU - Korystov, Dmitry

AU - Bazan, Guillermo C.

PY - 2005/1/26

Y1 - 2005/1/26

N2 - A series of α,ω-donor-substituted distyrylbenzene dimers held together by the [2.2]paracyclophane core were designed, synthesized, and characterized. Different substituents were chosen to modulate the strength of the donor nitrogen groups and to allow the molecules to be either neutral and soluble in nonpolar organic solvents or charged and water-soluble. The specific neutral structures are (in order of decreasing donor strength) 4,7,12,15-tetra[N,N-bis(6′′-chlorohexyl)-4′-aminostyryl]-[2.2]paracyclophane (1N), 4,7,12,15-tetra[(N-(6′′-chlorohexyl)carbazol-3′-yl)vinyl]-[2.2]paracyclophane (2N), and 4,7,12,15-tetra[N,N-bis(4′′-(6′″-chlorohexyl)phenyl)-4′-aminostyryl]-[2.2]paracyclophane (3N). The charged species are 4,7,12,15-tetra[N,N-bis(6′′-(N,N,N-trimethylammonium)hexyl)-4′-aminostyryl]-[2.2]paracyclophane octaiodide (1C), 4,7,12,15-tetra[(N-(6′′-(N,N,N-trimethylammonium)hexyl)carbazol-3′-yl)vinyl]-[2.2]paracyclophane octaiodide (2C), and 4,7,12,15-tetra[N,N-bis(4′′-(6′″-(N,N,N-trimethylammonium)hexyl)phenyl)-4′-aminostyryl]-[2.2]paracyclophane octaiodide (3C). Two-photon excitation spectra, measured using the two-photon induced fluorescence technique, show in toluene the following trend for the two-photon cross sections (δ): 3N > 2N > 1N. In water the δ values follow the same order, 3C ≈ 2C > 1C, but are smaller (approximately one-third). Significantly, the fluorescence quantum yield (η) in water decreases much more for 1, relative to 2 and 3. The two-photon action cross sections (δη) of 2C and 3C are 294 GM and 359 GM, respectively. These values are among the highest reported thus far. These results show that, to maximize the δη in this class of chromophores, one needs to fine-tune the magnitude of the charge transfer character of the excited state, to minimize fluorescence quenching in polar media.

AB - A series of α,ω-donor-substituted distyrylbenzene dimers held together by the [2.2]paracyclophane core were designed, synthesized, and characterized. Different substituents were chosen to modulate the strength of the donor nitrogen groups and to allow the molecules to be either neutral and soluble in nonpolar organic solvents or charged and water-soluble. The specific neutral structures are (in order of decreasing donor strength) 4,7,12,15-tetra[N,N-bis(6′′-chlorohexyl)-4′-aminostyryl]-[2.2]paracyclophane (1N), 4,7,12,15-tetra[(N-(6′′-chlorohexyl)carbazol-3′-yl)vinyl]-[2.2]paracyclophane (2N), and 4,7,12,15-tetra[N,N-bis(4′′-(6′″-chlorohexyl)phenyl)-4′-aminostyryl]-[2.2]paracyclophane (3N). The charged species are 4,7,12,15-tetra[N,N-bis(6′′-(N,N,N-trimethylammonium)hexyl)-4′-aminostyryl]-[2.2]paracyclophane octaiodide (1C), 4,7,12,15-tetra[(N-(6′′-(N,N,N-trimethylammonium)hexyl)carbazol-3′-yl)vinyl]-[2.2]paracyclophane octaiodide (2C), and 4,7,12,15-tetra[N,N-bis(4′′-(6′″-(N,N,N-trimethylammonium)hexyl)phenyl)-4′-aminostyryl]-[2.2]paracyclophane octaiodide (3C). Two-photon excitation spectra, measured using the two-photon induced fluorescence technique, show in toluene the following trend for the two-photon cross sections (δ): 3N > 2N > 1N. In water the δ values follow the same order, 3C ≈ 2C > 1C, but are smaller (approximately one-third). Significantly, the fluorescence quantum yield (η) in water decreases much more for 1, relative to 2 and 3. The two-photon action cross sections (δη) of 2C and 3C are 294 GM and 359 GM, respectively. These values are among the highest reported thus far. These results show that, to maximize the δη in this class of chromophores, one needs to fine-tune the magnitude of the charge transfer character of the excited state, to minimize fluorescence quenching in polar media.

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