Nonlinear optical properties and excited-state dynamics of highly symmetric expanded porphyrins

Zin Seok Yoon, Jung Ho Kwon, Min Chul Yoon, Mi Kyoung Koh, Su Bum Noh, Jonathan L. Sessler, Jeong Tae Lee, Daniel Seidel, Apolonio Aguilar, Soji Shimizu, Masaaki Suzuki, Atsuhiro Osuka, Dongho Kim

Research output: Contribution to journalArticle

127 Citations (Scopus)

Abstract

A strong correlation among calculated Nucleus-Independent Chemical Shift (NICS) values, molecular planarity, and the observed two-photon absorption (TPA) values was found for a series of closely matched expanded porphyrins. The expanded porphyrins in question consisted of [26]hexaphyrin, [28]-hexaphyrin, rubyrin, amethyrin, cyclo[6]pyrrole, cyclo[7]pyrrole, and cyclo[8]pyrrole containing 22, 24, 26, 28, and 30 π-electrons. Two of the systems, [28]hexaphyrin and amethyrin, were considered to be antiaromatic as judged from a simple application of Hückel's [4n + 2] rule. These systems displayed positive NICS(0) values (+43.5 and +17.1 ppm, respectively) and gave rise to TPA values of 2600 and 3100 GM, respectively. By contrast, a set of congeners containing 22, 26, and 30 π-electrons (cyclo[n]pyrrole, n = 6, 7, and 8, respectively) were characterized by a linear correlation between the NICS and TPA values. In the case of the oligopyrrolic macrocycles containing 26 π-electron systems, a further correlation between the molecular structure and various markers associated with aromaticity was seen. In particular, a decrease in the excited state lifetimes and an increase in the TPA values were seen as the flexibility of the systems increased. Based on the findings presented here, it is proposed that various readily measurable optical properties, including the two-photon absorption cross-section, can provide a quantitative experimental measure of aromaticity in macrocyclic π-conjugated systems.

Original languageEnglish
Pages (from-to)14128-14134
Number of pages7
JournalJournal of the American Chemical Society
Volume128
Issue number43
DOIs
Publication statusPublished - 2006 Nov 1

Fingerprint

Porphyrins
Photons
Excited states
Pyrroles
Optical properties
Chemical shift
Electrons
Molecular Structure
Molecular structure

All Science Journal Classification (ASJC) codes

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

Cite this

Yoon, Zin Seok ; Kwon, Jung Ho ; Yoon, Min Chul ; Koh, Mi Kyoung ; Noh, Su Bum ; Sessler, Jonathan L. ; Lee, Jeong Tae ; Seidel, Daniel ; Aguilar, Apolonio ; Shimizu, Soji ; Suzuki, Masaaki ; Osuka, Atsuhiro ; Kim, Dongho. / Nonlinear optical properties and excited-state dynamics of highly symmetric expanded porphyrins. In: Journal of the American Chemical Society. 2006 ; Vol. 128, No. 43. pp. 14128-14134.
@article{5d910b7d9e5c4b9e8a03a72c015b6e36,
title = "Nonlinear optical properties and excited-state dynamics of highly symmetric expanded porphyrins",
abstract = "A strong correlation among calculated Nucleus-Independent Chemical Shift (NICS) values, molecular planarity, and the observed two-photon absorption (TPA) values was found for a series of closely matched expanded porphyrins. The expanded porphyrins in question consisted of [26]hexaphyrin, [28]-hexaphyrin, rubyrin, amethyrin, cyclo[6]pyrrole, cyclo[7]pyrrole, and cyclo[8]pyrrole containing 22, 24, 26, 28, and 30 π-electrons. Two of the systems, [28]hexaphyrin and amethyrin, were considered to be antiaromatic as judged from a simple application of H{\"u}ckel's [4n + 2] rule. These systems displayed positive NICS(0) values (+43.5 and +17.1 ppm, respectively) and gave rise to TPA values of 2600 and 3100 GM, respectively. By contrast, a set of congeners containing 22, 26, and 30 π-electrons (cyclo[n]pyrrole, n = 6, 7, and 8, respectively) were characterized by a linear correlation between the NICS and TPA values. In the case of the oligopyrrolic macrocycles containing 26 π-electron systems, a further correlation between the molecular structure and various markers associated with aromaticity was seen. In particular, a decrease in the excited state lifetimes and an increase in the TPA values were seen as the flexibility of the systems increased. Based on the findings presented here, it is proposed that various readily measurable optical properties, including the two-photon absorption cross-section, can provide a quantitative experimental measure of aromaticity in macrocyclic π-conjugated systems.",
author = "Yoon, {Zin Seok} and Kwon, {Jung Ho} and Yoon, {Min Chul} and Koh, {Mi Kyoung} and Noh, {Su Bum} and Sessler, {Jonathan L.} and Lee, {Jeong Tae} and Daniel Seidel and Apolonio Aguilar and Soji Shimizu and Masaaki Suzuki and Atsuhiro Osuka and Dongho Kim",
year = "2006",
month = "11",
day = "1",
doi = "10.1021/ja064773k",
language = "English",
volume = "128",
pages = "14128--14134",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "American Chemical Society",
number = "43",

}

Yoon, ZS, Kwon, JH, Yoon, MC, Koh, MK, Noh, SB, Sessler, JL, Lee, JT, Seidel, D, Aguilar, A, Shimizu, S, Suzuki, M, Osuka, A & Kim, D 2006, 'Nonlinear optical properties and excited-state dynamics of highly symmetric expanded porphyrins', Journal of the American Chemical Society, vol. 128, no. 43, pp. 14128-14134. https://doi.org/10.1021/ja064773k

Nonlinear optical properties and excited-state dynamics of highly symmetric expanded porphyrins. / Yoon, Zin Seok; Kwon, Jung Ho; Yoon, Min Chul; Koh, Mi Kyoung; Noh, Su Bum; Sessler, Jonathan L.; Lee, Jeong Tae; Seidel, Daniel; Aguilar, Apolonio; Shimizu, Soji; Suzuki, Masaaki; Osuka, Atsuhiro; Kim, Dongho.

In: Journal of the American Chemical Society, Vol. 128, No. 43, 01.11.2006, p. 14128-14134.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Nonlinear optical properties and excited-state dynamics of highly symmetric expanded porphyrins

AU - Yoon, Zin Seok

AU - Kwon, Jung Ho

AU - Yoon, Min Chul

AU - Koh, Mi Kyoung

AU - Noh, Su Bum

AU - Sessler, Jonathan L.

AU - Lee, Jeong Tae

AU - Seidel, Daniel

AU - Aguilar, Apolonio

AU - Shimizu, Soji

AU - Suzuki, Masaaki

AU - Osuka, Atsuhiro

AU - Kim, Dongho

PY - 2006/11/1

Y1 - 2006/11/1

N2 - A strong correlation among calculated Nucleus-Independent Chemical Shift (NICS) values, molecular planarity, and the observed two-photon absorption (TPA) values was found for a series of closely matched expanded porphyrins. The expanded porphyrins in question consisted of [26]hexaphyrin, [28]-hexaphyrin, rubyrin, amethyrin, cyclo[6]pyrrole, cyclo[7]pyrrole, and cyclo[8]pyrrole containing 22, 24, 26, 28, and 30 π-electrons. Two of the systems, [28]hexaphyrin and amethyrin, were considered to be antiaromatic as judged from a simple application of Hückel's [4n + 2] rule. These systems displayed positive NICS(0) values (+43.5 and +17.1 ppm, respectively) and gave rise to TPA values of 2600 and 3100 GM, respectively. By contrast, a set of congeners containing 22, 26, and 30 π-electrons (cyclo[n]pyrrole, n = 6, 7, and 8, respectively) were characterized by a linear correlation between the NICS and TPA values. In the case of the oligopyrrolic macrocycles containing 26 π-electron systems, a further correlation between the molecular structure and various markers associated with aromaticity was seen. In particular, a decrease in the excited state lifetimes and an increase in the TPA values were seen as the flexibility of the systems increased. Based on the findings presented here, it is proposed that various readily measurable optical properties, including the two-photon absorption cross-section, can provide a quantitative experimental measure of aromaticity in macrocyclic π-conjugated systems.

AB - A strong correlation among calculated Nucleus-Independent Chemical Shift (NICS) values, molecular planarity, and the observed two-photon absorption (TPA) values was found for a series of closely matched expanded porphyrins. The expanded porphyrins in question consisted of [26]hexaphyrin, [28]-hexaphyrin, rubyrin, amethyrin, cyclo[6]pyrrole, cyclo[7]pyrrole, and cyclo[8]pyrrole containing 22, 24, 26, 28, and 30 π-electrons. Two of the systems, [28]hexaphyrin and amethyrin, were considered to be antiaromatic as judged from a simple application of Hückel's [4n + 2] rule. These systems displayed positive NICS(0) values (+43.5 and +17.1 ppm, respectively) and gave rise to TPA values of 2600 and 3100 GM, respectively. By contrast, a set of congeners containing 22, 26, and 30 π-electrons (cyclo[n]pyrrole, n = 6, 7, and 8, respectively) were characterized by a linear correlation between the NICS and TPA values. In the case of the oligopyrrolic macrocycles containing 26 π-electron systems, a further correlation between the molecular structure and various markers associated with aromaticity was seen. In particular, a decrease in the excited state lifetimes and an increase in the TPA values were seen as the flexibility of the systems increased. Based on the findings presented here, it is proposed that various readily measurable optical properties, including the two-photon absorption cross-section, can provide a quantitative experimental measure of aromaticity in macrocyclic π-conjugated systems.

UR - http://www.scopus.com/inward/record.url?scp=33750443918&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=33750443918&partnerID=8YFLogxK

U2 - 10.1021/ja064773k

DO - 10.1021/ja064773k

M3 - Article

C2 - 17061896

AN - SCOPUS:33750443918

VL - 128

SP - 14128

EP - 14134

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

IS - 43

ER -