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Large Hyperpolarizabilities at Telecommunication-Relevant Wavelengths in Donor–Acceptor–Donor Nonlinear Optical Chromophores
[Image: see text] Octopolar D(2)-symmetric chromophores, based on the MPZnM supermolecular motif in which (porphinato)zinc(II) (PZn) and ruthenium(II) polypyridyl (M) structural units are connected via ethyne linkages, were synthesized. These structures take advantage of electron-rich meso-arylporph...
Autores principales: | , , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American
Chemical Society
2016
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Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5200929/ https://www.ncbi.nlm.nih.gov/pubmed/28058285 http://dx.doi.org/10.1021/acscentsci.6b00291 |
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author | Nayak, Animesh Park, Jaehong De Mey, Kurt Hu, Xiangqian Duncan, Timothy V. Beratan, David N. Clays, Koen Therien, Michael J. |
author_facet | Nayak, Animesh Park, Jaehong De Mey, Kurt Hu, Xiangqian Duncan, Timothy V. Beratan, David N. Clays, Koen Therien, Michael J. |
author_sort | Nayak, Animesh |
collection | PubMed |
description | [Image: see text] Octopolar D(2)-symmetric chromophores, based on the MPZnM supermolecular motif in which (porphinato)zinc(II) (PZn) and ruthenium(II) polypyridyl (M) structural units are connected via ethyne linkages, were synthesized. These structures take advantage of electron-rich meso-arylporphyrin or electron-poor meso-(perfluoroalkyl)porphyrin macrocycles, unsubstituted terpyridyl and 4′-pyrrolidinyl-2,2′;6′,2″-terpyridyl ligands, and modulation of metal(II) polypyridyl-to-(porphinato)zinc connectivity, to probe how electronic and geometric factors impact the measured hyperpolarizability. Transient absorption spectra obtained at early time delays (t(delay) < 400 fs) demonstrate fast excited-state relaxation, and formation of a highly polarized T(1) excited state; the T(1) states of these chromophores display expansive, intense T(1) → T(n) absorption manifolds that dominate the 800–1200 nm region of the NIR, long (μs) triplet-state lifetimes, and unusually large NIR excited absorptive extinction coefficients [ε(T(1) → T(n)) ∼ 10(5) M(–1) cm(–1)]. Dynamic hyperpolarizability (β(λ)) values were determined from hyper-Rayleigh light scattering (HRS) measurements, carried out at multiple incident irradiation wavelengths spanning the 800–1500 nm spectral domain. The measured β(HRS) value (4600 ± 1200 × 10(–30) esu) for one of these complexes, RuPZnRu, is the largest yet reported for any chromophore at a 1500 nm irradiation wavelength, highlighting that appropriate engineering of strong electronic coupling between multiple charge-transfer oscillators provides a critical design strategy to realize octopolar NLO chromophores exhibiting large β(HRS) values at telecom-relevant wavelengths. Generalized Thomas–Kuhn sum (TKS) rules were utilized to compute the effective excited-state-to-excited-state transition dipole moments from experimental linear-absorption spectra; these data were then utilized to compute hyperpolarizabilities as a function of frequency, that include two- and three-state contributions for both β(zzz) and β(xzx) tensor components to the RuPZnRu hyperpolarizability spectrum. This analysis predicts that the β(zzz) and β(xzx) tensor contributions to the RuPZnRu hyperpolarizability spectrum maximize near 1550 nm, in agreement with experimental data. The TKS analysis suggests that relative to analogous dipolar chromophores, octopolar supermolecules will be likely characterized by more intricate dependences of the measured hyperpolarizability upon irradiation wavelength due to the interactions among multiple different β tensor components. |
format | Online Article Text |
id | pubmed-5200929 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2016 |
publisher | American
Chemical Society |
record_format | MEDLINE/PubMed |
spelling | pubmed-52009292017-01-05 Large Hyperpolarizabilities at Telecommunication-Relevant Wavelengths in Donor–Acceptor–Donor Nonlinear Optical Chromophores Nayak, Animesh Park, Jaehong De Mey, Kurt Hu, Xiangqian Duncan, Timothy V. Beratan, David N. Clays, Koen Therien, Michael J. ACS Cent Sci [Image: see text] Octopolar D(2)-symmetric chromophores, based on the MPZnM supermolecular motif in which (porphinato)zinc(II) (PZn) and ruthenium(II) polypyridyl (M) structural units are connected via ethyne linkages, were synthesized. These structures take advantage of electron-rich meso-arylporphyrin or electron-poor meso-(perfluoroalkyl)porphyrin macrocycles, unsubstituted terpyridyl and 4′-pyrrolidinyl-2,2′;6′,2″-terpyridyl ligands, and modulation of metal(II) polypyridyl-to-(porphinato)zinc connectivity, to probe how electronic and geometric factors impact the measured hyperpolarizability. Transient absorption spectra obtained at early time delays (t(delay) < 400 fs) demonstrate fast excited-state relaxation, and formation of a highly polarized T(1) excited state; the T(1) states of these chromophores display expansive, intense T(1) → T(n) absorption manifolds that dominate the 800–1200 nm region of the NIR, long (μs) triplet-state lifetimes, and unusually large NIR excited absorptive extinction coefficients [ε(T(1) → T(n)) ∼ 10(5) M(–1) cm(–1)]. Dynamic hyperpolarizability (β(λ)) values were determined from hyper-Rayleigh light scattering (HRS) measurements, carried out at multiple incident irradiation wavelengths spanning the 800–1500 nm spectral domain. The measured β(HRS) value (4600 ± 1200 × 10(–30) esu) for one of these complexes, RuPZnRu, is the largest yet reported for any chromophore at a 1500 nm irradiation wavelength, highlighting that appropriate engineering of strong electronic coupling between multiple charge-transfer oscillators provides a critical design strategy to realize octopolar NLO chromophores exhibiting large β(HRS) values at telecom-relevant wavelengths. Generalized Thomas–Kuhn sum (TKS) rules were utilized to compute the effective excited-state-to-excited-state transition dipole moments from experimental linear-absorption spectra; these data were then utilized to compute hyperpolarizabilities as a function of frequency, that include two- and three-state contributions for both β(zzz) and β(xzx) tensor components to the RuPZnRu hyperpolarizability spectrum. This analysis predicts that the β(zzz) and β(xzx) tensor contributions to the RuPZnRu hyperpolarizability spectrum maximize near 1550 nm, in agreement with experimental data. The TKS analysis suggests that relative to analogous dipolar chromophores, octopolar supermolecules will be likely characterized by more intricate dependences of the measured hyperpolarizability upon irradiation wavelength due to the interactions among multiple different β tensor components. American Chemical Society 2016-12-16 2016-12-28 /pmc/articles/PMC5200929/ /pubmed/28058285 http://dx.doi.org/10.1021/acscentsci.6b00291 Text en Copyright © 2016 American Chemical Society This is an open access article published under an ACS AuthorChoice License (http://pubs.acs.org/page/policy/authorchoice_termsofuse.html) , which permits copying and redistribution of the article or any adaptations for non-commercial purposes. |
spellingShingle | Nayak, Animesh Park, Jaehong De Mey, Kurt Hu, Xiangqian Duncan, Timothy V. Beratan, David N. Clays, Koen Therien, Michael J. Large Hyperpolarizabilities at Telecommunication-Relevant Wavelengths in Donor–Acceptor–Donor Nonlinear Optical Chromophores |
title | Large Hyperpolarizabilities at Telecommunication-Relevant
Wavelengths in Donor–Acceptor–Donor Nonlinear Optical
Chromophores |
title_full | Large Hyperpolarizabilities at Telecommunication-Relevant
Wavelengths in Donor–Acceptor–Donor Nonlinear Optical
Chromophores |
title_fullStr | Large Hyperpolarizabilities at Telecommunication-Relevant
Wavelengths in Donor–Acceptor–Donor Nonlinear Optical
Chromophores |
title_full_unstemmed | Large Hyperpolarizabilities at Telecommunication-Relevant
Wavelengths in Donor–Acceptor–Donor Nonlinear Optical
Chromophores |
title_short | Large Hyperpolarizabilities at Telecommunication-Relevant
Wavelengths in Donor–Acceptor–Donor Nonlinear Optical
Chromophores |
title_sort | large hyperpolarizabilities at telecommunication-relevant
wavelengths in donor–acceptor–donor nonlinear optical
chromophores |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5200929/ https://www.ncbi.nlm.nih.gov/pubmed/28058285 http://dx.doi.org/10.1021/acscentsci.6b00291 |
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