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Engineering hydrogen bonding to align molecular dipoles in organic solids for efficient second harmonic generation

Considering nearly infinite design possibilities, organic second harmonic generation (SHG) molecules are believed to have long-term promise. However, because of the tendency to form dipole-antiparallel crystals that lead to zero macroscopic polarization, it is difficult to design a nonlinear optical...

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Autores principales: Zhao, Ruyan, Zhu, Tong, Wang, Sasa, Jarrett-Wilkins, Charlie, Najjarian, Amin Morteza, Lough, Alan J., Hoogland, Sjoerd, Sargent, Edward H., Seferos, Dwight S.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: The Royal Society of Chemistry 2022
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9601317/
https://www.ncbi.nlm.nih.gov/pubmed/36349093
http://dx.doi.org/10.1039/d2sc03994j
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author Zhao, Ruyan
Zhu, Tong
Wang, Sasa
Jarrett-Wilkins, Charlie
Najjarian, Amin Morteza
Lough, Alan J.
Hoogland, Sjoerd
Sargent, Edward H.
Seferos, Dwight S.
author_facet Zhao, Ruyan
Zhu, Tong
Wang, Sasa
Jarrett-Wilkins, Charlie
Najjarian, Amin Morteza
Lough, Alan J.
Hoogland, Sjoerd
Sargent, Edward H.
Seferos, Dwight S.
author_sort Zhao, Ruyan
collection PubMed
description Considering nearly infinite design possibilities, organic second harmonic generation (SHG) molecules are believed to have long-term promise. However, because of the tendency to form dipole-antiparallel crystals that lead to zero macroscopic polarization, it is difficult to design a nonlinear optical (NLO) material based on organic molecules. In this manuscript, we report a new molecule motif that can form asymmetric organic solids by controlling the degree of hydrogen bonding through protonation. A conjugated polar organic molecule was prepared with a triple bond connecting an electron-withdrawing pyridine ring and an electron-donating thiophene ring. By controlling the degree of hydrogen bonding through protonation, two different crystal packing motifs are achieved. One crystallizes into the common dipole-antiparallel nonpolar P1̄ space group. The second crystallizes into the uncommon dipole-parallel polar P1 space group, in which the molecular dipoles are aligned along a single axis and thus exhibit a high macroscopic polarization in its solid-state form. Due to the P1 polar packing, the sample can generate second harmonic light efficiently, about three times the intensity of the benchmark potassium dihydrogen phosphate. Our findings show that crystal engineering by hydrogen bonding in a single molecular backbone can be used for controlling the macroscopic NLO properties.
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spelling pubmed-96013172022-11-07 Engineering hydrogen bonding to align molecular dipoles in organic solids for efficient second harmonic generation Zhao, Ruyan Zhu, Tong Wang, Sasa Jarrett-Wilkins, Charlie Najjarian, Amin Morteza Lough, Alan J. Hoogland, Sjoerd Sargent, Edward H. Seferos, Dwight S. Chem Sci Chemistry Considering nearly infinite design possibilities, organic second harmonic generation (SHG) molecules are believed to have long-term promise. However, because of the tendency to form dipole-antiparallel crystals that lead to zero macroscopic polarization, it is difficult to design a nonlinear optical (NLO) material based on organic molecules. In this manuscript, we report a new molecule motif that can form asymmetric organic solids by controlling the degree of hydrogen bonding through protonation. A conjugated polar organic molecule was prepared with a triple bond connecting an electron-withdrawing pyridine ring and an electron-donating thiophene ring. By controlling the degree of hydrogen bonding through protonation, two different crystal packing motifs are achieved. One crystallizes into the common dipole-antiparallel nonpolar P1̄ space group. The second crystallizes into the uncommon dipole-parallel polar P1 space group, in which the molecular dipoles are aligned along a single axis and thus exhibit a high macroscopic polarization in its solid-state form. Due to the P1 polar packing, the sample can generate second harmonic light efficiently, about three times the intensity of the benchmark potassium dihydrogen phosphate. Our findings show that crystal engineering by hydrogen bonding in a single molecular backbone can be used for controlling the macroscopic NLO properties. The Royal Society of Chemistry 2022-10-11 /pmc/articles/PMC9601317/ /pubmed/36349093 http://dx.doi.org/10.1039/d2sc03994j Text en This journal is © The Royal Society of Chemistry https://creativecommons.org/licenses/by/3.0/
spellingShingle Chemistry
Zhao, Ruyan
Zhu, Tong
Wang, Sasa
Jarrett-Wilkins, Charlie
Najjarian, Amin Morteza
Lough, Alan J.
Hoogland, Sjoerd
Sargent, Edward H.
Seferos, Dwight S.
Engineering hydrogen bonding to align molecular dipoles in organic solids for efficient second harmonic generation
title Engineering hydrogen bonding to align molecular dipoles in organic solids for efficient second harmonic generation
title_full Engineering hydrogen bonding to align molecular dipoles in organic solids for efficient second harmonic generation
title_fullStr Engineering hydrogen bonding to align molecular dipoles in organic solids for efficient second harmonic generation
title_full_unstemmed Engineering hydrogen bonding to align molecular dipoles in organic solids for efficient second harmonic generation
title_short Engineering hydrogen bonding to align molecular dipoles in organic solids for efficient second harmonic generation
title_sort engineering hydrogen bonding to align molecular dipoles in organic solids for efficient second harmonic generation
topic Chemistry
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9601317/
https://www.ncbi.nlm.nih.gov/pubmed/36349093
http://dx.doi.org/10.1039/d2sc03994j
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