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Extreme multi-point van der Waals interactions: isolable dimers of phthalocyanines substituted with pillar-like azaacenes

How strong are van der Waals interactions in determining the final outcome of self-assembled structures of small molecular systems? Herein we report isolable phthalocyanine (Pc) dimers bound by π–π interactions between monomeric Pcs which can be handled as single entities. Pc dimers have been contin...

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Autores principales: Saeki, Hidenori, Sakamaki, Daisuke, Fujiwara, Hideki, Seki, Shu
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Royal Society of Chemistry 2019
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6993618/
https://www.ncbi.nlm.nih.gov/pubmed/32055304
http://dx.doi.org/10.1039/c9sc01739a
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author Saeki, Hidenori
Sakamaki, Daisuke
Fujiwara, Hideki
Seki, Shu
author_facet Saeki, Hidenori
Sakamaki, Daisuke
Fujiwara, Hideki
Seki, Shu
author_sort Saeki, Hidenori
collection PubMed
description How strong are van der Waals interactions in determining the final outcome of self-assembled structures of small molecular systems? Herein we report isolable phthalocyanine (Pc) dimers bound by π–π interactions between monomeric Pcs which can be handled as single entities. Pc dimers have been continuously investigated as one of the simplest models of Pc aggregates. Pcs were substituted with eight dihydrodiazapentacene (DHDAP) moieties on the periphery, which act as pillar-like π-planes and these molecules form H-type dimers with the help of synergetic π–π interactions between two co-facial Pc rings and among the pillar-like DHDAP moieties. The dimer structures were fully confirmed by 1D and 2D NMR, ESR, and electronic absorption measurements. The dissociation of these dimers was observed in particular solvents such as o-dichlorobenzene, due to the good solubility of the larger π-conjugated molecules. On the other hand, in ethyl acetate the monomers were metastable species and underwent selective dimerization. Interestingly in THF, neither the dimerization of the monomers nor the dissociation of dimers was observed, suggesting that both the dimers and the monomers were kinetically well stabilized. For hours to days, we can handle these dimers as “a molecule” not only in solution but also even in mass spectrometry under ionization conditions without significant dissociation.
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spelling pubmed-69936182020-02-13 Extreme multi-point van der Waals interactions: isolable dimers of phthalocyanines substituted with pillar-like azaacenes Saeki, Hidenori Sakamaki, Daisuke Fujiwara, Hideki Seki, Shu Chem Sci Chemistry How strong are van der Waals interactions in determining the final outcome of self-assembled structures of small molecular systems? Herein we report isolable phthalocyanine (Pc) dimers bound by π–π interactions between monomeric Pcs which can be handled as single entities. Pc dimers have been continuously investigated as one of the simplest models of Pc aggregates. Pcs were substituted with eight dihydrodiazapentacene (DHDAP) moieties on the periphery, which act as pillar-like π-planes and these molecules form H-type dimers with the help of synergetic π–π interactions between two co-facial Pc rings and among the pillar-like DHDAP moieties. The dimer structures were fully confirmed by 1D and 2D NMR, ESR, and electronic absorption measurements. The dissociation of these dimers was observed in particular solvents such as o-dichlorobenzene, due to the good solubility of the larger π-conjugated molecules. On the other hand, in ethyl acetate the monomers were metastable species and underwent selective dimerization. Interestingly in THF, neither the dimerization of the monomers nor the dissociation of dimers was observed, suggesting that both the dimers and the monomers were kinetically well stabilized. For hours to days, we can handle these dimers as “a molecule” not only in solution but also even in mass spectrometry under ionization conditions without significant dissociation. Royal Society of Chemistry 2019-08-29 /pmc/articles/PMC6993618/ /pubmed/32055304 http://dx.doi.org/10.1039/c9sc01739a Text en This journal is © The Royal Society of Chemistry 2019 http://creativecommons.org/licenses/by-nc/3.0/ This article is freely available. This article is licensed under a Creative Commons Attribution Non Commercial 3.0 Unported Licence (CC BY-NC 3.0)
spellingShingle Chemistry
Saeki, Hidenori
Sakamaki, Daisuke
Fujiwara, Hideki
Seki, Shu
Extreme multi-point van der Waals interactions: isolable dimers of phthalocyanines substituted with pillar-like azaacenes
title Extreme multi-point van der Waals interactions: isolable dimers of phthalocyanines substituted with pillar-like azaacenes
title_full Extreme multi-point van der Waals interactions: isolable dimers of phthalocyanines substituted with pillar-like azaacenes
title_fullStr Extreme multi-point van der Waals interactions: isolable dimers of phthalocyanines substituted with pillar-like azaacenes
title_full_unstemmed Extreme multi-point van der Waals interactions: isolable dimers of phthalocyanines substituted with pillar-like azaacenes
title_short Extreme multi-point van der Waals interactions: isolable dimers of phthalocyanines substituted with pillar-like azaacenes
title_sort extreme multi-point van der waals interactions: isolable dimers of phthalocyanines substituted with pillar-like azaacenes
topic Chemistry
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6993618/
https://www.ncbi.nlm.nih.gov/pubmed/32055304
http://dx.doi.org/10.1039/c9sc01739a
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