Perylene Bisimide Cyclophanes: Structure–Property Relationships upon Variation of the Cavity Size
Abstract Five cyclophanes composed of two perylene bisimide (PBI) dyes and various CH2–arylene–CH2 linker units were synthesized. PM6-D3H4 geometry-optimized structures and a single crystal for one of these cyclophanes reveal well-defined distances between the two coplanar PBI units in these cycloph...
| Main Authors: | , , , , |
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| Format: | Article |
| Language: | English |
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Georg Thieme Verlag
2020-04-01
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| Series: | Organic Materials |
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| Online Access: | http://www.thieme-connect.de/DOI/DOI?10.1055/s-0040-1709998 |
| _version_ | 1811328071738851328 |
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| author | Jessica Rühe David Bialas Peter Spenst Ana-Maria Krause Frank Würthner |
| author_facet | Jessica Rühe David Bialas Peter Spenst Ana-Maria Krause Frank Würthner |
| author_sort | Jessica Rühe |
| collection | DOAJ |
| description | Abstract
Five cyclophanes composed of two perylene bisimide (PBI) dyes and various CH2–arylene–CH2 linker units were synthesized. PM6-D3H4 geometry-optimized structures and a single crystal for one of these cyclophanes reveal well-defined distances between the two coplanar PBI units in these cyclophanes, spanning the range from 5.0 to 12.5 Å. UV/vis absorption spectra reveal a redistribution of oscillator strength of the vibronic bands due to a H-type exciton coupling even for the cyclophane with the largest interchromophoric distance. A quantitative evaluation according to the Kasha–Spano theory affords exciton coupling strengths ranging from 64 cm−1 for the largest cyclophane up to 333 cm−1 for the smallest one and a surprisingly good fit to the cubic interchromophoric distance in the framework of the point-dipole approximation. Interchromophoric interaction is also noticed in fluorescence lifetimes that are significantly increased for all five cyclophanes as expected for H-coupled chromophores due to a decrease of the radiative rate. For the three largest cyclophanes with interchromophoric distances of >9 Å, fluorescence quantum yields remain high in chloroform (>88%), whilst for the smaller ones with interchromophoric distances <6 Å, additional nonradiative pathways lead to a pronounced fluorescence quenching. |
| first_indexed | 2024-04-13T15:19:48Z |
| format | Article |
| id | doaj.art-3fba018ab51147d79b005ed179620a29 |
| institution | Directory Open Access Journal |
| issn | 2625-1825 |
| language | English |
| last_indexed | 2024-04-13T15:19:48Z |
| publishDate | 2020-04-01 |
| publisher | Georg Thieme Verlag |
| record_format | Article |
| series | Organic Materials |
| spelling | doaj.art-3fba018ab51147d79b005ed179620a292022-12-22T02:41:43ZengGeorg Thieme VerlagOrganic Materials2625-18252020-04-01020214915810.1055/s-0040-1709998Perylene Bisimide Cyclophanes: Structure–Property Relationships upon Variation of the Cavity SizeJessica Rühe0David Bialas1Peter Spenst2Ana-Maria Krause3Frank Würthner4Institut für Organische Chemie, Universität Würzburg, Am Hubland, 97074 Würzburg, GermanyInstitut für Organische Chemie, Universität Würzburg, Am Hubland, 97074 Würzburg, GermanyInstitut für Organische Chemie, Universität Würzburg, Am Hubland, 97074 Würzburg, GermanyCenter for Nanosystems Chemistry, Universität Würzburg, Theodor-Boveri-Weg, 97074 Würzburg, GermanyInstitut für Organische Chemie, Universität Würzburg, Am Hubland, 97074 Würzburg, GermanyAbstract Five cyclophanes composed of two perylene bisimide (PBI) dyes and various CH2–arylene–CH2 linker units were synthesized. PM6-D3H4 geometry-optimized structures and a single crystal for one of these cyclophanes reveal well-defined distances between the two coplanar PBI units in these cyclophanes, spanning the range from 5.0 to 12.5 Å. UV/vis absorption spectra reveal a redistribution of oscillator strength of the vibronic bands due to a H-type exciton coupling even for the cyclophane with the largest interchromophoric distance. A quantitative evaluation according to the Kasha–Spano theory affords exciton coupling strengths ranging from 64 cm−1 for the largest cyclophane up to 333 cm−1 for the smallest one and a surprisingly good fit to the cubic interchromophoric distance in the framework of the point-dipole approximation. Interchromophoric interaction is also noticed in fluorescence lifetimes that are significantly increased for all five cyclophanes as expected for H-coupled chromophores due to a decrease of the radiative rate. For the three largest cyclophanes with interchromophoric distances of >9 Å, fluorescence quantum yields remain high in chloroform (>88%), whilst for the smaller ones with interchromophoric distances <6 Å, additional nonradiative pathways lead to a pronounced fluorescence quenching.http://www.thieme-connect.de/DOI/DOI?10.1055/s-0040-1709998cyclophanesexciton couplingfluorescenceorganic dyes |
| spellingShingle | Jessica Rühe David Bialas Peter Spenst Ana-Maria Krause Frank Würthner Perylene Bisimide Cyclophanes: Structure–Property Relationships upon Variation of the Cavity Size Organic Materials cyclophanes exciton coupling fluorescence organic dyes |
| title | Perylene Bisimide Cyclophanes: Structure–Property Relationships upon Variation of the Cavity Size |
| title_full | Perylene Bisimide Cyclophanes: Structure–Property Relationships upon Variation of the Cavity Size |
| title_fullStr | Perylene Bisimide Cyclophanes: Structure–Property Relationships upon Variation of the Cavity Size |
| title_full_unstemmed | Perylene Bisimide Cyclophanes: Structure–Property Relationships upon Variation of the Cavity Size |
| title_short | Perylene Bisimide Cyclophanes: Structure–Property Relationships upon Variation of the Cavity Size |
| title_sort | perylene bisimide cyclophanes structure property relationships upon variation of the cavity size |
| topic | cyclophanes exciton coupling fluorescence organic dyes |
| url | http://www.thieme-connect.de/DOI/DOI?10.1055/s-0040-1709998 |
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