Cyanine-like dyes with large bond-length alternation.
Herein, the synthesis and properties of alkyne-bridged carbocations, which are analogous in structure to cyanine dyes, are reported. An alkene-bridged dye, linked at the third position of the indole, was also synthesized as a reference compound. These new carbocations are stable under ambient condit...
| Автори: | , , , , , , |
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| Формат: | Journal article |
| Мова: | English |
| Опубліковано: |
2013
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| _version_ | 1826281561878691840 |
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| author | Thorley, K Hales, J Kim, H Ohira, S Brédas, J Perry, J Anderson, H |
| author_facet | Thorley, K Hales, J Kim, H Ohira, S Brédas, J Perry, J Anderson, H |
| author_sort | Thorley, K |
| collection | OXFORD |
| description | Herein, the synthesis and properties of alkyne-bridged carbocations, which are analogous in structure to cyanine dyes, are reported. An alkene-bridged dye, linked at the third position of the indole, was also synthesized as a reference compound. These new carbocations are stable under ambient conditions, allowing characterization by UV/Vis and NMR ((1)H and (13)C) spectroscopies. These techniques revealed a large degree of delocalization of the positive charge, similar to a previously reported porphyrin carbocation. The linear and nonlinear optical properties are compared with cyanine dyes and triarylmethyl cations, to investigate the effects of the bond-length alternation and the overall molecular geometry. The value of Re(γ), the real part of the third-order microscopic polarizability, of -1.3×10(-33) esu for the alkyne-linked cation is comparable to that of a cyanine dye of similar length. Nondegenerate two-photon absorption spectra showed that the alkene-bridged dye exhibited characteristics of cyanines, whereas the alkyne-bridged dye is reminiscent of octupolar chromophores, such as the triarylmethyl carbocation brilliant green. Such attributes were confirmed and rationalized by quantum chemical calculations. |
| first_indexed | 2024-03-07T00:30:39Z |
| format | Journal article |
| id | oxford-uuid:7fad033e-48f0-4a52-8498-bf43e1fb4a40 |
| institution | University of Oxford |
| language | English |
| last_indexed | 2024-03-07T00:30:39Z |
| publishDate | 2013 |
| record_format | dspace |
| spelling | oxford-uuid:7fad033e-48f0-4a52-8498-bf43e1fb4a402022-03-26T21:18:26ZCyanine-like dyes with large bond-length alternation.Journal articlehttp://purl.org/coar/resource_type/c_dcae04bcuuid:7fad033e-48f0-4a52-8498-bf43e1fb4a40EnglishSymplectic Elements at Oxford2013Thorley, KHales, JKim, HOhira, SBrédas, JPerry, JAnderson, HHerein, the synthesis and properties of alkyne-bridged carbocations, which are analogous in structure to cyanine dyes, are reported. An alkene-bridged dye, linked at the third position of the indole, was also synthesized as a reference compound. These new carbocations are stable under ambient conditions, allowing characterization by UV/Vis and NMR ((1)H and (13)C) spectroscopies. These techniques revealed a large degree of delocalization of the positive charge, similar to a previously reported porphyrin carbocation. The linear and nonlinear optical properties are compared with cyanine dyes and triarylmethyl cations, to investigate the effects of the bond-length alternation and the overall molecular geometry. The value of Re(γ), the real part of the third-order microscopic polarizability, of -1.3×10(-33) esu for the alkyne-linked cation is comparable to that of a cyanine dye of similar length. Nondegenerate two-photon absorption spectra showed that the alkene-bridged dye exhibited characteristics of cyanines, whereas the alkyne-bridged dye is reminiscent of octupolar chromophores, such as the triarylmethyl carbocation brilliant green. Such attributes were confirmed and rationalized by quantum chemical calculations. |
| spellingShingle | Thorley, K Hales, J Kim, H Ohira, S Brédas, J Perry, J Anderson, H Cyanine-like dyes with large bond-length alternation. |
| title | Cyanine-like dyes with large bond-length alternation. |
| title_full | Cyanine-like dyes with large bond-length alternation. |
| title_fullStr | Cyanine-like dyes with large bond-length alternation. |
| title_full_unstemmed | Cyanine-like dyes with large bond-length alternation. |
| title_short | Cyanine-like dyes with large bond-length alternation. |
| title_sort | cyanine like dyes with large bond length alternation |
| work_keys_str_mv | AT thorleyk cyaninelikedyeswithlargebondlengthalternation AT halesj cyaninelikedyeswithlargebondlengthalternation AT kimh cyaninelikedyeswithlargebondlengthalternation AT ohiras cyaninelikedyeswithlargebondlengthalternation AT bredasj cyaninelikedyeswithlargebondlengthalternation AT perryj cyaninelikedyeswithlargebondlengthalternation AT andersonh cyaninelikedyeswithlargebondlengthalternation |