MULTI REDOX-ACTIVE MACROCYCLIC HOST MOLECULES CONTAINING MULTIPLE BENZO CROWN-ETHER AND FERROCENYL MOIETIES THAT BIND BIPYRIDINIUM DICATIONS - SYNTHESES, COORDINATION AND ELECTROCHEMICAL PROPERTIES
The design, syntheses, co-ordination and electrochemical properties of novel multisite host molecules containing multiple benzo crown ether and ferrocenyl redox centres are described. The reaction of the macrocycle 2,8,14,20-tetraferrocenylpentacyclo[19.3.1.1.3,71 9,13.1 15,19]octacosa-1(25),3,5,7(2...
| Main Authors: | , , |
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| Format: | Journal article |
| Language: | English |
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1991
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| _version_ | 1797098902962307072 |
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| author | Beer, P Tite, E Ibbotson, A |
| author_facet | Beer, P Tite, E Ibbotson, A |
| author_sort | Beer, P |
| collection | OXFORD |
| description | The design, syntheses, co-ordination and electrochemical properties of novel multisite host molecules containing multiple benzo crown ether and ferrocenyl redox centres are described. The reaction of the macrocycle 2,8,14,20-tetraferrocenylpentacyclo[19.3.1.1.3,71 9,13.1 15,19]octacosa-1(25),3,5,7(28),9,11,13(27),15,17,19(26),21,23- dodecaen-4,6,10,12,16,18,22,24-octol 3 with propionic anhydride, benzoyl chloride or chlorocarbonylferrocene 6 gave new redox-active host molecules 4, 5 and 7 respectively. The acid-catalysed condensation of 15-formyl-2,3,5,6,8,9,11,12-octahydro-1,4,7,10,13-benzopentaoxacyclopentadecine with 1,3-dihydroxybenzene afforded a novel phenolic macrocycle 2,8,14,20-tetrakis(2,3,5,6,8,9,11,12-octahydro-1,4,7,10,13- benzopentaoxacyclopentadecin-15-yl)-pentacyclo[1.3.1.13,7.1 9,13.115,19]octacosa-1(25),3,5,7(28), 9,11,13(27),15,17,19(26),21,23-dodecaen-4,6,10,12,16,18,22,24-octol 14 which on reaction with propionic anhydride, benzoyl chloride, 6 or bromochloromethane gave respective host molecules 15, 16, 17 and 18 (the latter being the first crown ether cavitand host), each containing four benzo-15-crown-5 moieties. Electrochemical studies show the four ferrocenyl redox centres present in 5 to undergo two one-electron oxidations at +0.58 and +0.67 V in dichloromethane. Redox-active host 17, containing eight ferrocenyl moieties, was found to undergo independent reversible one-electron oxidations in dichloromethane. High-field 1H NMR complexation studies reversible one-electron oxidations in dichloromethane. High-field 1H NMR complexation studies revealed hosts 16-18 to form solution complexes with bipyridinium guest species, exclusively at the host's benzo crown ether binding site. |
| first_indexed | 2024-03-07T05:16:16Z |
| format | Journal article |
| id | oxford-uuid:dd4c3a1a-e40c-480e-8c29-2a4ba3193c74 |
| institution | University of Oxford |
| language | English |
| last_indexed | 2024-03-07T05:16:16Z |
| publishDate | 1991 |
| record_format | dspace |
| spelling | oxford-uuid:dd4c3a1a-e40c-480e-8c29-2a4ba3193c742022-03-27T09:24:06ZMULTI REDOX-ACTIVE MACROCYCLIC HOST MOLECULES CONTAINING MULTIPLE BENZO CROWN-ETHER AND FERROCENYL MOIETIES THAT BIND BIPYRIDINIUM DICATIONS - SYNTHESES, COORDINATION AND ELECTROCHEMICAL PROPERTIESJournal articlehttp://purl.org/coar/resource_type/c_dcae04bcuuid:dd4c3a1a-e40c-480e-8c29-2a4ba3193c74EnglishSymplectic Elements at Oxford1991Beer, PTite, EIbbotson, AThe design, syntheses, co-ordination and electrochemical properties of novel multisite host molecules containing multiple benzo crown ether and ferrocenyl redox centres are described. The reaction of the macrocycle 2,8,14,20-tetraferrocenylpentacyclo[19.3.1.1.3,71 9,13.1 15,19]octacosa-1(25),3,5,7(28),9,11,13(27),15,17,19(26),21,23- dodecaen-4,6,10,12,16,18,22,24-octol 3 with propionic anhydride, benzoyl chloride or chlorocarbonylferrocene 6 gave new redox-active host molecules 4, 5 and 7 respectively. The acid-catalysed condensation of 15-formyl-2,3,5,6,8,9,11,12-octahydro-1,4,7,10,13-benzopentaoxacyclopentadecine with 1,3-dihydroxybenzene afforded a novel phenolic macrocycle 2,8,14,20-tetrakis(2,3,5,6,8,9,11,12-octahydro-1,4,7,10,13- benzopentaoxacyclopentadecin-15-yl)-pentacyclo[1.3.1.13,7.1 9,13.115,19]octacosa-1(25),3,5,7(28), 9,11,13(27),15,17,19(26),21,23-dodecaen-4,6,10,12,16,18,22,24-octol 14 which on reaction with propionic anhydride, benzoyl chloride, 6 or bromochloromethane gave respective host molecules 15, 16, 17 and 18 (the latter being the first crown ether cavitand host), each containing four benzo-15-crown-5 moieties. Electrochemical studies show the four ferrocenyl redox centres present in 5 to undergo two one-electron oxidations at +0.58 and +0.67 V in dichloromethane. Redox-active host 17, containing eight ferrocenyl moieties, was found to undergo independent reversible one-electron oxidations in dichloromethane. High-field 1H NMR complexation studies reversible one-electron oxidations in dichloromethane. High-field 1H NMR complexation studies revealed hosts 16-18 to form solution complexes with bipyridinium guest species, exclusively at the host's benzo crown ether binding site. |
| spellingShingle | Beer, P Tite, E Ibbotson, A MULTI REDOX-ACTIVE MACROCYCLIC HOST MOLECULES CONTAINING MULTIPLE BENZO CROWN-ETHER AND FERROCENYL MOIETIES THAT BIND BIPYRIDINIUM DICATIONS - SYNTHESES, COORDINATION AND ELECTROCHEMICAL PROPERTIES |
| title | MULTI REDOX-ACTIVE MACROCYCLIC HOST MOLECULES CONTAINING MULTIPLE BENZO CROWN-ETHER AND FERROCENYL MOIETIES THAT BIND BIPYRIDINIUM DICATIONS - SYNTHESES, COORDINATION AND ELECTROCHEMICAL PROPERTIES |
| title_full | MULTI REDOX-ACTIVE MACROCYCLIC HOST MOLECULES CONTAINING MULTIPLE BENZO CROWN-ETHER AND FERROCENYL MOIETIES THAT BIND BIPYRIDINIUM DICATIONS - SYNTHESES, COORDINATION AND ELECTROCHEMICAL PROPERTIES |
| title_fullStr | MULTI REDOX-ACTIVE MACROCYCLIC HOST MOLECULES CONTAINING MULTIPLE BENZO CROWN-ETHER AND FERROCENYL MOIETIES THAT BIND BIPYRIDINIUM DICATIONS - SYNTHESES, COORDINATION AND ELECTROCHEMICAL PROPERTIES |
| title_full_unstemmed | MULTI REDOX-ACTIVE MACROCYCLIC HOST MOLECULES CONTAINING MULTIPLE BENZO CROWN-ETHER AND FERROCENYL MOIETIES THAT BIND BIPYRIDINIUM DICATIONS - SYNTHESES, COORDINATION AND ELECTROCHEMICAL PROPERTIES |
| title_short | MULTI REDOX-ACTIVE MACROCYCLIC HOST MOLECULES CONTAINING MULTIPLE BENZO CROWN-ETHER AND FERROCENYL MOIETIES THAT BIND BIPYRIDINIUM DICATIONS - SYNTHESES, COORDINATION AND ELECTROCHEMICAL PROPERTIES |
| title_sort | multi redox active macrocyclic host molecules containing multiple benzo crown ether and ferrocenyl moieties that bind bipyridinium dications syntheses coordination and electrochemical properties |
| work_keys_str_mv | AT beerp multiredoxactivemacrocyclichostmoleculescontainingmultiplebenzocrownetherandferrocenylmoietiesthatbindbipyridiniumdicationssynthesescoordinationandelectrochemicalproperties AT titee multiredoxactivemacrocyclichostmoleculescontainingmultiplebenzocrownetherandferrocenylmoietiesthatbindbipyridiniumdicationssynthesescoordinationandelectrochemicalproperties AT ibbotsona multiredoxactivemacrocyclichostmoleculescontainingmultiplebenzocrownetherandferrocenylmoietiesthatbindbipyridiniumdicationssynthesescoordinationandelectrochemicalproperties |