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- W2080556687 endingPage "3197" @default.
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- W2080556687 abstract "Pseudo-para[2.2]paracyclophane- and [2.1]orthocyclophane-bridged diruthenium complexes 2 and 3 with two interlinked electroactive styryl ruthenium moieties have been prepared and investigated. Both complexes undergo two reversible consecutive one-electron oxidation processes which are separated by 270 or 105 mV. Stepwise electrolysis of the neutral complexes to first the mixed-valent radical cations and then the dioxidized dications under IR monitoring reveal incremental shifts of the charge-sensitive Ru(CO) bands and allow for an assignment of their radical cations as moderately or very weakly coupled mixed-valent systems of class II according to Robin and Day. Ground-state delocalization in the mixed-valent forms of these complexes as based on the CO band shifts is considerably larger for the “closed” paracyclophane as for the “half-open” orthocyclophane. Experimental findings are backed by the calculated IR band patterns and spin density distributions for radical cations of slightly simplified model complexes 2Me+ and 3Me+ with the PiPr3 ligands replaced by PMe3. Radical cations 2+ and 3+ feature a characteristic NIR band that is neither present in their neutral or fully oxidized forms nor in the radical cation of the monoruthenium [2.2]paracyclophane complex 1 with just one vinyl ruthenium moiety. These bands are thus assigned as intervalence charge-transfer (IVCT) transitions. Our results indicate that, for the radical cations, electronic coupling “through-space” via the stacked styrene decks is significantly more efficient than the “through-bond” pathway." @default.
- W2080556687 created "2016-06-24" @default.
- W2080556687 creator A5020629189 @default.
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- W2080556687 creator A5067859993 @default.
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- W2080556687 creator A5083893259 @default.
- W2080556687 date "2011-10-01" @default.
- W2080556687 modified "2023-09-25" @default.
- W2080556687 title "Electron delocalization in vinyl ruthenium substituted cyclophanes: Assessment of the through-space and the through-bond pathways" @default.
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