Photoinduced energy and electron transfer processes in supramolecular species. Tris(bipyridine) complexes of Ru(II)/Os(II), Ru(II)/Ru(III), Os(II)/Os(III), and Ru(II)/Os(III) separated by a rigid spacer

Journal Article · Wed Nov 10 00:00:00 EST 1993 · Inorganic Chemistry; (United States)

DOI:https://doi.org/10.1021/ic00075a048· OSTI ID:5035433

De Cola, L; Balzani, V ^[1]; Barigelletti, F; Flamigni, L ^[2]; Belser, P; Zelewsky, A von ^[3]; Frank, M; Voegtle, F ^[4]

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1. Univ. of Bologna (Italy)
2. FRAE-CNR, Bologna (Italy)
3. Univ. of Fribourg (Switzerland)
4. Univ. of Bonn (Germany)

The bis(bipyridine) bridging ligand 1,4-bis[2-(2,2[prime]-bipyridin-5-yl)ethenyl]bicyclo[2.2.2]octane(bpy-S-bpy), where S is a rigid spacer made of a bicyclooctane unit symmetrically linked to two ethylene-type units in an E, E-configuration, has been synthesized and its complexes (bpy)[sub 2]Ru(bpy-S-bpy)[sup 2+] (Ru[sup II][center dot]A), (bpy)[sub 2]Os(bpy-S-bpy)[sup 2+] (Os[sup II][center dot]A), (bpy)[sub 2]-Ru(bpy-S-bpy)Ru(bpy)[sub 2][sup 4+] (Ru[sup II][center dot]A[center dot]Ru[sup II]), (bpy)[sub 2]Os(bpy-S-bpy)Os(bpy)[sub 2][sup 4+] (Os[sup II][center dot]A[center dot]Os[sup II]), (bpy)[sub 2]Ru(bpy-S-bpy)-Os(bpy)[sub 2][sup 4+] (Ru[sup II][center dot]A[center dot]Os[sup II]) have been prepared as PF[sub 6[minus]] salts. The length of the rigid spacer S is 9 [angstrom], and the center-to-center separation distance in the dinuclear complexes is 17 [angstrom]. In all these novel compounds, each Ru-based and Os-based unit displays its own absorption spectrum and electrochemical properties, regardless of the presence of a second metal-based unit. The homometallic dinuclear compounds exhibit the same luminescence properties as the corresponding mononuclear species, whereas in the heterometallic dinuclear Ru[sup II][center dot]A[center dot]Os[sup II] species 91% of the Ru-based luminescence intensity is quenched by energy transfer to the Os-based unit, whose luminescence is accordingly sensitized (acetonitrile solution, room temperature).

• OSTI ID: 5035433
• Journal Information: Inorganic Chemistry; (United States), Vol. 32:23; ISSN 0020-1669
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
14 SOLAR ENERGY
OSMIUM COMPLEXES
ELECTRON TRANSFER
ENERGY TRANSFER
RUTHENIUM COMPLEXES
ABSORPTION SPECTROSCOPY
BIPYRIDINES
ELECTROCHEMISTRY
KINETICS
LUMINESCENCE
AZINES
CHEMISTRY
COMPLEXES
HETEROCYCLIC COMPOUNDS
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
PYRIDINES
SPECTROSCOPY
TRANSITION ELEMENT COMPLEXES
400500* - Photochemistry
140505 - Solar Energy Conversion- Photochemical
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& Thermochemical Conversion- (1980-)