title: Phthalocyanine-Perylenediimide Cart Wheels.
abstract: The electronic features of Zn(II) and Ru(II) phthalocyanines (Pcs) have been modulated by direct peripheral attachment of up to eight ferrocenes. The presence of peripheral ferrocenes noticeably impacts the electronic properties of the corresponding ZnPc and RuPc complexes 7, 12 and 9, 15, respectively-a notion that is supported by optical spectroscopy with bathochromic shifts of up to 8-10 nm per ferrocene unit. Cyclic voltammetry and optical spectroscopy reveal long-distance (10-11 bonds) electronic interaction between ferrocene units. The ZnPc and RuPc complexes have been integrated into a series of orthogonal, supramolecular bis(phthalocyanine)-perylenediimide electron donor-acceptor conjugates, 2a,b and 3a,b. In these cart-wheel-shaped arrays, coordination of ditopic perylenediimide 16, containing two pyridyl substituents at its imido positions, enabled selective interactions with the metal centers of phthalocyanines 7, 12, 9, and 15. The presence of ferrocenes in, for example, Zn complexes 2a and 3a triggers a fast energy transfer from the excited-state PDI to ZnPc. In the RuPc-PDI conjugates, substitution with ferrocenes produces a slight acceleration of the charge separation upon photoexcitation of the PDI chromophore. However, charge recombination is accelerated by 2 orders of magnitude in ferrocene-containing conjugates when compared to that in the analogous tert-butyl-substituted array 1b.
authors: Departamento de Química Orgánica, Universidad Autónoma de Madrid , Cantoblanco, 28049 Madrid, Spain.
authors: Javier
authors: J
authors: Fernández-Ariza
authors: Department of Chemistry and Pharmacy & Interdisciplinary Center for Molecular Materials (ICMM), University of Erlangen-Nuremberg , Egerlandstraße 3, 91058 Erlangen, Germany.
authors: Rafael M
authors: RM
authors: Krick Calderón
authors: Departamento de Química Orgánica, Universidad Autónoma de Madrid , Cantoblanco, 28049 Madrid, Spain.
authors: M Salomé
authors: MS
authors: Rodríguez-Morgade
authors: Department of Chemistry and Pharmacy & Interdisciplinary Center for Molecular Materials (ICMM), University of Erlangen-Nuremberg , Egerlandstraße 3, 91058 Erlangen, Germany.
authors: Dirk M
authors: DM
authors: Guldi
authors: Departamento de Química Orgánica, Universidad Autónoma de Madrid , Cantoblanco, 28049 Madrid, Spain.|IMDEA-Nanociencia , c/ Faraday 9, Cantoblanco, 28049 Madrid, Spain.
authors: Tomás
authors: T
authors: Torres