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Caballero Calvo, Maria EsmeraldaAutor o CoautorRodriguez Morgade, Maria SalomeAutor o CoautorTorres Cebada, TomasAutor o Coautor

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Ruthenoarenes versus phenol derivatives as axial linkers for subporphyrazine dimers and trimers

Publicado en:CHEMISTRY-A EUROPEAN JOURNAL. 20 (21): 6518-6525 - 2014-05-19 20(21), DOI: 10.1901/jeab.1979.32-419

Autores: Caballero, Esmeralda; Romero-Nieto, Carlos; Strauss, Volker; Salome Rodriguez-Morgade, M; Guldi, Dirk M; Sessler, Jonathan L; Torres, Tomas

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Resumen

The subporphyrazine (SubPz) dimer diboron(III) [μ-1',4'-benzenediolato] [bis-(1,2,6,7,11,12-hexapropylsubporphyrazinato)] (2) and trimer triboron(III)[μ-1',3',5'-benzenetriolato][tris-(1,2,6,7,11, 12-hexapropylsubporphyrazinato)] (4), consisting of SubPz units assembled through their axial positions by hydroquinone- and phloroglucinol-linkers, respectively, have been prepared. Selective ruthenium-π-coordination to the linking aromatic rings afforded SubPz arrays 8 and 9, respectively. These latter systems displayed different degrees of electronic communication between the macrocycles relative to 2 and 4 as inferred from analyses of the ground- and excited-state features. For instance, as revealed by time-resolved pump probe transient absorption spectroscopy, the excited singlet states of dimer 2 and trimer 4 undergo rather rapid deactivation. In contrast, the presence of a ruthenoarene linker, as in 8 and 9, serves to increase the SubPz singlet excited state lifetimes; these now reach values similar to those seen in the case of monomeric SubPz compounds that either do or do not contain ruthenoarene subunits (i.e., 7 and 6, respectively). These findings are ascribed to the redox active nature of the hydroquinone and phloroglucinol linkers in 2 and 4 and a change in the electronics that results from organometallic functionalization. Making a connection: Cyclopentadienylruthenium π-coordination to the axial phenolic substituent that functions to link individual subporphyrazine (SubPz) subunits in dimers and trimers serves to modify the interactions between the macrocyclic constituents (see figure). The ground and excited states of the SubPz dimers and trimers of this study reflect the nature of the bridging spacer, with the extent of inter-subunit coupling being relatively increased in the case of the ruthenoarene bridged systems. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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