title: Excited-state energy-transfer dynamics of self-assembled imine-linked porphyrin dyads.
abstract: Toward the development of new strategies for the synthesis of multiporphyrin arrays, we have prepared and characterized (electrochemistry and static/time-resolved optical spectroscopy) a series of dyads composed of a zinc porphyrin and a free base porphyrin joined via imine-based linkers. One dyad contains two zinc porphyrins. Imine formation occurs under gentle conditions without alteration of the porphyrin metalation state. Five imine linkers were investigated by combination of formyl, benzaldehyde, and salicylaldehyde groups with aniline and benzoic hydrazide groups. The imine-linked dyads are quite stable to routine handling. The excited-state energy-transfer rate from zinc to free base porphyrin ranges from (70 ps)(-)(1) to (13 ps)(-)(1) in toluene at room temperature depending on the linker employed. The energy-transfer yield is generally very high (>97%), with low yields of deleterious hole/electron transfer. Collectively, this work provides the foundation for the design of multiporphyrin arrays that self-assemble via stable imine linkages, have predictable electronic properties, and have comparable or even enhanced energy-transfer characteristics relative to those of other types of covalently linked systems.
authors.affiliation: Department of Chemistry, Washington University, St Louis, Missouri 63130-4899, USA.
authors.forename: Igor V
authors.initials: IV
authors.lastname: Sazanovich
authors.forename: Arumugham
authors.initials: A
authors.lastname: Balakumar
authors.forename: Kannan
authors.initials: K
authors.lastname: Muthukumaran
authors.forename: Eve
authors.initials: E
authors.lastname: Hindin
authors.forename: Christine
authors.initials: C
authors.lastname: Kirmaier
authors.forename: James R
authors.initials: JR
authors.lastname: Diers
authors.forename: Jonathan S
authors.initials: JS
authors.lastname: Lindsey
authors.forename: David F
authors.initials: DF
authors.lastname: Bocian
authors.forename: Dewey
authors.initials: D
authors.lastname: Holten