Efficient Excitation Energy Transfer in Long Meso−Meso Linked Zn(II) Porphyrin Arrays Bearing a 5,15-Bisphenylethynylated Zn(II) Porphyrin Acceptor

Citations Over TimeTop 10% of 2003 papers

Abstract

Electronically coupled porphyrin arrays are suitable for artificial light harvesting antenna in light of a large absorption cross-section and fast excitation energy transfer (EET). Along this line, an artificial energy transfer model system has been synthesized, comprising of an energy donating meso-meso linked Zn(II) porphyrin array and an energy accepting 5,15-bisphenylethynylated Zn(II) porphyrin linked via a 1,4-phenylene spacer. This includes an increasing number of porphyrins in the meso-meso linked Zn(II) porphyrin array, 1, 2, 3, 6, 12, and 24 (Z1A, Z2A, Z3A, Z6A, Z12A, and Z24A). The intramolecular singlet-singlet EET processes have been examined by means of the steady-state and time-resolved spectroscopic techniques. The steady-state fluorescence comes only from the acceptor moiety in Z1A-Z12A, indicating nearly the quantitative EET. In Z24A that has a molecular length of ca. 217 A, the fluorescence comes largely from the acceptor moiety but partly from the long donor array, indicating that the intramolecular EET is not quantitative. The transient absorption spectroscopy has provided the EET rates in real time scale: (2.5 ps)(-1) for Z1A, (3.3 ps)(-1) for Z2A, (5.5 ps)(-1) for Z3A, (21 ps)(-1) for Z6A, (63 ps)(-1) for Z12A, and (108 ps)(-1) for Z24A. These results have been well explained by a revised Förster equation (Sumi formula), which takes into account an exciton extending coherently over several porphyrin pigments in the donor array, whose length is not much shorter than the average donor-acceptor distance. Advantages of such strongly coupled porphyrin arrays in light harvesting and transmission are emphasized in terms of fast EET and a large absorption cross-section for incident light.

Related Papers

• → Synthesis of porphyrin-2,3,12,13- and -2,3,7,8-tetraones: building blocks for the synthesis of extended porphyrin arrays(1995)101 cited
• → Synthesis and Shuttling Behavior of [2]Rotaxanes with a Pyrrole Moiety(2016)26 cited
• → Metalloporphyrins in the Biomimetic Oxidation of Lignin and Lignin Model Compounds: Development of Alternative Delignification Strategies(2003)4 cited
• Design, synthesis and evaluation of novel hydroxyethylamine derivatives with nitrogen heterocyclic moiety at N-terminal as BACE1 inhibitors(2010)
• [UV-Vis spectroscopic characterization of LB films of hydroxyl-substituted porphyrin derivatives].(1999)