Mechanisms, pathways, and dynamics of excited-state energy flow in self-assembled wheel-and-spoke light-harvesting architectures

Article Abstract:

The characterization of the multiple pathways for excited-state energy flow in cyclic hexameric arrays (Z[n.sub.6], Z[n.sub.3]F[b.sub.3]) and the corresponding self-assembled host-guest constructs (Z[n.sub.6].TP, Z[n.sub.6].DPFb) is reported. The results form a framework for elucidating the complex energy flow patterns in arrays, in which one or two Fb porphyrins within the host wheel serve as way stations for energy transfer to the guest and could be used to design the next-generation light-harvesting systems for use in artificial solar-energy conversion systems.

United States

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Conformational and electronic effects of phenyl-ring fluorination on the photophysical properties of nonplanar dodecaarylporphyrins

Article Abstract:

The relationships between molecular composition, macrocycle planarity, electronic characteristics, and photophysical behavior is explored to investigate a series of free-base and zinc dodecaarylporphyrins with varying degrees of fluorination of the peripheral phenyl rings. The resulting photophysical behavior clearly indicated that all the complexes are nonplanar and separates the porphyrins into two distinct classes.

Observations, Electric properties, Electrochemistry, Fluorination

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Photoinduced evolution on the conformational landscape of nonplanar dodecaphenylporphyrin: picosecond relaxation dynamics in the (super 1)[pi, pi(super *)] excited state

Article Abstract:

The photoexcitation of the nonplanar porphyrin 2,3,5,7,8,10,12,13,15,17,18,20-dodecaphenylporphyrin (H2DPP) are examined using transient absorption spectroscopy. It is shown that H2DPP undergoes conformational/vibrational relaxation and equilibration in the (super 1)[pi,pi(super *)] excited state that takes ~10 ps, and that this process is not observed for the nominally planar 5,10,15,20-tetraphenylporphyrin system.

Usage, Chemistry, Physical and theoretical, Physical chemistry, Absorption spectra

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