Document Detail

Synthesis and Characterization of Tetrachlorodiarylethyne-Linked Porphyrin Dimers. Effects of Linker Architecture on Intradimer Electronic Communication.
MedLine Citation:
PMID:  11670323     Owner:  NLM     Status:  Publisher    
The effects of incorporating chloro groups at all ortho positions of a diphenylethyne linker that bridges the zinc and free base (Fb) components of a porphyrin dimer (ZnFbB(Cl(4))) have been investigated in detail via various static and time-resolved spectroscopic methods. The excited-state energy-transfer rate in ZnFbB(Cl(4)) ((134 ps)(-)(1)) is 5-fold slower than that in the corresponding dimer having an unsubstituted linker (ZnFbU, (24 ps)(-)(1)) but is only modestly slower than that in the dimer having o-methyl groups on the linker (ZnFbB(CH(3))(4), (115 ps)(-)(1)). The ground-state hole/electron-hopping rates in the oxidized bis-Zn analogues of all three dimers are much slower than the excited-state energy-transfer rates. There is no discernible difference between the hole/electron-hopping rates in the o-chloro- and o-methyl-substituted arrays. The similar ground- and excited-state dynamics observed for the o-chloro- and o-methyl-substituted arrays is attributed to the dominance of torsional constraints in mediating the extent of through-bond electronic communication. These constraints attenuate intradimer communication by restricting the rotation toward coplanarity of the phenyl rings of the linker and the porphyrin rings. Thus, the o-chloro groups on the linker decrease electronic communication via a steric, rather than purely electronic, mechanism.
Jon-Paul Strachan; Steve Gentemann; Jyoti Seth; William A. Kalsbeck; Jonathan S. Lindsey; Dewey Holten; David F. Bocian
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Publication Detail:
Journal Detail:
Title:  Inorganic chemistry     Volume:  37     ISSN:  1520-510X     ISO Abbreviation:  Inorg Chem     Publication Date:  1998 Mar 
Date Detail:
Created Date:  2001-Oct-23     Completed Date:  -     Revised Date:  -    
Medline Journal Info:
Nlm Unique ID:  0366543     Medline TA:  Inorg Chem     Country:  -    
Other Details:
Languages:  ENG     Pagination:  1191-1201     Citation Subset:  -    
Departments of Chemistry, North Carolina State University, Raleigh, North Carolina 27695-8204, Washington University, St. Louis, Missouri 63130-4899, and University of California, Riverside, California 92521-0403.
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