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Synthesis of Zn‐, Mn‐, and Fe‐Containing Mono‐ and Heterometallated Ethanediyl‐Bridged Porphyrin Dimers
Author(s) -
Borovkov Victor V.,
Lintuluoto Juha M.,
Inoue Yoshihisa
Publication year - 1999
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/(sici)1522-2675(19990609)82:6<919::aid-hlca919>3.0.co;2-p
Subject(s) - porphyrin , chemistry , dimer , free base , transition metal , metal , electron transfer , photochemistry , zinc , crystallography , manganese , fluorescence , base (topology) , metal ions in aqueous solution , catalysis , organic chemistry , mathematical analysis , salt (chemistry) , physics , mathematics , quantum mechanics
New ethanediyl‐bridged unsymmetrical mono‐ and heterometallated dimers of 2,3,7,8,12,13,17,18‐octaethyl‐21 H ,23 H ‐porphyrin (H 2 oep) containing transition‐metal ions (Mn and Fe) were synthesized by a facile stepwise metallation/demetallation process under mild conditions. The novel metallation strategy initially involved the predominant insertion of Zn into one of the two porphyrin rings of the free‐base dimer, followed by the incorporation of Mn or Fe into the other porphyrin ring under exceptionally mild conditions, giving corresponding heterometallic dimers; the subsequent removal of Zn yielded mono‐transition‐metal dimers. The emission spectrum of the monozinc dimer predominantly exhibited fluorescence bands of the free‐base porphyrin component, indicating a very efficient energy‐transfer process. Conversely, emission of the free‐base or Zn porphyrin component of transition metal containing dimers was strongly quenched due to photoinduced electron transfer.