ROM polymerization-capture-release strategy for the chromatography-free synthesis of novel unsymmetrical porphyrazines.
[reaction: see text] Crossover-Linstead macrocyclization reactions of two norbornenyl-tagged diaminomaleonitriles with dipropylmaleonitrile gave access to crude mixtures of porphyrazines containing diamino-hexapropyl-porphyrazine magnesium complexes. The mixtures were subjected to ring-opening metathesis polymerization to yield the insoluble diaminoporphyrazine-functionalized polymers. Acid-mediated cleavage from the polymer backbone followed by acylation of the resultant sensitive macrocyclic diamines gave monoacetyl-, monotrifluoroacetyl-, and ditrifluoroacetyl-substituted porphyrazinediamines. Conversion of these amido-porphyrazines to the corresponding zinc macrocycles and studies of their electronic absorption and emission spectra, electrochemistry, and photophysics are described.
Fuchter
Matthew J
MJ
Department of Chemistry, Imperial College London, London SW7 2AZ, UK.
Vesper
Benjamin J
BJ
Murphy
Karen A
KA
Collins
Hazel A
HA
Phillips
David
D
Barrett
Anthony G M
AG
Hoffman
Brian M
BM