Tetra-2,3-pyrazinoporphyrazines with externally appended pyridine rings. 8. Central (Zn(II), Cu(II), Mg(II)(H2O), Cd(II)) and exocyclic (Pd(II)) metal ion binding in heteropentametallic complexes from tetrakis-2,3-[5,6-di(2-pyridyl)pyrazino]porphyrazine

Inorganic Chemistry
Maria Pia DonzelloKarl M Kadish

Abstract

A series of heteropentametallic porphyrazine macrocycles, represented as [(PdCl(2))(4)LM], where L = dianion of tetrakis-2,3-[5,6-di(2-pyridyl)pyrazino]porphyrazine and M = Zn(II), Cu(II) Mg(II)(H(2)O) or Cd(II), were prepared by reaction of the corresponding mononuclear [LM] species, and their behavior was examined by UV-visible and NMR spectroscopy, electrochemistry, and thin layer spectroelectrochemistry in nonaqueous media. The PdCl(2) units in [(PdCl(2))(4)LM] are coordinated at the pyridine N atoms of the external dipyridinopyrazine fragments ("py-py" coordination) and are displaced out of the plane of the central pyrazinoporphyrazine macrocycle as verified by (1)H and (13)C NMR data on [(PdCl(2))(4)LZn]. The same arrangement is also strongly suggested by similar NMR data on the Mg(II) and Cd(II) analogues. The predominant component in the synthesized materials among the four predictable macrocyclic isomers has the four exocyclic N(2(py))PdCl(2) square planar coordination sites on the same side of the central macrocyclic framework (4:0 isomer, C(4v) symmetry), and this is accompanied by a minor isomeric component (2:2 cis or trans), in line with previous findings on the pentapalladated species [(PdCl(2))(4)LPd]. IR, UV-vi...Continue Reading

References

Jun 24, 1998·Journal of the National Cancer Institute·T J DoughertyQ Peng
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Jun 9, 2005·Chemical Reviews·Konrad SzaciłowskiGrazyna Stochel

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Citations

Mar 18, 2015·Dalton Transactions : an International Journal of Inorganic Chemistry·Antonin CidlinaPetr Zimcik
Oct 19, 2019·Photochemical & Photobiological Sciences : Official Journal of the European Photochemistry Association and the European Society for Photobiology·Lukas SchneiderBernhard Spingler

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