Porphyrazines metal complexes

Subsequent reaction of porphyrazines 170 and 171 with Cu(OAc)2 resulted in the selective metalation within the macrocyclic cavity to provide the corresponding copper complexes 166 (62%) and 172 (47%). Treatment of pz 170 with manganese acetate and iron sulfate in dimethyl sulfate gave the dmso adducts 173 (70%) and 174 (85%), respectively (168). Axial ligation was also observed when other metals were incorporated such as cobalt acetate, nickel acetate, and zinc acetate to give the metal complexes 175 (83%), 176 (70%), and 177 (90%) as the hydrates. The axial ligand of... 

Monoazaporphyrins, and their metal complexes, show absorption maxima at 380-410 nm (Soret, e as 105), 500-550 nm QS, eas 104) and 560-590 nm (a, as 104).177 Both a and / bands of the metal-free bases split into two with an interval of 35 nm and 50 nm respectively. Similarly, of 320-350 nm (Soret, e as 104), 530-550 nm (/ , as 104) and 570-600nm (a, as 104) are observed for the tetraaza analogues.178 Detailed energy level calculations were reported on metal-free and metallo porphyrazines.179... 

Mg and Cd are easily dissociated from their porphyrazine complexes in acetic acid.188,190 Demetallation of Mg- and Cd-Ph8Tap in pyridine-acetic acid is first order in the metal complexes and second order in the solvated proton. Similar results are reported on the Zn- and Ni-Ph8Tap-DMS0-H2S04 H20 system. 

Keywords TDDFT Excitation energies Excited states Transition metal complexes Electronic spectra Metallotetrapyrroles Metallocarbonyls a-diimine complexes Porphyrins Porphyrazines Phthalocyanines Werner complexes Sandwich complexes... 

With the purpose of further increasing the number of adjustable photochromic parameters of the subunit, a binuclear metal complexe of porphyrazine bearing six bis(trimethylthiophenyl) functionalities at the periphery was synthesized in our laboratory [40] (Scheme 12). The structure of binuclear porphyrazine was rigidly constrained in a coplanar arrangement with extended n-conjugated subunits. 

Figure 12. Supramolecular porphyrins obtained by coordination of transition metal complexes to the periphery of the macrocyclic ring (a similar scheme can be extended to the 3-TPyP and analogous porphyrazine species), [dmso = dimethyl sulfoxide (ligand), form = A,A-9-di- -tolyformamidinate, and TFA = trifluoroacetate.l...

Vagin SI, Hanack M (2002) Synthesis emd spectroscopic properties of non-symmetrical benzo-annulated porphyrazines and their metal complexes. Eur J Org Chem 2(X)2 2859-2865... 

Duggan SA, Eallon G, Eangford SJ, Eaau VL, Satchell JF, Paddon-Row MN (2001) Crown-linked porphyrin systems. J Org Chem 66(12) 4419-4426. doi 10.1021/jo001700p Efimova SV, Korzhnevskiy AB, Koyfman 01 (2008) Metal complexes of tetra(6-rert-butyl-2,3-quinolino)porphyrazine I Synthesis. Russ J Gen Chem 78(7) 1614-1621. doi 10. 1134/S1070363208080252... 

Meso substitution of porphyrines to give tetraazaporphyrines, so-called porphyrazines, modulates the electronic character of the macrocycle. While porphyrazines have received considerably less attention than porphyrines over many years, this has changed due to the development of efficient syntheses of soluble derivatives.1 6-1809 Also, various porphyrazines (and phtalocyanines) with peripheral groups for metal ion coordination have been prepared and used for the construction of multimetallic complexes.1806 Ni porphyrazines (695) typically show absorptions spectra with a strong Q band at around 615nm. 

In this chapter, the porphyrazines are named in one of two ways. For simple substitution patterns, substituents will be denoted directly for example, Cu(II) oc-taethylporphyrazine can be written Cu[pz(Et)g], When the pattern is more complex, or general concepts are discussed, the porphyrazines are systematically named based on the nature of their substituents, using the general formula, M[pz (AmB4 ), where M represents the metal ion and its axial ligands (or two hydro-... 

Nitrogen substituted porphyrazines were the second type of heteroatom-deriva-tized pz macrocycle reported and were prepared from the readily derivatized diami-nomalconitrilc (DAMN) (7). Octakis(dimethylamino)porphyrazines are extremely electron-rich systems and have been used to prepare charge-transfer complexes with Cgo, as well as to peripherally chelate metals or convert to crown appended systems (38, 39). The unsymmetrical dimethylaminoporphyrazine analogues have also been reported (29), as well as the first example of the desymmetrized seco-pz from the dimethylaminoporphyrazine (8, 40). The nitrogen substituted porphyrazines are discussed in Section V. 

Titrations of Ag+ with porphyrazines 81c and 81h resulted in a decrease and broadening of the Q band up to 2 equiv of metal coupled with the appearance of at least five isobestic points. Further addition of Ag+ resulted in a visible change from purple to blue and a decrease of the 675-nm band and appearance of a sharp peak at 650 nm, which reached a maximum at 6 equiv of Ag+. The n-n transition disappeared between 0 and 6 equiv. The Hg+ ion gave similar results. Compound pz 81f displayed more complex interactions in titrations with AgC104. 

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