Formation of porphyrins in the presence of acid-labile metalloporphyrins: a new route to mixed-metal multiporphyrin arrays.
The ability to incorporate distinct metalloporphyrins at designated sites in multiporphyrin arrays is essential for diverse applications in materials and biomimetic chemistry. The synthesis of such mixed-metal arrays via acid catalyzed reactions has largely been restricted to metalloporphyrins of stability class II (e.g., Cu, Co, Ni) or I. We describe routes for the rational synthesis of mixed-metal arrays via acid-catalyzed condensations that are compatible with metalloporphyrins of stability class III (e.g., Zn) and IV (e.g., Mg). The routes are demonstrated for p-phenylene-linked arrays. The key finding is that several mild Lewis acids [InCl(3), Sc(OTf)(3), Yb(OTf)(3), and Dy(OTf)(3)], which are known to catalyze the dipyrromethane + dipyrromethane-dicarbinol condensation in CH(2)Cl(2) at room temperature without acidolysis, do not demetalate zinc or magnesium porphyrins under the same conditions. Rational routes to porphyrin dyads and triads employ reaction of a (porphyrin)-dipyrromethane and a (porphyrin)-dipyrromethane-dicarbinol. The porphyrin-forming reactions (six examples) proceed in yields of 18-28%. The metalation states of the arrays prepared in this manner include Zn-free base (ZnFb), MgFb, ZnFbMg, ZnFbZn, and ZnFbFb. Studies of the catalysis process indicate that the dipyrromethane + dipyrromethane-dicarbinol condensation is catalyzed by both the Lewis acid and a Brønsted acid derived in situ from the Lewis acid. Taken together, the ability to employ otherwise "acid-labile" metalloporphyrins as precursors in condensation procedures should broaden the scope of accessible mixed-metal multiporphyrin arrays and motivate further studies of the application of mild Lewis acid catalysts in porphyrin chemistry.
Speckbacher
Markus
M
Department of Chemistry, North Carolina State University, Raleigh, North Carolina 27695-8204, USA.
Yu
Lianhe
L
Lindsey
Jonathan S
JS
D040761:Biomimetic Materials; D002384:Catalysis; D002855:Chromatography, Thin Layer; D007202:Indicators and Reagents; D009682:Magnetic Resonance Spectroscopy; D013058:Mass Spectrometry; D008665:Metalloporphyrins / Q000737:chemistry*; D008670:Metals / Q000737:chemistry*; D011166:Porphyrins / Q000138:chemical synthesis*; D013056:Spectrophotometry, Ultraviolet
D007202:Indicators and Reagents; D008665:Metalloporphyrins; D008670:Metals; D011166:Porphyrins