SYNTHESIS, CHARACTERIZATION, AND REACTIVITY TOWARD DIOXYGEN OF COPPER MANGANESE COFACIAL PORPHYRINS - CRYSTAL AND MOLECULAR-STRUCTURES OF A HETEROBIMETALLIC BIPHENYLENE-PILLARED COFACIAL DIPORPHYRIN

The synthesis of a novel family of heterobinuclear cofacial biphenylene-bridged or anthracene-bridged bisporphyrin, (DP)CuMnX, is reported, DP being either 1,8-bis(2,8,13,17-tetraethyl-3,7,12,18-tetramethylporphyrin-5-yl)biphenylene, DPB, or 1,8-bis(2,8,13,17-tetraethyl-3,7,12,18-tetramethylporphyrin-5-yl)anthracene, DPA, Each complex has been characterized by mass spectrometry, UV-vis, IR, and ESR spectroscopies, and magnetic measurements. Metal-metal interactions are clearly established on the basis of various spectroscopic data. At room temperature the copper(II)-manganese(II) diporphyrin biphenylene complex forms a reversible dioxygen adduct. Moreover, the molecular structure of (DPB)CuMnCl has been solved by X-ray diffraction. (DPB)CuMnCl.C8H10 (C76H76N8CuMnCl.C8H10) crystallizes in the triclinic: system, space group P (1) over bar with lattice constants a = 13.232(5) Angstrom, b = 15.228(6) Angstrom, c = 18.997(5) Angstrom, alpha = 103.22(3)degrees, beta = 101.63(3)degrees, gamma = 94.86(3)degrees, V = 3615 Angstrom(3), Z = 2, R(F) = 6.95%, R(W)(F) = 6.75%, and GOF = 1.47 for 2942 reflections with I greater than or equal to 3 sigma(I). In (DPB)CuMnCl, the metal-metal distance is 4.127(3) Angstrom and both porphyrin moieties are slipped by alpha = 25.8 degrees.