ABSTRACT
Energy conversion cycles are aimed at driving unfavorable, small-molecule activation reactions with a photon harnessed by a transition metal complex. A challenge that has occupied researchers for several decades is to create molecular photocatalysts to promote the production of hydrogen from homogeneous solution. We now report the use of a two-electron mixed-valence dirhodium compound to photocatalyze the reduction of hydrohalic acid to hydrogen. In this cycle, photons break two RhII-X bonds of a LRh0-RhIIX2 core in the presence of a halogen trap to regenerate the active LRh0-Rh0 catalyst, which reacts with hydrohalic acid to produce hydrogen.
ABSTRACT
The synthesis and characterization of cofacial bisporphyrins juxtaposed by xanthene-bridged pillars are presented. The one-pot preparation of the xanthene dialdehyde avoids the lengthy bridge synthesis accompanying other cofacial porphyrin systems, thus allowing for the facile preparation of homobimetallic zinc (10), copper (11), and nickel (12) complexes. The cofacial orientation of the two porphyrin macrocycles was confirmed by X-ray crystallography. Structural data are provided for bisporphyrins 10-12: 10 (C79H82N8OZn2), triclinic, space group P1, a = 11.2671(2) A, b = 14.9809(2) A, c = 20.4852(2) A, alpha = 101.6680(10) degrees, beta = 100.8890(10) degrees, gamma = 101.8060(10) degrees, Z = 2; 11 (C79H82N8OCu2), triclinic, space group P1, a = 11.21410(10) A, b = 14.9539(5) A, c = 20.6915(7) A, alpha = 101.810(2) degrees, beta = 101.044(2) degrees, gamma = 101.722(2) degrees, Z = 2; 12 (C79H82N8ONi2), monoclinic, space group C2/c, a = 24.1671(4) A, b = 10.669 A, c = 50.5080(9) A, beta = 99.553(2) degrees, Z = 8. Exciton interactions between the porphyrin rings are apparent in electronic spectra, consistent with the cofacial superstructure. The combination of structural and spectroscopic data provides a basis for the design of additional metal derivatives for the activation of dioxygen and other small molecules.
