On surface chemical reactions of free-base and titanyl porphyrins with r-TiO₂(110): a unified picture

Abstract

In this Perspective we present a comprehensive study of the multiple reaction products of metal-free porphyrins (2H-Ps) in contact with the rutile TiO2(110) surface. In absence of peripheral functionalization by...

Charge and adsorption height dependence of the self-metalation of porphyrins on ultrathin MgO(001) films

“…For example, TPP readily metalates on CoO(111) and Co 3 O 4 (111) 9,14 films at room temperature, but requires thermal activation on TiO 2 (110), 13 where initially the diacid (4H-TPP) is formed and the metalation process might be triggered by the diffusion of interstitial Ti to the surface. 15–17 In addition, a strong dependence of the self-metalation activity on oxides on the adsorption geometry has been noted. The introduction of specific anchor groups, e.g.…”

Seeding the vertical growth of laterally coherent coordination polymers on the rutile-TiO2(110) surface

“…16 These porphyrins adsorb on the protruding rows of oxygen atoms (O br ) yielding a commensurate (2 × 4)-oblique phase, like that observed also for 2H-TPP and its titanyl counterparts. 17,18 According to DFT calculations, the adsorption site of Co-and Zn-TPP is driven by direct linking of their metal atom atop one O br atom. In the case of Ni-and Cu-TPP, the adsorption is only driven by the network of weak hydrogen bonds among the C-H phenyl moieties and the adjacent O br rows, while the central metal atom (and its heteroaromatic macrocycle) floats unperturbed above the O br rows with no direct interaction.…”