A zinc(II) tetraphenylporphyrin peripherally functionalized with redox-active “trans-[(η5-C5H5)Fe(η5-C5H4)CC](κ2-dppe)2Ru(CC)-” substituents: Linear electrochromism and third-order nonlinear optics

A nonametallic organometallic-coordination complex (4), assembled from redox-active ferrocenyl (Fc) and Ru(κ2-dppe)2 fragments (dppe = 1,2-bis(diphenylphosphino)ethane) as peripheral donor groups and a central Zn(II) tetraphenylporphyrin (ZnTPP) core, has been prepared and characterized. Complex 4 is obtained in one step from a pentametallic organometallic porphyrin precursor following substitution of the peripheral chloride ligands by ferrocenylalkynyl moieties (CCFc). The spectroelectrochemistry of 4, and that of previously reported porphyrins featuring related peripheral electron-rich d6-transition metal alkynyl units, has been investigated; the optical and redox properties of 4 are briefly discussed, and its potential, and that of a related pentanuclear tetraferrocenyl ZnTPP complex, to function as redox-switchable chromophores is examined. Preliminary studies of the cubic NLO properties of 4 have been undertaken by Z-scan studies at 560 nm and 630 nm, the results from which are also reported.

Graphical abstractThe synthesis and characterization of a new Zn(II) tetraphenylporphyrin derivative (4) featuring eight redox-active centers at the periphery (four trans-Ru(κ2-dppe)2 fragments and four ferrocenyl endgroups) is reported, and its linear spectroelectrochemistry and third-order nonlinear optical properties at 560 nm and 630 nm are discussed.Figure optionsDownload full-size imageDownload as PowerPoint slide