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

A nonametallic organometallic-coordination complex (4), assembled from redox-active ferrocenyl (Fc) and Ru(K2-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 (CFc). The spectroelectrochemistry of 4, and that of previously reported porphyrins featuring related peripheral electron-rich d5.-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. (C) 2014 Elsevier Ltd. All rights reserved.