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

Abstract

A nonametallic organometallic-coordination complex (4), assembled from redox-active ferrocenyl (Fc) and Ru( 2-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 (CCFc). The spectroelectrochemistry of 4, and that of previously reported porphyrins featuring related peripheral electron-rich d 6-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.

A hybrid ruthenium alkynyl/zinc porphyrin “Cross Fourchée” with large cubic NLO properties

“…Finally, IR spectroscopy confirmed the presence of Ru(II)-alkynyl linkages, which are revealed by the presence of a broad absorption at ca. [27][28][29][30] The UV-Vis absorption spectrum of 2 in CH 2 Cl 2 resembles that of compound 1-H ( Fig. 19 In addition, a second and less intense absorption at 2200 cm −1 was also detected for 2, which corresponds to the various overlapped ν CuC modes of the tolane spacers.…”

Iron and Ruthenium Alkynyl Complexes with 2‐Fluorenyl Groups: Some Linear and Nonlinear Optical Absorption Properties

“…Z‐Scan Measurements: Third‐order nonlinear optical properties were investigated as described previously, but with some modifications. The laser system consisted of a Quantronix Integra‐C3.5F pumping a Quantronix Palitra‐FS optical parametric amplifier, tunable over a wavelength range from 500 nm to 2000 nm.…”

Fluorenylporphyrins functionalized by electrochromic ruthenium units as redox-triggered fluorescence switches

“…Complex 1 is therefore a potentially useful fluorescence switch although its fluorescence quantum yield is quite low (Ф lum = 1.5%). 6 While this study was underway, one of us independently verified that the redox-modulation of luminescence can actually be effected using porphyrins functionalized by electroactive [trans-Ru(dppe) 2 Cl(C≡C-)] or A c c e p t e d m a n u s c r i p t [trans-Ru(dppe) 2 (C≡CAr)(C≡C-)] units with dyad C, even when they present lower luminescence quantum yield in their than 1 Ru(II) state (Ф lum ≈ 0.4 % for C). 7 In these systems, the redox switching of luminescence operates in a reverse way to that reported for the dyads A and B.…”

“…Finally, these results will be discussed and rationalized in the light of the available data from A-C and from isoelectronic Fe(II) and Ru(II) alkynyl complexes. 13,14,15 As shown in Scheme 1, the desired organometallic compound 2 can be synthesized from porphyrin 3 16 6 ] in good yield. 17 The reaction mixture was stirred at room temperature and its progress was followed by 31…”