Synthesis, Crystal Structures, and Second-Order Nonlinear Optical Properties of New Chiral Ferrocenyl Materials

Abstract

A series of chiral enantiomerically pure analogues of (E)-(2-(4-nitrophenyl)ethenyl)ferrocene (2), substituted by R (3, R = Me; 4, R = CH2OH; 5, R = SiMe3), in the 2-position on the cyclopentadienyl ring, were synthesized. Measurements by electric-field-induced second-harmonic generation (EFISH) and calculations by INDOS/CI-SOS show that the different chromophores have closely related molecular NLO responses. However, the crystal packings for the different compounds, observed by X-ray diffraction on a monocrystal, are completely different. In any case, the chirality of the constituting molecules avoids the centrosymmetry of the crystals and therefore preserves the NLO efficiency in the solid state. In the case of 3, the crystal packing is close to the centrosymmetry and so the bulk NLO efficiency is low (6 times that of urea, λ = 1.907 μm) but not nil, as is the case for 2. For 4, the crystal packing is much better for NLO (efficiency 20 times that of urea, λ = 1.907 μm) and is almost optimized for 5 (efficiency 100 times that of urea, λ = 1.907 μm). The correlation between molecular and bulk NLO responses was studied using the model proposed by Zyss.

N‐Ferrocenyl‐Substituted Planar‐Chiral N‐Heterocyclic Carbenes and Their PdII Complexes

“…(2S,4S)-2-Ferrocenyl-4-(hydroxymethyl)-1,3-dioxane, [20] (2S,4S)-2-ferrocenyl-4-(methoxymethyl)-1,3-dioxane, [20] (2S,4S,R Fc )-4-(methoxymethyl)-2-(2-methylferrocenyl)-1,3-dioxane (3), [43] (R)-2-methylferrocenecarboxaldehyde (4), [43] and ferrocenecarboxylic acid (6b) [22] were prepared as reported. …”

Ferrocenyl D–π–A conjugated polyenes with 3-dicyanomethylidene-1-indanone and 1,3-bis(dicyanomethylidene)indane acceptor groups: Synthesis, linear and second-order nonlinear optical properties and electrochemistry

“…''Push-pull'' compounds containing ferrocenyl (Fc) donor group bound to a conjugated polyenic chain capped by an acceptor moiety A, (Fc-p-A), have attracted considerable interest as second-order nonlinear optical (NLO) chromophores [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15]. They display large first hyperpolarizabilities (b), and some of them second harmonic generation (SHG) ability in the solid state.…”

Synthesis and characterization of meso-ferrocenylethynyl 5,15-diphenylporphyrins

“…Such a molecular design facilitates the electronic communication between the donor and the acceptor through the porphyrin framework. Since ferrocene is a well-known electron donor for push-pull NLO chromophores [7], we like to extend the study to meso-ferrocenylethynyl 5,15-diphenylporphyrins with an electron withdrawing group at the remaining meso position. The preparation and spectroscopic properties of such a series of compounds, as well as the molecular structure of one of the ferrocenyl porphyrins, namely [5-ferrocenylethynyl-15-(4 0 -nitrophenylethynyl)-10,20-diphenylporphyrinato]nickel(II) (11) are reported herein.…”