Anthracene-based ferrocenylselenoethers: syntheses, crystal structures, Cu(i) complexes and sensing property

Abstract

Three novel anthracene-based ferrocenylselenoethers, 1,5-diselena-3-(anthracen-9 0 -ylmethyl)- [5] ferrocenophane (L3), 1,3-bis(ferrocenylseleno)-2-(anthracen-9 0 -ylmethyl)propane (L4) and N,N-bis[2-(ferrocenylselena)ethyl]-N-(anthracen-9 0 -ylmethyl)amine (L5) and their Cu(I) complexes, [Cu 2 Br 2 (L2) 2 ] (L2 ¼ 1,1 0 -bis[2-(anthracen-9 0 -yloxy)-ethylseleno]ferrocene) (1), [Cu 2 I 2 (L2) 2 ] (2), [Cu 2 I 2 (L3) 2 ]$1.25CH 2 Cl 2 (3) and[Cu 4 I 4 (L5) 2 ]$CH 2 Cl 2 (4), have been prepared and structurally characterized. The X-ray crystallography analysis reveals that the complexes 1-3 possess a rhomboidal Cu 2 X 2 core which is sandwiched by two L ligands through two Se atoms to form a dimer, while 4 owns a distorted cubane-like Cu 4 I 4 core which is double-bridging linked by two L5 ligands via two Se atoms to produce a 1D loop chain. Each Cu(I) ion in 1-4 displays a distorted tetrahedral geometry. The unique structural feature in L3-L5 is the coexistence of a redox moiety (ferrocenyl) and a fluorescent chromogenic group (anthracenyl). In the cation sensing study, L3 and L4 present multiresponsive signals for Cu 2+ and Hg 2+ , L5 for Cu 2+ , Zn 2+ and Hg 2+ . The selectivity can be tuned by incorporating an additional donor N atom, and/or oxidation of the ferrocene unit.

Effective Antitumor Candidates Based upon Ferrocenylseleno-Dopamine Derivatives: Growth Inhibition by Induction Cell Apoptosis and Antivascular Effects

“…The half-wave potentials for oxidation of the ferrocene moiety of L1 – L5 are all more negative than those of B1 – B5 , which means the ferrocene moiety is easier to oxidize after the incorporation of the DA unit. It is not surprising to find that the ferrocene moiety in the ferrocenophane L5 is easier to oxidize than that of the acyclic analogues, which is in agreement with our previous studies . Studies have shown that the lower half -wave potential for oxidation of the ferrocene moiety is related to better anticancer activity. , The oxidation of the ferrocene moiety can induce the catechol group to form reactive o -quinone products, which have much greater advantages in inhibiting the thioredoxin reductases, the key targets in anticancer drug action mechanisms…”

“…Our continued interest in the study of ferrocenyl selenoethers led us to investigate their potential biomedical properties . Dopamine ( DA ) as a kind of neurotransmitter, has been reported to modulate tumor angiogenesis and immunity by inhibiting VEGF .…”

Copper(i) halide clusters based upon ferrocenylchalcogenoether ligands: donors, halides and semi-rigidity effects on the geometry and catalytic activity

“…19,20 Our group has recently obtained four new copper(I) clusters built from ferrocenylseleno-anthracenes, which are dimers with a rhomboidal Cu 2 X 2 core or 1D loop chain polymers with a distorted cubane Cu 4 I 4 core. 21 No neutral tellurium-based ones have been synthesized until now. The structure and characteristics of CuX-Te/Se clusters will be the subject of intense research effort for understanding the interaction of Cu(I)-Te/Se in chalcogeno-complexes which have shown potential biological activities.…”

Macrocyclic Se4N2[7,7]ferrocenophane and Se2N[10]ferrocenophane containing benzyl unit: synthesis, complexation, crystal structures, electrochemical and optical properties

“…[64][65][66][67] Several reports have shown that Cu 2+ can oxidize the ferrocene unit into ferrocenium, Cu 2+ is then reduced to non-quenching Cu + because of its d 10 electron configuration. 26,64,65 In the field of NLO studies, the ferrocene unit mainly behaved as an electron donor in the charge transfer process, and the NLO properties of ferrocenyl derivatives can be readily and reversibly switched via the Fe III/II redox couple. [67][68][69][70][71] Furthermore, investigations have shown that the γ value of two-dimensional macrocycles, such as phthalocyanines, depends on contributions coming from a larger number of components.…”

“…The band around 468 nm can be ascribed to a MLCT transition of the Cu + complex, and the wide absorption centered at 894 nm can be defined as the charge transfer to ferrocenium. 26,69,74 The changes in the absorption spectra are accompanied by a color change from faint yellow to red, which provides the potential for "naked eye" detection. The red solution was stable at room temperature, due to the strong affinity of the Se donor and Cu + .…”