Synthesis, Electrochemistry, and Optical Properties of Half‐Sandwich Ruthenium Complexes Bearing Triarylamine‐Anthracenes

Abstract

Invited for the cover of this issue is the group of Alexander Hildebrandt from Technische Universität Chemnitz, Germany. The cover image shows a light‐operated switch, which takes the complex between the mono‐oxidized and dicationic states reversibly.

Synthesis, crystal structure, polymorphism and microscopic luminescence properties of anthracene derivative compounds

“…A slight bending was observed for the lateral chains involving the alkyne group: the distances from the least-squares plane for C15, C16 and Si1 were 0.024 (1), 0.047 (2) and 0.117 (2) Å , respectively, while for C20, C21 and Si2 were 0.074 (2), 0.135 (3) and 0.280 (3) Å , respectively. As usual for anthracenyl units, the peripheral aromatic rings were distorted from the hexagonal geometry with shortening of some bond distances (Kovalski et al, 2018): the bond distances C5-C6, C7-C8, C1-C14, C12-C13 were 1.341 (3), 1.346 (3), 1.378 (3) and 1.364 (3) Å , respectively, while the rest of bond distances were between 1.389 (3) and 1.445 (3) Å . The mean value of the C-C bonds was 1.4098 (30) Å (ring C1-C2-C11-C12-C13-C14), 1.4042 (30) Å (ring C2-C3-C4-C9-C10-C11) and 1.3938 (30) Å (ring C4-C5-C6-C7-C8-C9).…”

(Spectro)electrochemical Properties of Anthracene Containing Triarylamine Platinum(II) Acetylides

“…9-Bromo-10-di(p-anisyl)aminoanthracene (1) was prepared by a literature described synthetic route. [26,33] The synthetic pathway involved a three step procedure; starting with the bromination of anthracene, [33] subsequent Buchwald-Hartwig amination, [34] and the bromination of the resulting anthracenyl-amine in 10-position. [26,33] The bromoanthracene 1 and trimethylsilylacetylene were converted to acetylene 2SiMe 3 using a Sonogashira-Hagihara C,C cross-coupling protocol with [PdCl 2 (PPh 3 ) 2 ] as catalyst in the presence of CuI (see Scheme 1).…”

“…[26,33] The synthetic pathway involved a three step procedure; starting with the bromination of anthracene, [33] subsequent Buchwald-Hartwig amination, [34] and the bromination of the resulting anthracenyl-amine in 10-position. [26,33] The bromoanthracene 1 and trimethylsilylacetylene were converted to acetylene 2SiMe 3 using a Sonogashira-Hagihara C,C cross-coupling protocol with [PdCl 2 (PPh 3 ) 2 ] as catalyst in the presence of CuI (see Scheme 1). [35] Anthracenyl-acetylene 2H was accessible by deprotection of the acetylene moiety in almost quantitative yield using tetrabutylammonium fluoride as a mild deprotection reagent.…”

“…At the end of the measurements the analyte was reduced at À 500 mV vs Ag/AgCl for 20 min, and an additional spectrum was recorded to prove the reversibility of the oxidations. Synthesis 10-Bromo-9-N,N-di(p-anisyl)aminoanthracene (1): The compounds were synthesized according to published procedures: [33] 9-Di(panisyl)amino-anthracene (1.29 g, 3.2 mmol) and N-bromosuccinimide (NBS) (0.66 g, 3.7 mmol) were dissolved in glacial acetic acid (18 mL) and the solution was stirred at 50°C for 2 h. After completion of the reaction, an orange-red precipitate was separated by filtration and washed with saturated NaOH-solution and afterwards with cold n-hexane. 1 was obtained in 72 % yield (1.11 g, 2.3 mmol).…”

“…The spectroscopic data correspond with those reported previously. [26] 10-Trimethylsilyl(ethinyl)-9-N,N-di(p-anisyl)amino-anthracene (2SiMe 3 ): The compound was not synthesized according to the published procedure, [57] but following this synthetic protocol:, [33] [PdCl 2 (PPh 3 ) 2 ] (13 mg, 0.02 mmol, 1 mol-%) and CuI (21 mg, 0.11 mmol, 6 mol-%) were dissolved in dry, degassed diisopropylamine (45 mL) under an argon atmosphere and stirred at room temperature for 10 min. Anthracene 1 (891 mg, 1.84 mmol), trimethylsilylacetylene (0.3 mL, 2.02 mmol, 0.69 g mL À 1 ) and PPh 3 (29 mg, 0.11 mmol, 6 mol-%) were added in one portion to the yellow solution and the mixture heated to reflux overnight.…”