Phenanthrylene-butadiynylene and Phenanthrylene-thienylene Macrocycles: Synthesis, Structure, and Properties

Abstract

A series of macrocycles consisting of 9,10-substituted phenanthrenes connected by butadiynylene linkers in positions 3 and 6 has been described as well as their transformation into the corresponding phenanthrylene-thienylene macrocycles. Structure and properties of the macrocycles, such as self-association in solution and optical and electrochemical properties, were studied and reported in a comparative manner with respect to the effects of the different sizes and shapes of the macrocycles and the character and length of their side chains.

Ferrocenyl‐Pyrenes, Ferrocenyl‐9,10‐Phenanthrenediones, and Ferrocenyl‐9,10‐Dimethoxyphenanthrenes: Charge‐Transfer Studies and SWCNT Functionalization

“…However,t he synthetic methodology described by Phulwale et al for the reduction of the ketonef unctionalities in 10 did not lead to the formation of the respective 3,6-diferrocenyl-9,10-dimethoxyphenanthrene compound 12. [46] Nevertheless, this compound was accessible when the reduction of 9 was performed prior to the CÀC cross-coupling reaction. Thus, compound 11 could be isolated in virtualq uantitative yield.…”

“…Ferrocene boronic acid was synthesized from lithioferrocene and triethyl borate on the basis of a procedure by Nesmejanow et al . 3,6‐Dibromo‐9,10‐dimethoxyphenanthrene was prepared according to the procedure published by Phulewale et al …”

“…Ac ommercial SWCNT dispersion, NanoIntegris IsoSol S-100,b atch SP31-176, was purchased from commercial suppliers and used without any further purification. Ferrocene boronic acid was synthesized from lithioferrocene [45] and triethyl borate on the basis of ap rocedure by Nesmejanow et al [107] 3,6-Dibromo-9,10-dimethoxyphenanthrene was prepared according to the procedure published by Phulewale et al [46] NMR spectra were recorded with aB ruker AvanceI II 500 spectrometer operating at 500.3 MHz for 1 Ha nd 125.7 MHz for 13 C{ 1 H} in the Fourier transform mode at ambient temperature. Chemical shifts are reported in d (ppm) downfield from tetramethylsilane with the solvent as the reference signal ( 1 HNMR, CDCl 3 d = 7.26 ppm; 13 C{ 1 H} NMR d = 77.16 ppm).…”

Global Aromaticity in Macrocyclic Cyclopenta‐Fused Tetraphenanthrenylene Tetraradicaloid and Its Charged Species

“…Palladiumcatalyzed Suzuki-Miyaura borylation of the phenanthrene dibromide 1 [14] gave the pinacol borate 2,a nd as ubsequent Suzuki coupling reaction between equimolar amounts of 2 and 3 [13] afforded the tetraaldehyde macrocycle 4 in 8% yield after separation by recycling preparative GPC.T reatment of 4 with 2-mesitylmagnesium bromide gave the corresponding tetra-alcohol, and then intramolecular Friedel-Crafts alkylation mediated by BF 3 ·Et 2 Oprovided the tetrahydro precursor 5.O xidative dehydrogenation of 5 with 2,3-dichloro-5,6dicyano-p-benzoquinone (DDQ) in toluene gave the final product CPTP-M,w hich was purified by normal silica-gel column chromatography. Palladiumcatalyzed Suzuki-Miyaura borylation of the phenanthrene dibromide 1 [14] gave the pinacol borate 2,a nd as ubsequent Suzuki coupling reaction between equimolar amounts of 2 and 3 [13] afforded the tetraaldehyde macrocycle 4 in 8% yield after separation by recycling preparative GPC.T reatment of 4 with 2-mesitylmagnesium bromide gave the corresponding tetra-alcohol, and then intramolecular Friedel-Crafts alkylation mediated by BF 3 ·Et 2 Oprovided the tetrahydro precursor 5.O xidative dehydrogenation of 5 with 2,3-dichloro-5,6dicyano-p-benzoquinone (DDQ) in toluene gave the final product CPTP-M,w hich was purified by normal silica-gel column chromatography.…”

Global Aromaticity in Macrocyclic Cyclopenta‐Fused Tetraphenanthrenylene Tetraradicaloid and Its Charged Species

“…Ab ulky mesityl group was attached at the most reactive site of each cyclopenta ring, and as table CPTP derivative CPTP-M was synthesized according to Scheme 1. Palladiumcatalyzed Suzuki-Miyaura borylation of the phenanthrene dibromide 1 [14] gave the pinacol borate 2,a nd as ubsequent Suzuki coupling reaction between equimolar amounts of 2 and 3 [13] afforded the tetraaldehyde macrocycle 4 in 8% yield after separation by recycling preparative GPC.T reatment of 4 with 2-mesitylmagnesium bromide gave the corresponding tetra-alcohol, and then intramolecular Friedel-Crafts alkylation mediated by BF 3 ·Et 2 Oprovided the tetrahydro precursor 5.O xidative dehydrogenation of 5 with 2,3-dichloro-5,6dicyano-p-benzoquinone (DDQ) in toluene gave the final product CPTP-M,w hich was purified by normal silica-gel column chromatography.…”