A series of near infrared (NIR) absorbing dinuclear ruthenium dicarbonylhydrazine complexes (DCH-Ru),[{Ru(bpy)_2)_2μ-DCH]^(n+) (where bpy = 2,2'-bipyridinc and n = 2, 3 or 4), were prepared. The DCH-Ru complexes ...A series of near infrared (NIR) absorbing dinuclear ruthenium dicarbonylhydrazine complexes (DCH-Ru),[{Ru(bpy)_2)_2μ-DCH]^(n+) (where bpy = 2,2'-bipyridinc and n = 2, 3 or 4), were prepared. The DCH-Ru complexes areelectrochromic in the NIR region with a high absorption coefficient at 1550-1600 nm typically over 10000 M^(-1)cm^(-1). DCH-Ru complex polymers with good NIR electrochromic properties were also obtained and processed to make a device foroptical attenuation at a wavelength of 1550 nm. The potential of these DCH-Ru polymers for use in a variable opticalattenuator has been demonstrated with an attenuating power at the 1550-nm telecommunication wavelength over 7.0 dB permicron of polymer film thickness. Other classes of NIR active materials are the pentacenediquinones and the correspondingpoly(ether pentacenediquinone)s. These polymers can be electrochemically reduced to the corresponding semiquinone(radical anion) having NIR absorption within a telecom window (e. g., 1310 nm).展开更多
Preparation of large rylenes often needs the use of solubilizing groups along the rylene backbone,which results in the distortion of the skeleton and thus broadening of the absorption spectrum.In this work,we successf...Preparation of large rylenes often needs the use of solubilizing groups along the rylene backbone,which results in the distortion of the skeleton and thus broadening of the absorption spectrum.In this work,we successfully synthesized 2,5,8,16,19,22-hexakis[2,6-bis(tri-fluoromethyl)phenyl]hexarylene(H)by using an oxidative fusion reaction of perylene trimer in 5%yield.The product is soluble in common organic solvents and could be purified with column chromatography.Single-crystal X-ray diffraction analysis revealed that the hexarylene core is not disturbed by the substituents very much and is almost planar.The longest absorption of H exhibits a sharp peak at 831 nm and an on-set at 875 nm in toluene with a small full-width-at-half-maximum(FWHM)of 660 cm^(-1).The molar extinction coefficient is as large as 131,000 M^(-1)cm^(-1).The substituents could not perturb the electronic properties of the hexarylene because aryl groups are perpendicular to the hexarylene core and the carbon atoms at 2,5,16,19-positions have negligible coeffi-cients on its HOMO and LUMO,estimated by theoretical calculations.As a result,the hexarylene having less absorption at the visible light region was stable enough in solution under the LED room light for more than 1 week.This strategy gives a useful guideline to establish the near-infrared materials that exhibit stability under ambient conditions.展开更多
基金This work was supported by the Natural Sciences and Engineering Research Council of Canada and Nortel Networks.
文摘A series of near infrared (NIR) absorbing dinuclear ruthenium dicarbonylhydrazine complexes (DCH-Ru),[{Ru(bpy)_2)_2μ-DCH]^(n+) (where bpy = 2,2'-bipyridinc and n = 2, 3 or 4), were prepared. The DCH-Ru complexes areelectrochromic in the NIR region with a high absorption coefficient at 1550-1600 nm typically over 10000 M^(-1)cm^(-1). DCH-Ru complex polymers with good NIR electrochromic properties were also obtained and processed to make a device foroptical attenuation at a wavelength of 1550 nm. The potential of these DCH-Ru polymers for use in a variable opticalattenuator has been demonstrated with an attenuating power at the 1550-nm telecommunication wavelength over 7.0 dB permicron of polymer film thickness. Other classes of NIR active materials are the pentacenediquinones and the correspondingpoly(ether pentacenediquinone)s. These polymers can be electrochemically reduced to the corresponding semiquinone(radical anion) having NIR absorption within a telecom window (e. g., 1310 nm).
基金supported by Grants-in-Aid for Scientific Research(Nos.JP20H02816(HH),JP20H00379(HY),JP20H05833(HY),JP20H02711(NA),JP22H19067(NA),JP22K05225(KM),JP20K15261(KM))。
文摘Preparation of large rylenes often needs the use of solubilizing groups along the rylene backbone,which results in the distortion of the skeleton and thus broadening of the absorption spectrum.In this work,we successfully synthesized 2,5,8,16,19,22-hexakis[2,6-bis(tri-fluoromethyl)phenyl]hexarylene(H)by using an oxidative fusion reaction of perylene trimer in 5%yield.The product is soluble in common organic solvents and could be purified with column chromatography.Single-crystal X-ray diffraction analysis revealed that the hexarylene core is not disturbed by the substituents very much and is almost planar.The longest absorption of H exhibits a sharp peak at 831 nm and an on-set at 875 nm in toluene with a small full-width-at-half-maximum(FWHM)of 660 cm^(-1).The molar extinction coefficient is as large as 131,000 M^(-1)cm^(-1).The substituents could not perturb the electronic properties of the hexarylene because aryl groups are perpendicular to the hexarylene core and the carbon atoms at 2,5,16,19-positions have negligible coeffi-cients on its HOMO and LUMO,estimated by theoretical calculations.As a result,the hexarylene having less absorption at the visible light region was stable enough in solution under the LED room light for more than 1 week.This strategy gives a useful guideline to establish the near-infrared materials that exhibit stability under ambient conditions.
