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
Structurally well-defined arenes with higher numbers of linearly-fused six-member rings(n≥10)are important and highly desirable not only because of their experimental challenges but also due to their fundamental inte...Structurally well-defined arenes with higher numbers of linearly-fused six-member rings(n≥10)are important and highly desirable not only because of their experimental challenges but also due to their fundamental interests and the curiosity of their structure-property relationships.In this research,we successfully synthesized a novel large N-heteroarene(N20)with 20 linearly-fused six-membered rings,which is the longest N-heteroarene(4.7 nm)confirmed by single-crystal X-ray diffraction(SCXRD)analysis so far.The as-prepared arene displays a wave-like framework rather than a rigid plane.Moreover,N20 shows high molar absorptivity of 364,000 M^(−1) cm^(−1) with its fluorescence extended to the near-infrared region.展开更多
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.
基金The work at NAIST was supported by Grant-in-Aid for Scientific Research No.JP20H02711(NA).
文摘Structurally well-defined arenes with higher numbers of linearly-fused six-member rings(n≥10)are important and highly desirable not only because of their experimental challenges but also due to their fundamental interests and the curiosity of their structure-property relationships.In this research,we successfully synthesized a novel large N-heteroarene(N20)with 20 linearly-fused six-membered rings,which is the longest N-heteroarene(4.7 nm)confirmed by single-crystal X-ray diffraction(SCXRD)analysis so far.The as-prepared arene displays a wave-like framework rather than a rigid plane.Moreover,N20 shows high molar absorptivity of 364,000 M^(−1) cm^(−1) with its fluorescence extended to the near-infrared region.
