TY - JOUR
T1 - Arene-Inserted Extended Germa[n]pericyclynes
T2 - Synthesis, Structure, and Phosphorescence Properties
AU - Tanimoto, Hiroki
AU - Mori, Junta
AU - Ito, Shunichiro
AU - Nishiyama, Yasuhiro
AU - Morimoto, Tsumoru
AU - Tanaka, Kazuo
AU - Chujo, Yoshiki
AU - Kakiuchi, Kiyomi
N1 - Publisher Copyright:
© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
PY - 2017/7/26
Y1 - 2017/7/26
N2 - This report describes the synthesis and characterization of arene-inserted extended (ArEx) germa[n]pericyclynes composed of germanium and 1,4-diethynylbenzene units. These novel cyclic germanium-π unit materials were synthesized with diethynylbenzene and germanium dichloride. X-ray crystallographic analysis revealed their structures, and the planar conformation of ArEx germa[4]pericyclyne along with the regular aromatic rings. UV/Vis absorption spectra and fluorescence emission spectra showed considerably unique and highly improved character compared to previously reported germa[n]pericyclynes. Even in the absence of transition metal components, phosphorescence emissions were observed, and the emission lifetimes were dramatically improved. ArEx germa[n]pericyclynes showed high photoluminescence quantum yields, whereas low photoluminescence quantum yields were observed for acyclic compounds. Density functional theory calculations show delocalized orbitals between skipped alkyne units through a germanium tether, and an increase in the HOMO energy level, leading to a small HOMO–LUMO energy gap.
AB - This report describes the synthesis and characterization of arene-inserted extended (ArEx) germa[n]pericyclynes composed of germanium and 1,4-diethynylbenzene units. These novel cyclic germanium-π unit materials were synthesized with diethynylbenzene and germanium dichloride. X-ray crystallographic analysis revealed their structures, and the planar conformation of ArEx germa[4]pericyclyne along with the regular aromatic rings. UV/Vis absorption spectra and fluorescence emission spectra showed considerably unique and highly improved character compared to previously reported germa[n]pericyclynes. Even in the absence of transition metal components, phosphorescence emissions were observed, and the emission lifetimes were dramatically improved. ArEx germa[n]pericyclynes showed high photoluminescence quantum yields, whereas low photoluminescence quantum yields were observed for acyclic compounds. Density functional theory calculations show delocalized orbitals between skipped alkyne units through a germanium tether, and an increase in the HOMO energy level, leading to a small HOMO–LUMO energy gap.
KW - X-ray crystallography
KW - fluorescence emission
KW - germanium
KW - pericyclynes
KW - phosphorescence emission
UR - http://www.scopus.com/inward/record.url?scp=85020436716&partnerID=8YFLogxK
U2 - 10.1002/chem.201701359
DO - 10.1002/chem.201701359
M3 - 学術論文
C2 - 28422338
AN - SCOPUS:85020436716
SN - 0947-6539
VL - 23
SP - 10080
EP - 10086
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
IS - 42
ER -