jp9b01810_si_003.cif (72.36 kB)
Photoluminescence Properties of [Core+exo]‑Type Au6 Clusters: Insights into the Effect of Ligand Environments on the Excitation Dynamics
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posted on 2019-02-26, 00:00 authored by Yukatsu Shichibu, Mingzhe Zhang, Takeshi Iwasa, Yuriko Ono, Tetsuya Taketsugu, Shun Omagari, Takayuki Nakanishi, Yasuchika Hasegawa, Katsuaki KonishiThe
use of multidentate chelating ligands enriches the geometric
diversity of coordinated gold clusters, offering much knowledge to
benefit the understanding of their unique electronic structures and
optical properties. Herein we report different behaviors of [core+exo]-type Au6 clusters bearing C3- and C4-bridged
diphosphines (1 and 2), highlighting profound
effects of the steric constraints of the ligand environments on the
excited-state structural dynamics. Although the Au6 geometries
of 1 and 2 in the crystalline states were
somewhat different, their absorption spectra in solution were almost
similar. However, marked differences were found in the photoluminescence
properties; phosphorescent-type emission was dominantly observed for 1, whereas 2 gave both fluorescence- and phosphorescence-type
emissions. Theoretical calculations showed that the bridging chains
influence the geometries of the Au6 unit in the excited
states, leading to the observed differences in emission behaviors.
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6 unitgold clustersligand environmentsExcitation Dynamicsphosphorescence-type emissionsC 4-bridged diphosphinesC 3-6 geometriesLigand Environmentschains influencephotoluminescence properties6 ClustersPhotoluminescence PropertiesTheoretical calculationssteric constraintsemission behaviorsabsorption spectra6 clustersexophosphorescent-type emissionmultidentate chelating ligands
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