TY - JOUR
T1 - Photophysical Properties of Simple Palladium(0) Complexes Bearing Triphenylphosphine Derivatives
AU - Kakizoe, Daichi
AU - Nishikawa, Michihiro
AU - Ohkubo, Takuma
AU - Sanga, Masashi
AU - Iwamura, Munetaka
AU - Nozaki, Koichi
AU - Tsubomura, Taro
N1 - Publisher Copyright:
©
PY - 2021/7/5
Y1 - 2021/7/5
N2 - Pd(0) complexes with monodentate phosphine ligands, [Pd(P)n] (n = 3, 4), are well-known catalysts. However, the nature of the Pd(0) complex, especially the basic photophysical properties of the Pd(0) complexes, has not been extensively explored. In this work, we measured the general photophysical properties and crystal structures of Pd(0)-bearing PPh3 derivatives in the solid state and in solution. In the solid state, four-coordinated Pd(0) complexes exhibited blue-yellow emission. On the other hand, three-coordinated Pd(0) complexes displayed yellow-orange emission. In solution, orange emission of three-coordinated complexes was observed, and prompt fluorescence was detected using time-resolved emission spectroscopy, which suggests a thermally activated delayed fluorescence mechanism. Density functional theory (DFT) and time-dependent DFT calculations show that the difference in the transition mechanism between the [Pd(PPh3)4] and [Pd(PPh3)3] complexes explains the different emission colors. The emitting states of both complexes have metal-To-ligand charge-Transfer character, but the metal-centered d → p transition is considerably incorporated for emission of the tris complex.
AB - Pd(0) complexes with monodentate phosphine ligands, [Pd(P)n] (n = 3, 4), are well-known catalysts. However, the nature of the Pd(0) complex, especially the basic photophysical properties of the Pd(0) complexes, has not been extensively explored. In this work, we measured the general photophysical properties and crystal structures of Pd(0)-bearing PPh3 derivatives in the solid state and in solution. In the solid state, four-coordinated Pd(0) complexes exhibited blue-yellow emission. On the other hand, three-coordinated Pd(0) complexes displayed yellow-orange emission. In solution, orange emission of three-coordinated complexes was observed, and prompt fluorescence was detected using time-resolved emission spectroscopy, which suggests a thermally activated delayed fluorescence mechanism. Density functional theory (DFT) and time-dependent DFT calculations show that the difference in the transition mechanism between the [Pd(PPh3)4] and [Pd(PPh3)3] complexes explains the different emission colors. The emitting states of both complexes have metal-To-ligand charge-Transfer character, but the metal-centered d → p transition is considerably incorporated for emission of the tris complex.
UR - http://www.scopus.com/inward/record.url?scp=85108532815&partnerID=8YFLogxK
U2 - 10.1021/acs.inorgchem.1c00631
DO - 10.1021/acs.inorgchem.1c00631
M3 - 学術論文
C2 - 34105940
AN - SCOPUS:85108532815
SN - 0020-1669
VL - 60
SP - 9516
EP - 9528
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 13
ER -