TY - JOUR
T1 - Triarylboron/Triarylamine-Functionalized 2,2′-Bipyridine Ligands and Their Copper(I) Complexes
AU - Zhao, Zhenhui
AU - Yin, Xiaodong
AU - Peng, Tai
AU - Wang, Nan
AU - Wang, Suning
N1 - Publisher Copyright:
© 2020 American Chemical Society.
PY - 2020/6/1
Y1 - 2020/6/1
N2 - We report herein three new either -BMes2 (Mes = mesityl) or -NPh2 group-functionalized 2,2′-bipyridine ligands - 4,4′-(p-BMes2-phenyl-CC)2-2,2′-bpy (BB-bpy), 4-(p-BMes2-phenyl-CC)-4′-(p-NPh2-phenyl-CC)-2,2′-bpy (BN-bpy), and 4,4′-(p- NPh2-phenyl-CC)2-2,2′-bpy (NN-bpy) - along with their heteroleptic copper(I) complexes Cu(L)(PPh3)2(BF4) (L = BB-bpy, BN-bpy, and NN-bpy, respectively). The electron-donor and -acceptor units are connected to the bipyridine core via acetylene linkers. The incorporation of acetylene linkers decreases the dihedral angle between the bridging phenyl and pyridine rings, resulting in a nearly coplanar geometry of the ligands. All free ligands display temperature-dependent luminescence changes, which may be explained by the twisted intramolecular charge-transfer mechanism. Binding with Cu(I) results in significantly red-shifted emission maxima for the heteroleptic complexes Cu(NNbpy)(PPh3)2(BF4) [Cu(NNbpy)] and Cu(BNbpy)(PPh3)2(BF4) [Cu(BNbpy)] relative to those of the free ligands. The electronic and photophysical properties of all compounds were investigated by electrochemical, absorption, and emission spectroscopic analyses as well as density functional theory calculations.
AB - We report herein three new either -BMes2 (Mes = mesityl) or -NPh2 group-functionalized 2,2′-bipyridine ligands - 4,4′-(p-BMes2-phenyl-CC)2-2,2′-bpy (BB-bpy), 4-(p-BMes2-phenyl-CC)-4′-(p-NPh2-phenyl-CC)-2,2′-bpy (BN-bpy), and 4,4′-(p- NPh2-phenyl-CC)2-2,2′-bpy (NN-bpy) - along with their heteroleptic copper(I) complexes Cu(L)(PPh3)2(BF4) (L = BB-bpy, BN-bpy, and NN-bpy, respectively). The electron-donor and -acceptor units are connected to the bipyridine core via acetylene linkers. The incorporation of acetylene linkers decreases the dihedral angle between the bridging phenyl and pyridine rings, resulting in a nearly coplanar geometry of the ligands. All free ligands display temperature-dependent luminescence changes, which may be explained by the twisted intramolecular charge-transfer mechanism. Binding with Cu(I) results in significantly red-shifted emission maxima for the heteroleptic complexes Cu(NNbpy)(PPh3)2(BF4) [Cu(NNbpy)] and Cu(BNbpy)(PPh3)2(BF4) [Cu(BNbpy)] relative to those of the free ligands. The electronic and photophysical properties of all compounds were investigated by electrochemical, absorption, and emission spectroscopic analyses as well as density functional theory calculations.
UR - http://www.scopus.com/inward/record.url?scp=85085662102&partnerID=8YFLogxK
U2 - 10.1021/acs.inorgchem.0c00102
DO - 10.1021/acs.inorgchem.0c00102
M3 - Article
C2 - 32402197
AN - SCOPUS:85085662102
SN - 0020-1669
VL - 59
SP - 7426
EP - 7434
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 11
ER -