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Development of Polymer Materials
Based on Fused Azobenzene–Boron Complexes
Department of Polymer Chemistry, Kyoto University, Masayuki Gon
[1]
[2]
B–NLUMO
― 42 ―
2,2'-Dihydroxyazobenzene 1
BAz-H100 °C 3 BAz-H
63% 1BAz-H
BAz-H
4-Bromo-2-methoxyaniline 2 MnO2
Az-Br BBr3
31
BAz-BrTotal 48%
Az-H
2 BAz-Br Az-H
BAz-BrStille
BAz-Br B–N
24MeOH
P-BAz 85% P-Az 79%P-BAz, Mn = 21,400, Mw =
55,600, Mw/Mn = 2.54; P-Az, Mn = 20,900, Mw = 52,100, Mw/Mn = 2.50
3
X
6 5
R S
BAz-H
NH2
OMe
MnO2
2
Br NN
OMe
MeO
Az-Br, 69%
BrBr BBr3
NN
OH
HO
3, 91%
BrBr
NN
O BOF
BAz-Br, 77%
BrBr
Toluene70 °C48 h
CH2Cl2–78 °C to rt6 h
BF3•Et2OEt3N
Toluene100 °C10 h
― 43 ―
Az-H, BAz-H, P-Az, P-BAz
1.0×10 5 M
Az-H 372 nm – * 460 nm n– *
BAz-H[2]
– * HOMO –LUMO
P-BAzB–N LUMO
Az-H P-Az
BAz-H
P-BAz632 nm 751 nm
PL 25%
P-BAz1.0 mg / 300 L
1000 rpm
821 nmPL = 3.8%
BAz-HAz-H
BAz-H 1,4-Dioxane1.0×10 4 M 1,4-Dioxane/H2O = 1/99
1.0×10 4 MAz-H
BAz-HPL < 0.1%PL = 2.3%
AIE
AIE
― 44 ―
AIE BAz-H
C–N–N–C165°
141°
0.1 Å
LUMO
1.0×10 3 MTetrabutylammonium Hexafluoro-
phosphate NBu4PF6, 0.1 MAg/Ag+
Pt ferrocene/ ferrocenium Fc/Fc+
Eonsetred
LUMOAz-H LUMO 3.00 eV
LUMO 2.86 eVBAz-H
LUMO 3.87 eV
P-Az P-BAz LUMO3.20 eV 3.98 eV
LUMO
LUMO
― 45 ―
HOMO 1, HOMO, LUMOn *
Az-HHOMO 1
HOMO n
HOMO–LUMOS0 S1 S0–S1
f = 0.0000 Az-H f = 0.0305 f
HOMO 1 LUMOS0–S2
f = 0.7705 Az-Hf = 0.5018
Az-H
nHOMO
S0–S1 – *f = 0.3118 BAz-H
LUMO
365 nm
AIE
16H06888P24102013
[1] Chujo, Y.; Tanaka, K. Bull. Chem. Soc. Jpn. 2015, 88, 633 643. [2] Yoshino, J.; Kano, N.; Kawashima, T. Chem. Commun. 2007, 559 561.
1. 66
29 1Pc003 2. A Highly-Efficient Near-Infrared-Emissive Copolymer with N=N Double-Bond -Conjugated System Based on a Fused Azobenzene-Boron Complex: Gon, M.; Tanaka, K.; Chujo, Y. Angew. Chem. Int. Ed. 2018, 57, in press.
― 46 ―