Development of Polymer Materials

Based on Fused Azobenzene–Boron Complexes

Department of Polymer Chemistry, Kyoto University, Masayuki Gon

[1]

[2]

B–NLUMO

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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

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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

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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

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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.

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