Professor Chien-Tien Chen Department of Chemistry National Tsing Hua University Doubly Ortho-linked...
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Professor Chien-Tien Chen
Department of ChemistryNational Tsing Hua University
Doubly Ortho-linked Triarylethene, Hybrids for Chirochromic Optical Switch
Applications
方泰山 教授榮退研討會
O
OCH3
OCH3
O
H3COOCH3
O
H3CO OCH3
OO
O
H3CO OCH3
O
O
學術研究的第一道光 (1986-1988)Oxa-di-i-methane rearrangement
It was damn difficult!!!
Triarylcarbenium Ions in Catalysis
Asymmetric Mukaiyama Aldol AdditionAsymmetric Allylation
Dibenzosuberene-based Helicenes as Chirochromic Optical Switches in LC Materials
Iminostilbene and Dibenzosuberene-basedSpiro Bipolar Triarylamines and Tetraarylmethanes in Optoelectronic Applications
G G
R R
R
X
G = Me, Et; G-G = THFX = Cl, ClO4, SbF6, PF6
J. Am. Chem. Soc. 1997, 119, 11341.JOC 1999, 64, 1090.
J. Am. Chem. Soc. 2006, 128, 10992.J. Am. Chem. Soc. 2007, 129, 7478.J. Am. Chem. Soc. 2009, 131, 6698.Chem. Commun. 2011, feature article.
J. Am. Chem. Soc. 2000, 122, 7662-7672.Org. Lett. 2010, 12,1472.Chem. Eur. J. 2010, 16, 12822 (frontispiece).
C7H15OOC7H15
NN NN
Y
Q Ar
N
NX G
acceptordonor
XN
N
Ar
X = N, C-Ar
G
G
G
G
GG
G = N-Ar2 or 4-CH3OC6H4
R R
Br
R = CH3, OCH3, OC7H15
學術研究的第二道光 (1998-)
LC Chirochromic Switches with Binary Logic
enantiomericchiral dopant(s)
in nematic LC
chiral dopant(s)
in nematic LC
mediator?
center chirality
helical chiralitymodulated by light
cholesteric phaseCNC5H11O C5H11 CN
ZLI-1167p = (M x c x eepss)
-1K-15
twisting power of dopant(s)
chiral dopant(s)
nematic phase
180o turn
enantiomericchiral dopant(s)
right handed(+)
left handed(-)
1/2 p
JACS 2000, 122 (32), 7662.
Stacked Plot of CD Spectra for the Photoisomerization of (10R,11R)-Diethyl-DBS-based (P)-Helicene in Hexane at 280 nm
[de]pss = (P – M’)/(P + M’) = [(M’M’→P - PP→M’)/(M’M’→P + PP→M’)]
200 250 300 350 400-100
0
100
200
300
400
500
600
w ave leng th (nm )
280 nm
(R,R)-P (R,R)-M'0.4:99.6
P > M'
M' > P
254 nmvery slow
isodichroic
isodichroic
lowM’→P
Droplets of K-15 containing (left) 1% (10Droplets of K-15 containing (left) 1% (10RR,11,11RR,,PP) ) (right) 1% (10(right) 1% (10RR,11,11RR,,M’M’) suspended in glycerol ) suspended in glycerol
viewed at 200x magnification at room temperatureviewed at 200x magnification at room temperature
p: Distance betweenconcentric rings
Modulation of Photoswitching Profiles by 10,11-Dialkoxymethyl Substituents in C2-Symmetric DBS-based Helicenes
(10R,11R,P)-6c
Brhexanes
(P)-6c : (M')-6c<1 : >99 (290 nm)
(P)-6c : (M')-6c90 : 10 (330 nm)50 : 50 (310 nm)
OC7H15C7H15OOC7H15C7H15O
(10R,11R,M')-6c
Br
h
spin-orbit perturbationM’→P ~ P→M’ better solubility in LC
Chen, C.-T.; * Chen, W.-C.; Lin, B.-C. Chem. Eur. J. 2010, 16, 12822 as a frontispiece.
LC Optical Switch with Ternary Logic
m
200 m
330 nm310 nm 310 nm
BA
200m200m
290 nm
CD
200m
310 nm
200m
Cholesteric-I(+)-state
Cholesteric-II(-)-state
Cholesteric-I(+)-state
Nearly nematicoff state
N*-LC(R,R,P)6c
Standard LC
N*-LC(R,R,P)6c
Standard LC
p = 13.9 mp = 8.2 m
p = 16.3 m
L
P2
Grandjean wedge-shaped sample preparation
darkline
darkline
p ~ 0 m
p = 2 × L × tan
Photoswitching Profiles by 10,11-Dialkoxymethyl Substituents in C2-Symmetric DBS-based Helicenes
Bearing Flexible Axial Chirality
Entry Solvent λ(nm) d.r.(M:P)a d.e.b
1 n-hexane 240 <1 : >99 -98
2 n-hexane 260 50 : 50 0
3 n-hexane 280 96 : 4 +92
hv
(10R,11R,P )-28
OC7H15C7H15OOC7H15C7H15O
(10R,11R,M)-28
hv
(10R,11R,P )-27
OOOO
(10R,11R,M)-27
OC7H15 C7H15O
hv
(10R,11R,P)
OOOO
(10R,11R,M)
Helicene/Azobenzene Hybrid System as a Dual-mode Synergistic Optical Switch
C7H15OOC7H15
(P)-E,E -1
(P)-Z,Z -1
OC7H15C7H15O
300nm & 480nm (1 min)
254nm & 480nm (1 min)
380nm480nm
NN
C7H15O
N
OC7H15
(M)-E,E -1
(M)-Z,Z -1
380nm480nm
N NN NN
NN NN
(M)-E,E:(P)-E,E8:92
(M)-E,E:(P)-E,E97:3
(E,E):(Z,Z)>99:<1
(E,E):(Z,Z)19:81
(E,E):(Z,Z)>99:<1
(E,E):(Z,Z)19:81
OC7H15C7H15O
NN NN
Y Y
YY
Y =
O
O
300nm & 380nm (1min)
254nm & 380nm (1 min)
(M)-Z,Z:(P)-Z,Z12:88
(M)-Z,Z:(P)-Z,Z94:6
C7H15OOC7H15
(P)-E,E -1
300nm & 480nm
254nm & 480nm
NN
C7H15O
N
OC7H15
(M)-E,E -1
N NN NN
(M)-E,E:(P)-E,E8:92
(M)-E,E:(P)-E,E97:3
Y Y
Chirochromic Switching
Chen, C.-T.; * Chen, W.-C. Org. Lett. 2010, 12, 1472.
Summary
RR
Br
R = CH3, OCH3, OC7H15
C7H15OOC7H15
NN NN
Y
ORO O
Ternary logicDual mode
•高的非鏡像選擇性 (P/M’, < 1/> 99 to 96/4)•將螺旋稀化合物摻雜於向列相液晶 E7中,能夠誘導生成膽固醇相液 晶,並且可以藉由光異構化反應可以調控膽固醇相液晶的螺距及相對 手性,成為具有三元邏輯的開關記憶材料。•增加 C10和 C11位置取代基的立體效應,增加其在近軸向構型的穩定 性,而大幅增加其光學切換的選擇性,有增效作用。
Molecular Design for cis-STIF Trimer Systems
3
G = H, (C6H5)2N
**
STIF basedtrimer
GG
STIF as el. accepting template
H-Tri-STIF: G = HN-Tri-STIF: G = NPh2
G G
SPF-STIF-SPF
Abs. max[a,b]
(nm): (M·+)Abs. max
[b,c]
(nm): (M·-)Abs. max
[d]
(nm)
Em. max[d,e]/Int.[d]
(nm/%)
SPF-STIF-SPF
620 (3.9) 670 (7.1) 650 463 (63)/60
Tri-STIF 620 (3.5) 685 (13.3) 700 473 (61)/64
N-Tri-STB 570 (11.3) 690 (14.2) 655 521 (89)/109
Tri-SPF 550 (7.1) 570 (5.1) 667 425 (62)/100
[a] Measured in DCE. [b] The data in parentheses correspond to half-lives (ms). [c] Measured in DMF. [d] Measured in bz (the total amount of emission relative to that of 12 is 100%). [e] The data in parentheses correspond to full width at half-maximum.
Time Resolved Transient Absorption Spectra in Ar-saturated DCE, DMF, and Bz
By Wei, Y.; Chen, C.-T.*; and Majima, T.* et al.JACS 2009, 131, 6698.
Comparison between Spiro-Fluorene and Spiro-STIFFused Systems
max: 445 (81); Trilayer deviceext: 4.5%c: 9.2 cd/A; p: 3.0 lm/wL20: 1847 cd/m2
RR R
R
RR R
R
RR
R
N N
RR R
R
R
max: 468 (76); with host CBP (10 wt%)ext: 2.5%c: 5.2 cd/A; p: 2.7 lm/wLmax: 5494 cd/m2
2.3
5.0
6.2
2.7
R R
LCOptical Switches
GX X
XN
N
Ar
G
G
spiro-Q-LED
G
GAr
R R
Carbenium Ions
X
X = N, C
doubly o-linked
N
G2
G1S
NC
C
DSSC applications
O
O
TiO2
那個光的故事
Acknowledgments
Collaborator: Prof. Yu-Tai Tao (Academia Sinica)Prof. Testsuro Majima (ISIR, Osaka Univ.)
Prof. Eiichi Nakamura (Univ. of Tokyo)
Dr. Yi WeiMr. Wei-Shang Chao
Mr. How-wei LiuDr. Bor-Chiao Lin
Mr. Wen-Ching ChenMr. Chien-Hsiang Chen
Financial Supports:
National Science Council Department of Chemistry
National Taiwan Normal UniversityNational Tsing-Hua University