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那

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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 Among Spiro-STIF Fused Systems

RR R

R RR R

R

RR

R

N N

RR R

R

R

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

Future Outlooks

G G

O

OR

RR R

R

RR R

R

R R

N N

RR R

R

R R

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

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