Professor Chien-Tien Chen Department of Chemistry National Tsing Hua University Doubly Ortho-linked Triarylethene, Hybrids for Chirochromic Optical Switch Applications 方泰山 教授榮退研討會

學術研究的第一道光 ( ) Oxa-di-  i-methane rearrangement It was damn difficult!!!

Triarylcarbenium Ions in Catalysis Asymmetric Mukaiyama Aldol Addition Asymmetric Allylation Dibenzosuberene-based Helicenes as Chirochromic Optical Switches in LC Materials Iminostilbene and Dibenzosuberene-based Spiro Bipolar Triarylamines and Tetraarylmethanes in Optoelectronic Applications J. Am. Chem. Soc. 1997, 119, JOC 1999, 64, J. Am. Chem. Soc. 2006, 128, J. Am. Chem. Soc. 2007, 129, J. Am. Chem. Soc. 2009, 131, Chem. Commun. 2011, feature article. J. Am. Chem. Soc. 2000, 122, Org. Lett. 2010, 12,1472. Chem. Eur. J. 2010, 16, (frontispiece). 學術研究的第二道光 (1998-)

LC Chirochromic Switches with Binary Logic

JACS 2000, 122 (32), 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 -  P  P → M ’ )/( M ’  M ’→ P +  P  P → M ’ )] isodichroic low  M’→P

Droplets of K-15 containing (left) 1% (10R,11R,P) (right) 1% (10R,11R,M’) suspended in glycerol viewed at 200x magnification at room temperature p: Distance between concentric rings

Modulation of Photoswitching Profiles by 10,11-Dialkoxymethyl Substituents in C 2 -Symmetric DBS-based Helicenes spin-orbit perturbation  M’→P ~  P→M’ better solubility in LC Chen, C.-T.; * Chen, W.-C.; Lin, B.-C. Chem. Eur. J. 2010, 16, as a frontispiece.

LC Optical Switch with Ternary Logic  m  200m 330 nm 310 nm BA 200  m 290 nm C D 200  m 310 nm 200  m N*-LC (R,R,P)6c Standard LC N*-LC (R,R,P)6c Standard LC p = 13.9  m p = 8.2  m p = 16.3  m p ~ 0  m p = 2 × L × tan 

Photoswitching Profiles by 10,11-Dialkoxymethyl Substituents in C 2 -Symmetric DBS-based Helicenes Bearing Flexible Axial Chirality EntrySolventλ(nm)d.r.(M:P) a d.e. b 1n-hexane n-hexane : n-hexane : 4 +92

Helicene/Azobenzene Hybrid System as a Dual-mode Synergistic Optical Switch

Chirochromic Switching Chen, C.-T.; * Chen, W.-C. Org. Lett. 2010, 12, 1472.

Summary Ternary logic Dual 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 STIF as el. accepting template

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) (63)/60 Tri-STIF 620 (3.5)685 (13.3) (61)/64 N-Tri-STB 570 (11.3)690 (14.2) (89)/109 Tri-SPF 550 (7.1)570 (5.1) (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

Comparison between Spiro-Fluorene and Spiro-STIF Fused Systems max : 445 (81); Trilayer device  ext : 4.5%  c : 9.2 cd/A;  p : 3.0 lm/w L 20 : 1847 cd/m 2 max : 468 (76); with host CBP (10 wt%)  ext : 2.5%  c : 5.2 cd/A;  p : 2.7 lm/w L max : 5494 cd/m 2 PEDOT EML TPBi

Future Outlooks

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 Wei Mr. Wei-Shang Chao Mr. How-wei Liu Dr. Bor-Chiao Lin Mr. Wen-Ching Chen Mr. Chien-Hsiang Chen Financial Supports: National Science Council Department of Chemistry National Taiwan Normal University National Tsing-Hua University

結語和祝語