ORGANIC
LETTERS
2006
Vol. 8, No. 7
1363-1366
Novel H-Shaped Persistent Architecture
Based on a Dispiro Building Block
System
Ling-Hai Xie, Xiao-Ya Hou, Chao Tang, Yu-Ran Hua, Rui-Jie Wang,
Run-Feng Chen, Qu-Li Fan, Lian-Hui Wang, Wei Wei, Bo Peng, and
Wei Huang*,†,‡
Institute of AdVanced Materials (IAM), Fudan UniVersity, Shanghai 200433, China
wei-huang@fudan.edu.cn; chehw@nus.edu.sg
Received January 14, 2006
ABSTRACT
A novel dispiro building block, dispiro[fluorene-9,5′(7′H)-diindeno[2,1-b:1′,2′-d]thiophene-7′,9′′-fluorene], and its two derivatives, TBP-DSFDITF
and TDOF-DSFDITF, were designed and synthesized. Because of the rigidity and orthogonality of the spiro structure, TBP-DSFDITF exhibits
a well-defined H-shaped architecture, which consists of two ter(biphenyls) as the arms of the H-shape and 3,4-diphenylthiophene as the rung,
connecting via completely rigid dispiro linkages with two sp3 carbon atoms.
Shape-persistent molecular architectures on the nanometer
scale,1 e.g., macromolecular disks,2 helical macromolecules,3
π-conjugated macrocycle molecules,4 and ladder macromol-
ecules,5 have currently attracted a great deal of attention
because of their many applications in the fields of supramo-
lecular chemistry and organic electronics. For example,
π-conjugated macrocycles have assembled into discotic liquid
crystals or nanotubes,4b and helicenes with a precisely ordered
stereostructure have been applied to chiral separation and
molecular recognition.6 The common feature of these mol-
ecules is a typical π-conjugated or helical conjugated
backbone. One strategy for devising new shape-persistent
molecular architectures with special self-assembly behavior
is to incorporate the stiff semiconjugated or π-interrupted
backbones into the above architectures.7 By doing this, new
supramolecular phenomena can occur, e.g., calix[4]arenes
for molecular recognition8 and bicyclic ring-bridged iptycene
for molecular motor devices,9 although strong π-π stacking
supramolecular interaction is not found.
† Institute of Advanced Materials (IAM), Nanjing University, Nanjing
210093, China.
‡ Department of Chemical and Biomolecular Engineering, National
University of Singapore, Singapore 119260, Republic of Singapore.
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10.1021/ol060109x CCC: $33.50
© 2006 American Chemical Society
Published on Web 03/08/2006