Geckeler K.E., Nishide H. (Eds.) Advanced Nanomaterials

5.3 Helical Polymer-Based Functional Films 185

5.3.2

Chiroptical Transfer and Ampliﬁ cation in Binary Helical Polysilane Films

In addition to controlling the chiroptical properties such as memory and switch,

chiroptical transfer and ampliﬁ cation have also been achieved based on the concept

of the “ sergeants and soldiers ” principle [57] in binary helical polysilane ﬁ lms.

Optically active poly{ n - decyl - ( S ) - 2 - methylbutylsilane} (as “ sergeants ” , 5 :

M

w

= 2.11 × 1 0

5

, M

w

/ M

n

= 1.77) with an almost 7

3

helix and optically inactive

poly( n - decyl - 3 - methylbutyl - silane) (as “ soldiers ” , 8 : M

w

= 1.11 × 1 0

5

, M

w

/ M

n

= 1.75)

and poly( n - decyl - i - butylsilane) (as “ soldiers ” , 9 : M

w

= 3.36 × 1 0

4

, M

w

/ M

n

= 1.17)

were used for this study, as shown in Scheme 5.5 . Polymers 8 and 9 have equal

populations of right and left 7

3

helices; however, the rigidities of 5 , 8 , and 9 are

different. The polymers 5 and 9 , with β - branching methyl groups in the side

chains, were classiﬁ ed into rigid rod - like polymers with a persistent length of about

70 nm, while 8 belonged to a semi - rigid polymer with a persistent length of only

6 nm [31] .

The CD spectra of a grafted 5 - spin - coated 8 bilayer system prepared on quartz

substrate were measured before and after annealing, as shown in Figure 5.24 . The

CD spectra of both the grafted 5 - spin - coated 8 bilayer system and a grafted 5

system alone showed a bisignate CD signal with a positive Cotton band at about

309 nm and a negative Cotton band at about 324 nm, as shown in Figure 5.24 . For

the grafted 5 - spin - coated 8 bilayer system, both positive - and negative - Cotton CD

intensity were greatly increased after thermal annealing. The enhancement in the

CD signal intensities was a result of a chiroptical transfer to spin - coated 8 either

from the chiral side chain of grafted 5 or the polymer backbone itself, and it was

drastically ampliﬁ ed after annealing. On the other hand, no signiﬁ cant changes

Figure 5.23 Thermal cycle responses of relative Kuhn ’ s

dissymmetry ratios Δ OD/OD of the solid ﬁ lm of 7 . Thermal

cycles were conducted by heating to 20 ° C, followed by cooling

to − 20 ° C.

186 5 Helical Polymer-Based Supramolecular Films

of CD signal intensities were observed for only immobilized grafted 5 after anneal-

ing. In Figure 5.24 , a decrease of the UV absorbance of the grafted 5 - spin - coated

8 bilayer system was observed after the annealing treatment. This result implies

that most of the polymer chains lie down before annealing in the quartz substrate

plane, as the ﬁ lm was prepared by a spin - coating technique. The thermal anneal-

ing treatment may impact some of the polymer chain segments of semi - rigid

spin - coated 8 in the perpendicular orientation and/or tilt of the substrate plane,

leading to the decrease of the apparent UV absorbance at 321 nm, as illustrated in

Figure 5.25 [58] .

Figure 5.26 shows the change in the relative Kuhn ’ s dissymmetry ratios

( g

solid

= Δ OD/OD ), after ( g

AA

) and before ( g

BA

) annealing with the varied ﬁ lm thick-

ness. As was evident, the ratios increased with the decrease in the thickness of 8 .

The magnitude of the g

AA

/ g

BA

value was found to be signiﬁ cantly higher in grafted

5 (ﬁ lled squares) than in spin - coated 5 (ﬁ lled circles), presumably due to the partial

penetration of spin - coated 5 polymer chains into the surface during the spin -

coating process of 8 , leading to the similar solvent solubility behaviors of 5 and 8 .

A tiny amount of immobilized, optically active 5 could induce and effectively

amplify the optical activity in the optically inactive 8 layer by thermal treatment.

Weak van der Waals interactions at the surface between these two polymers might

be responsible for the transfer and ampliﬁ cation of the optical activity in 8 . The

positional segmental movement of polymer chains in 8 (melting point 40 ° C, as

estimated by DSC) would easily occur, which would be responsible for the helical

Scheme 5.5 Chemical structures of optically inactive

poly( n - decyl - 3 - methylbutylsilane) (as “ soldiers ” , 8 ) and

poly( n - decyl - i - butylsilane) (as “ soldiers ” , 9 ).

5.3 Helical Polymer-Based Functional Films 187

Figure 5.24 Circular dichroism (CD) and UV

spectra of grafted 5 - spin - coated 8 bilayer

system onto quartz substrate before and after

annealing. The initial UV absorbance of 8 was

0.04, and total UV absorbance of grafted

5 - spin - coated 8 bilayer system was 0.39. In

this case, the spectra do not signiﬁ cantly

affect the spectral intensity with rotation of

the solid ﬁ lms at different angles.

Figure 5.25 Schematic representation of thermo - driven

chiroptical transfer and ampliﬁ cation in the “ soldier ” optically

inactive polysilane 8 from the “ sergeant ” optically active

helical polysilane 5 on quartz.

transfer from 5 to 8 in the solid ﬁ lm. This could be regarded as a “ sergeants and

soldiers ” system in the solid state. In the case of the 5 - spin - coated 9 bilayer system,

the optical activity transfer phenomenon was not seen, due to the higher transition

energy barrier (no transition was observed by DSC) originating from the rigid

rod - like conformation by the help of β - branched side chain.

188 5 Helical Polymer-Based Supramolecular Films

5.3.3

Summary of Helical Polymer - Based Functional Films

In this section, attention is focused on the fabrication of helical polymer - based

solid ﬁ lms as supramolecular assemblies that possess functionality based on chi-

roptical properties, such as switch, memory, transfer, and ampliﬁ cation. In Section

5.3.1 , simple molecular mass control and thermal modulation were shown to be

capable of realizing various chiroptical properties, such as the inversion “ − 1 ” and

“ +1 ” switch and memory with RW and WORM modes. Furthermore, different

types of polysilane were used to construct on - off “ 0 ” and “ +1 ” switching. For practi-

cal use of those systems, without the threat of polymer degradation by UV light

for example, a laser - assisted heat - mode RW system which is based on a dye dis-

persed in the switchable polysilanes may be feasible, provided that the applied

wavelengths of the dye and laser are much longer than those of the polysilanes.

A high - power, circularly polarized laser - diode would be effective to directly heat

the dye, leading to an indirect heating of the polysilane ﬁ lm above the T

c

.

. Control-

ling the cooling rate of the ﬁ lm would enable the switching or memorizing of the

chiroptical state above the T

c

.

. In order to access data from the polysilane ﬁ lm, a

controlled modulation of the laser to the dye, including the power, pulse irradia-

tion time, and periods, would be effective to erase with a heat mode and to read

with a photon mode.

Figure 5.26 Relative Kuhn ’ s dissymmetry ratios Δ OD/OD of a

grafted 8 - spin - coated 9 bilayer system (

䊏

) and spin - coated

8 - spin - coated 9 (

䊉

) on a quartz surface before ( g

BA

) and after

( g

AA

) annealing, as a function of the ﬁ lm thickness.

Acknowledgments 189

In Section 5.3.2 , the optical activity of rigid rod - like polysilane was discussed,

both in terms of grafted and spin - coated ﬁ lms, with a preferential helical sense,

which was transferred and greatly ampliﬁ ed to an optically inactive semi - rigid,

helical spin - coated polysilane layer at the solid surface by thermal annealing. Selec-

tion of the correct rigidity of the optically inactive helical polysilane was important

for the emergence of a helical polymer command surface of the “ sergeants and

soldiers ” type, a chiroptical ampliﬁ cation system in the solid ﬁ lm states.

It should be emphasized here that the weak van der Waals interactions between

polymers are key to the assembly of various chiroptical systems that possess

switch, memory, transfer, and ampliﬁ cation properties. Optically active polysilane

is unique in natural and synthetic helical polymers, and allows for the possibility

of creating a wide variety of supramolecular architectures with a range of chiropti-

cal properties.

Acknowledgments

The authors thank Professors M. M. Green (Polytechnic University), J. Michl

(University of Colorado), R. West (University of Wisconsin), K. Tamao (Kyoto

University), G. Basu (Bose Institute), R. G. Jones (University of Kent), T. M.

Swager (Massachusetts Institute of Technology), Y. Kawakami (JAIST), A.

Teramoto (Ritsumeikan University), T. Sato (Osaka University), and E. Yashima

(Nagoya University) for collaborations and fruitful discussions on the considera-

tion of optical properties of polysilanes in solution and in the solid state. They also

thank Professors J. Watanabe and S. Kawauchi of the Tokyo Institute of Tech-

nology for collaborations and discussions on the structural properties of poly( γ -

l - glutamates). Thanks are also extended to T. Hagihara, and F. Asanoma for

technical assistance and discussion, and to Doctors T. Imase, S. - Y. Kim, A. Saxena,

K. Okoshi, M. Naito, G. Kwak, M. Ishikawa, T. Kawabe, G. - Q. Guo, and Y. - G. Yang

for fruitful discussions.

A.O., M.F., and M.K. are supported by grants from CREST - JST, “ Syntheses

of the Cooperative Hyper Helical Polymers and Understanding of Structure -

Property - Functionality Relationship ” and “ Nanoelectronic - Device Fabrication

Based on the Fine Molecular Design. ” A.O. is also supported by grants from the

Ministry of Economy, Trade and Industry, Japan. M.F. is supported in part by

grants from the Ministry of Education, Science, Sports, and Culture of Japan and

by a Grant - in - Aid for Scientiﬁ c Research “ Experimental Test of Parity Nonconser-

vation at Helical Polymer Level ” (No. 16655046) and “ Design, Synthesis, Novel

Functionality of Nanocircle and Nanorod Conjugating Macromolecules ” (No.

16205017).

190 5 Helical Polymer-Based Supramolecular Films

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