Preferential screw sense

Preferential Screw Sense Helical Ordering of Polysilanes... 

Preferential Screw Sense Homopolymers with Enantiopure Chiral Side Chains... 

Copolymers with Preferential Screw Sense and Sergeants-and-Soldiers Principle... 

Switching Preferential Screw Sense by Helix-Helix Transition... 

Preferential screw sense helix induced by chiral side groups and/or chiral chemical influence... 

On the other hand, noticeable cooperative preferential screw sense induction was reported in rodlike polysilane copolymers bearing (.S )-2-mcthylbutyl and 2-methylpropyl groups (10) and (R)-2-melhylbutyl and 2-methylpropyl groups (11) in isooctane (Chart 4.3). Since the UV-CD spectral features of the polysilane copolymers are almost identical with those of 4-6 and the Xmax varies sensitively with changes in the molar fraction of chiral substituents and temperature,28 the copolymer systems are suitable for testing the sergeants-and-soldiers phenomenon by their CD-UV spectra. 

Kira and co-workers described the first single-crystal X-ray structure, CD, and UV spectra of hexasilane oligomers with preferential screw sense induced by... 

We also reported an intriguing chiral termini effect in rodlike poly(n-hexyl-(2-methylpropyl)silane) with (5)-2-me(hylbu(yl termini (15).28g Although the value of gabs is only +1 x 10-5, which indicates a very weak preferential screw sense in 15, it is noted that the preferential screw sense of 15 was opposite to that of 4, bearing the same (5)-2-me(hylbutyl side groups.28d,28f,28k... 

In this section, we comprehensively focused on the controlled synthesis, chiroptical characterization, and manipulation of optically active poly(dialkyl-silane)s. Although many artificial polymers adopting preferential screw sense... 

In order to discuss the preferential screw sense capability qualitatively in a series of 44 and 45 helical copolymers with chiral-achiral side chains, we compared the UV and CD spectral characteristics of 44 and 45 as a function of the chiral molar composition in detail. 

In this part, two series of 44 copolymers with coiled main-chain structures and 45 copolymers with stiff main-chain conformations were described. It was concluded that both optically inactive 42 and 43 adopt helical conformations with an equal proportion of P and M screw senses by means of UV and CD spectra as well as molecular mechanics calculations. A marked positive cooperative induction effect of the preferential screw sense in 44 and 45 copolymers was found. However, there is a marked difference in the helical cooperativity between 44 and 45, probably because of the differences in their global and local conformations. This difference can be related to the persistence of the helical conformation against defects allowing change of... 

In contrast, the CD spectra of 50, 51, and 52 exhibit negative Cotton effects, as shown in Figure 4.36 for 50. This implies a helical conformation, but of the opposite preferential screw sense to 48 and 49, even though the enantiopure chiral moiety in all cases is the (5 )-2-methylbutyl group. Similarly, the Cotton effect is of greatest magnitude (negative) at low temperature and almost very much reduced at 80°C. 

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