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12944291447
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note
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For pseudochiral polysilanes, such as poly(p-tolylsilane), each silicon atom of the polymer chain is a stereogenic center. The stereochemical arrangement of adjacent Si centers dictates the degree of stereoregularity (also called tacticity) of the polymer chain. Isotactic and syndiotactic stereoregular polysilanes respectively arise from the repeating and alternating arrangement of adjacent Si centers. An atactic polysilane refers to the random arrangement of adjacent Si centers. See ref 23 for a complete description.
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12944249371
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note
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Representative XRD and DSC spectra of PTSi are provided in the Supporting Information.
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64
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12944317143
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note
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The triad model of the polysilane chain describes the diastereomeric relationship between three adjacent Si stereogenic centers. For an isotactic polysilane, the diastereomeric relationship of the central Si atom to both neighboring Si centers is mesoid, labeled mm. For a syndiotactic polysilane, the diastereomeric relationship of the configuration of the central Si atom to both neighboring Si centers is racemic, labeled rr. For an atactic polysilane, the diastereomeric relationship of the configuration of the central Si atom to one neighboring Si centers is mesoid and racemic to the second neighboring center, labeled mr. In terms of NMR spectroscopy, separate resonances for the rr, mr, and mm stereoequences can be detected and thereby used as a gauge of polymer stereoregularity. See ref 23 for a complete description.
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