Stille Polycondensation: A Versatile Synthetic Approach to Functional Polymers

Zheng, Tianyue; Schneider, Alexander M.; Yu, Luping

doi:10.1002/9783527695959.ch1

Cited by 8 publications

(5 citation statements)

References 151 publications

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“…Molecules 1 – 8 were obtained from c and d in either Stille or Suzuki cross reactions. In our experience, coupling cross-coupling reactions involving thiophene derivatives proceed better via Stille than via Suzuki reactions . Accordingly, 3 and 4 were successfully obtained via Stille cross-coupling of c with tributyl(4-hexylthiophen-2-yl)stannane and tributyl(5-hexylthiophen-2-yl)stannane, which were obtained following a literature procedure .…”

Section: Resultsmentioning

confidence: 97%

“…In our experience, coupling cross-coupling reactions involving thiophene derivatives proceed better via Stille than via Suzuki reactions. 51 Accordingly, 3 and 4 were successfully obtained via Stille cross-coupling of c with tributyl(4-hexylthiophen-2-yl)stannane and tributyl(5-hexylthiophen-2-yl)stannane, which were obtained following a literature procedure. 52 The attempted synthesis of 2 by Stille cross-coupling was, however, unsuccessful and resulted in a wide range of products.…”

Section: Resultsmentioning

confidence: 99%

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Tuning the Optical Characteristics of Diketopyrrolopyrrole Molecules in the Solid State by Alkyl Side Chains

et al. 2020

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The optical properties of two sets of donor–acceptor–donor molecules with terminal bithiophene donor units and a central diketopyrrolopyrrole (DPP) acceptor unit are studied. The two sets differ in the alkyl chains on the DPP, which are either branched at the α-carbon (3-pentyl) ( 1 – 4 ) or linear ( n -hexyl) ( 5 – 8 ). Within each set, the molecules differ by the absence or presence of n -hexyl chains on the terminal thiophene rings in the 3′, 4′, or 5′ positions. While in solution, the optical spectra differ only subtly; they differ dramatically in the solid state. In contrast to 5 – 8 , 1 – 4 are nonplanar as a consequence of the sterically demanding 3-pentyl groups, which inhibit π-stacking of the DPP units. Using the crystal structures of 2 (brick layer stacking) and 6 (slipped stacking), we quantitatively explain the solid state absorption spectra. By computing the molecular transition charge density and solving the dispersion relation, the optical absorption of the molecules in the crystal is predicted and in agreement with experiments. For 2 , a single resonance frequency is obtained, while for 6 two transitions are seen, with the lower-energy transition being less intense. The results demonstrate how subtle changes in substitution exert large effects in optical properties.

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Section: Resultsmentioning

confidence: 97%

Section: Resultsmentioning

confidence: 99%

Tuning the Optical Characteristics of Diketopyrrolopyrrole Molecules in the Solid State by Alkyl Side Chains

et al. 2020

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“…Furthermore, polymers produced by Stille polycondensation may contain palladium colloids as well as difficult‐to‐remove tin impurities, which not only have an influence on the optical and electronic properties but also pose a serious health risk. [ 51 ]…”

Section: Synthesismentioning

confidence: 99%

“…[50] The tin-monomer is typically synthesized by using highly toxic tin trialkylstannanes and organolithium reagents. [51] The Stille methodology is especially advantageous in the context of functional group compatibility as the tin moieties show an even higher functional group tolerance than the boron-based moieties of Suzuki monomers. [47,51] However, the Stille polycondensation shows similar limitations like the Suzuki-based polymerization (SPC): in case of the AA/BB-approach a very precise stoichiometric balance of the monomers is crucial for high-molecular weights.…”

Section: Other Cross-coupling Based Polymerizations: Stille-polyconde...mentioning

confidence: 99%

“…[51] The Stille methodology is especially advantageous in the context of functional group compatibility as the tin moieties show an even higher functional group tolerance than the boron-based moieties of Suzuki monomers. [47,51] However, the Stille polycondensation shows similar limitations like the Suzuki-based polymerization (SPC): in case of the AA/BB-approach a very precise stoichiometric balance of the monomers is crucial for high-molecular weights. Since Stille monomers are laborious to purify and they tend to undergo homocoupling, the control of stoichiometry is difficult.…”

Section: Other Cross-coupling Based Polymerizations: Stille-polyconde...mentioning

confidence: 99%

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A Polymer Lost in the Shuffle: The Perspective of Poly(para)phenylenes

Kleybolte

Vagin

Rieger

2023

Macro Chemistry & Physics

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During 1990s, poly(para)phenylenes (PPPs) are one of the most prominent and hyped classes of conjugated polymers. Even though they have been heavily investigated for different applications, they are now eking out a rather niche existence. It is believed that this decline of interest partly has come from the early obstacle of synthesizing high-molecular weight, processable, and defect-free PPPs. Early examples of PPPs are not only rather oligomers than polymers but also contain many regiochemical and structural defects. Furthermore, early unsubstituted materials are infusible and insoluble, which have made their practical application almost impossible. Another reason for the decline of research interest in PPPs may be their underperformance in early applications, particularly in organic light-emitting diodes (OLEDs), which ultimately lead to a lack of follow-up publications. However, over the last two decades not only more precise and advanced synthesis methods have arisen but also a more profound understanding of those applications has been achieved within which new technological approaches have emerged. It is believed that PPPs would benefit from this development. Accordingly, in this perspective, the synthesis, structures, properties, and applications of PPPs reported so far as well as their potential in future technologies are discussed.

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Phenacyl Bromide as a Single‐Component Photoinitiator: Photoinduced Step‐Growth Polymerization ofN‐Methylpyrrole andN‐Methylindole

et al. 2022

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The synthesis of step-growth polymers by photoinduced methods is a challenging issue in synthetic chemistry. Here, we report a single component near UV responsive photopolymerization system for step-growth polymerization of N-methylpyrrole (MPyr) and N-methylindole (MIn) by using phenacyl bromide (PAB). The obtained high molecular weight conjugated polymers were characterized by spectral and chromatographic methods. Detailed laser flash photolysis and spectroscopic studies revealed that polymerization proceeds by successive photoinduced cleavage of PAB followed by electron transfer, proton release and coupling processes. After photolysis, chain growth continues also in daylight or dark by acidic oxidation. The structural features of the polymers were investigated. PAB single component photoinitiator enables an efficient, rapid, room temperature step-growth polymerization process of MPyr and MIn that can be applied to other conjugated monomers.

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Stille Polycondensation: A Versatile Synthetic Approach to Functional Polymers

Cited by 8 publications

References 151 publications

Tuning the Optical Characteristics of Diketopyrrolopyrrole Molecules in the Solid State by Alkyl Side Chains

Tuning the Optical Characteristics of Diketopyrrolopyrrole Molecules in the Solid State by Alkyl Side Chains

A Polymer Lost in the Shuffle: The Perspective of Poly(para)phenylenes

Phenacyl Bromide as a Single‐Component Photoinitiator: Photoinduced Step‐Growth Polymerization ofN‐Methylpyrrole andN‐Methylindole

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