All-conjugated donor–acceptor block copolymers featuring a pentafulvenyl-polyisocyanide-acceptor

Schraff, Sandra; Maity, Sudeshna; Schleeper, Laura; Dong, Yifan; Lucas, Sebastian; Bakulin, Artem A.; Hauff, Elizabeth von; Pammer, Frank

doi:10.1039/c9py01879d

Cited by 5 publications

(2 citation statements)

References 47 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Another effective strategy to this end involves the introduction of additional conjugated polymers to form all-conjugated block copolymers (BCPs) because they exhibit characteristics of microphase separation . With the development of Kumada catalyst-transfer polymerization (KCTP), many conjugated BCPs, particularly electron-rich polyarenes, such as poly(3-alkylthiophenes) (P3ATs), have been synthesized. − Due to the limited type of monomers compatible with KCTP, controlled synthesis of electron-rich and electron-deficient donor–acceptor BCPs is very rare. − Most of the P3AT-based conjugated BCPs are categorized into three classes: P3AT- b -P3AT BCPs comprising different alkyl side-chain lengths or topologies, − P3AT- b -P3AT BCPs comprising side-chain functional groups, − and BCPs comprising different types of main backbones. − These rod–rod BCPs have been systematically investigated regarding their syntheses, crystalline structures, and applications in transistors and photovoltaic cells.…”

Section: Introductionmentioning

confidence: 99%

Interrogating the Effect of Block Sequence on Cocrystallization, Microphase Separation, and Charge Transport in All-Conjugated Triblock Copolymers

Zhan

Chen

et al. 2022

Macromolecules

View full text Add to dashboard Cite

Despite impressive progress in the research of all-conjugated diblock copolymers, there is a quite limited investigation into triblock counterparts. Moreover, regarding the block sequence, which is peculiar to triblock copolymers, its effect on their crystallization and microphase separation is still poorly understood. Herein, we design and synthesize a family of all-conjugated triblock copolymers comprising poly(3-butylthiophene) (P3BT), poly(3-hexylselenophene) (P3HS), and poly(3-dodecylthiophene) (P3DDT) of various block sequences, i.e., P3BT-b-P3DDT-b-P3HS, P3BT-b-P3HS-b-P3DDT, and P3HS-b-P3BT-b-P3DDT, elucidate the impact of the block sequence on their crystalline structures in conjunction by utilizing various solvents and thermal annealing, and investigate the charge transport properties of these different crystalline structures. Remarkably, the block sequence with the P3DDT block located in the central position (P3BT-b-P3DDT-b-P3HS) and faster solvent evaporation favor the cocrystals, while the P3DDT block situated at terminals (P3BT-b-P3HS-b-P3DDT and P3HS-b-P3BT-b-P3DDT), slower evaporation of the solvent, and heating lead to microphase separation over cocrystallization. Intriguingly, three different microphase-separated structures, which are correlated to the block sequence, are observed after high-temperature annealing (240 °C). Moreover, these various crystalline structures of triblock copolymers influence their charge mobilities in organic field-effect transistors (OFETs) closely. Thus, this work comprehensively elucidates the effect of the block sequence (intrinsic factor), solvent, and heating temperature (extrinsic factors) on the crystalline structure and electrical properties of conjugated triblock copolymers.

show abstract

Section: Introductionmentioning

confidence: 99%

Interrogating the Effect of Block Sequence on Cocrystallization, Microphase Separation, and Charge Transport in All-Conjugated Triblock Copolymers

Zhan

Chen

et al. 2022

Macromolecules

View full text Add to dashboard Cite

show abstract

“…We recently reported a first series of fulvenyl-functionalized arylisocyanides and investigated the properties of their corresponding polyisocyanides. − To explore the possibilies of the monomers in coordination chemistry, we also prepared and characterized the corresponding gold(I) chloride complexes (Chart C) . Isocyanides are among the most widely used ligands in gold(I) chemistry, which itself is a highly vibrant field of research due the potential use of gold(I) complexes as functional materials .…”

Section: Introductionmentioning

confidence: 99%

Electronic Properties and Solid-State Packing of Isocyanofulvenes and Their Gold(I) Chloride Complexes

et al. 2020

Self Cite

View full text Add to dashboard Cite

Two methods for the synthesis of isocyanofulvenes are reported, and a series of ligands of the type R 5-dibenzo[a,d]cycloheptenylidene; f, 9-thioxanthenylidene; and g, 2,5-dimethyl-3,4-diphenylcyclopentadienylidene) were prepared along with their gold(I) chloride complexes (R 2 CHNC AuCl, 5a−f). A comprehensive study of the properties of the precursors, free ligands, and gold(I) complexes is reported and complemented by DFT calculations. Solid-state structure of two complexes (5a and 5c) show extensive aurophilic interactions and π−π stacking of the ligands. The metal centers are not involved in optical transitions. However, metal coordination leads to a consistent bathochromic shift in the absorption spectra, which signifies the effective conjugation between the isocyano group and the π-systems of the ligands. Furthermore, an additional DFT study of carbonyl complexes of the type R 2 CH−NC−M(CO) 5 (M = Cr, Mo, and W; R 2 CHNC = 4a) indicates very effective metal-to-ligand charge transfer when isocyanopentafulvenes are used as ligands.

show abstract

Asymmetric chain‐growth synthesis of polyisocyanide with chiral nickel precatalysts

Schraff

Kreienborg

Trampert

et al. 2020

Journal of Polymer Science

View full text Add to dashboard Cite

Nickel(II)‐aryl complexes [(L2)Ni(Ar)Br] bearing either chiral phosphine ligands (L2 = RR‐ or SS‐DIPAMP, Ar = ortho‐anisyl), or a chiral aryl‐group have been prepared, and their structural optical an chiroptical properties have been characterized. Enantiomeric pairs of both catalysts have been used for the asymmetric polymerization of different isocyanides (M1, M2, M3), to give well defined polyisocyanides (P1, P2, P3). Their polymerization behavior has been studied, which confirmed chain‐growth polymerization in all cases. The asymmetric induction has been verified by circular dichroism spectroscopy on enantiomeric pairs of all three polymers.

show abstract

All-conjugated donor–acceptor block copolymers featuring a pentafulvenyl-polyisocyanide-acceptor

Abstract: A fulvenyl-functionalized polyisocyanide (PIC2) with a high electron mobility of μe = 10−2 cm2 V−1 s−1 has been incorporated into donor–acceptor block copolymers. Their self-assembly and bulk-morphology have been studied, and potential device applications have been explored.

Cited by 5 publications

References 47 publications

Interrogating the Effect of Block Sequence on Cocrystallization, Microphase Separation, and Charge Transport in All-Conjugated Triblock Copolymers

Interrogating the Effect of Block Sequence on Cocrystallization, Microphase Separation, and Charge Transport in All-Conjugated Triblock Copolymers

Electronic Properties and Solid-State Packing of Isocyanofulvenes and Their Gold(I) Chloride Complexes

Asymmetric chain‐growth synthesis of polyisocyanide with chiral nickel precatalysts

Contact Info

Product

Resources

About