Conformation Control of Conjugated Polymers.

Published on Dec 9, 2020in Chemistry: A European Journal4.857
· DOI :10.1002/CHEM.202000220
Zi-Di Yu5
Estimated H-index: 5
(PKU: Peking University),
Yang Lu16
Estimated H-index: 16
(PKU: Peking University)
+ 1 AuthorsJian Pei74
Estimated H-index: 74
(PKU: Peking University)
In the past few decades, conjugated polymers have aroused extensive interest in organic electronic applications. The electrical performance of conjugated polymers has a close relationship with their backbone conformation. The conformation of the polymer backbone strongly affects the pi-electron delocalization along polymer chains, the energy bandgap, interchain interactions, and further affecting charge transport properties. To realize a rigid coplanar backbone that usually possesses efficient intrachain charge transport properties and enhanced pi-pi stackings, such conformation control becomes a useful strategy to achieve the high-performance (semi)conducting polymers. This review summarizes the most important polymer structures through conformation control at molecular levels, and then divides these rigid coplanar conjugated polymers into three categories: 1) non-covalent interactions locked conjugated polymers; 2) double-bond linked conjugated polymers; 3) ladder conjugated polymers. The effect of the conformation control on physical nature, optoelectronic properties, and their device performance is also discussed, as well as the challenges of chemical synthesis and structural characterization.
📖 Papers frequently viewed together
819 Citations
1 Author (Beiyue Shao)
#10Qiang Zhang (WSU: Washington State University)
To improve methane storage capacity of porous organic materials, this work demonstrates that a rigid ladder-type backbone is more entropically favorable for gas adsorption and leads to a high gas uptake per unit surface area. A porous ladder polymer network was designed and synthesized as the model material via cross-coupling polymerization and subsequent ring-closing olefin metathesis, followed by characterization by solid-state nuclear magnetic resonance (NMR) spectroscopy. This material exhib...
12 CitationsSource
#1Yang Lu (PKU: Peking University)H-Index: 16
#2Zi-Di Yu (PKU: Peking University)H-Index: 5
Last. Jian Pei (PKU: Peking University)H-Index: 74
view all 11 authors...
: Low n-doping efficiency and inferior stability restrict the thermoelectric performance of n-type conjugated polymers, making their performance lag far behind of their p-type counterparts. Reported here are two rigid coplanar poly(p-phenylene vinylene) (PPV) derivatives, LPPV-1 and LPPV-2, which show nearly torsion-free backbones. The fused electron-deficient rigid structures endow the derivatives with less conformational disorder and low-lying lowest unoccupied molecular orbital (LUMO) levels,...
62 CitationsSource
#1Yang Lu (PKU: Peking University)H-Index: 16
#2Jie-Yu Wang (PKU: Peking University)H-Index: 43
Last. Jian Pei (PKU: Peking University)H-Index: 74
view all 3 authors...
In the past several decades, conducting polymers have achieved remarkable progress and have been widely applied as the active materials for optoelectronics. So far, p-type conducting polymers exhibit high conductivities over 1000 S cm–1 and thermoelectric performance comparable to that of inorganic materials; however, only a few n-type conducting polymers showed conductivities over 1 S cm–1 after doping. The low conductivity of n-type conducting polymers is considered as the major barrier for fu...
72 CitationsSource
#1Congzhi Zhu (A&M: Texas A&M University)H-Index: 8
#2Alexander J. Kalin (A&M: Texas A&M University)H-Index: 7
Last. Lei Fang (A&M: Texas A&M University)H-Index: 34
view all 3 authors...
ConspectusMolecular conformation and rigidity are essential factors in determining the properties of individual molecules, the associated supramolecular assemblies, and bulk materials. This correlation is particularly important for π-conjugated molecular and macromolecular systems. Within such an individual molecule, a coplanar conformation facilitates the delocalization of not only molecular orbitals but also charges, excitons, and spins, leading to synergistically ensembled properties of the e...
31 CitationsSource
#1Maciej Barłóg (Texas A&M University at Qatar)H-Index: 11
#2Ihor Kulai (Texas A&M University at Qatar)H-Index: 7
Last. Mohammed Al-Hashimi (Texas A&M University at Qatar)H-Index: 21
view all 9 authors...
A series of 11 novel fluorinated and non-fluorinated di(thiazolyl)benzenes have been synthesized via microwave assisted Stille coupling and characterized using X-ray crystallography. A comparative analysis of nonbonding interactions in bis-heteroaryl-phenylene derivatives depending on the heterocycle structure and degree of fluorination of the central aromatic unit has been reported. We have systematically studied the effect of fluorination on the intramolecular interactions, π–π stacking, CH⋯F ...
7 CitationsSource
#1Markus Grandl (Hess Corporation)H-Index: 6
#2Jonas Schepper (University of Ulm)H-Index: 2
Last. Frank Pammer (University of Ulm)H-Index: 13
view all 6 authors...
A poly(biphenylene–pyrazinylene) (PPz, Egopt = 3.10 eV) and a head-to-tail regioregular polypyridine (rr-P4Py, Egopt = 3.25 eV) equipped with 1-alkenyl side chains have been prepared and postfunctionalized by hydroboration with different hydroboranes (9H-BBN, (C6F5)2B-H (BPF-H), Cl2B-H) to give the corresponding ladder polymers featuring intramolecular coordinative N → B bonds. Characterization of the optical and electrochemical properties of the postfunctionalized polymers shows that the boryla...
15 CitationsSource
The introduction of B ← N coordinate bond—isoelectronic to C–C single bond—into π-systems represents a promising strategy to impart exotic redox and electrochromic properties into conjugated organic molecules and macromolecules. To achieve both reductive and oxidative activities using this strategy, a cruciform ladder-type molecular constitution was designed to accommodate oxidation-active, reduction-active, and B ← N coordination units into a compact structure. Two such compounds (BN-F and BN-P...
27 CitationsSource
#1Ada Onwubiko (Imperial College London)H-Index: 5
#2Wan Yue (Imperial College London)H-Index: 7
Last. Iain McCulloch (Imperial College London)H-Index: 108
view all 16 authors...
Conventional semiconducting polymer synthesis typically involves transition metal-mediated coupling reactions that link aromatic units with single bonds along the backbone. Rotation around these bonds contributes to conformational and energetic disorder and therefore potentially limits charge delocalisation, whereas the use of transition metals presents difficulties for sustainability and application in biological environments. Here we show that a simple aldol condensation reaction can prepare p...
71 CitationsSource
#1Congzhi Zhu (A&M: Texas A&M University)H-Index: 8
#2Lei Fang (A&M: Texas A&M University)H-Index: 34
Torsional conformation of the backbone of a π-conjugated molecule or macromolecule shapes its solubility, optoelectronic characteristics, rheological behaviors, and ultimately solid-state functions. In order to tailor these molecular, supramolecular, and materials properties, the desired coplanar conformation in π-conjugated systems can be locked by using dynamic noncovalent bonds. In this article, the syntheses, characterizations, and unique properties of conjugated molecules/polymers involving...
36 CitationsSource
#1Yu-Qing Zheng (PKU: Peking University)H-Index: 22
#2Ze-Fan Yao (PKU: Peking University)H-Index: 12
Last. Jian Pei (PKU: Peking University)H-Index: 74
view all 10 authors...
Polymer self-assembly in solution prior to film fabrication makes solution-state structures critical for their solid-state packing and optoelectronic properties. However, unraveling the solution-state supramolecular structures is challenging, not to mention establishing a clear relationship between the solution-state structure and the charge-transport properties in field-effect transistors. Here, for the first time, it is revealed that the thin-film morphology of a conjugated polymer inherits th...
58 CitationsSource
Cited By7
#1Mitsuhiko Morisue (Kyoto Institute of Technology)H-Index: 12
#2Miho Kawanishi (Kyoto Institute of Technology)H-Index: 1
Last. Koichi Nozaki (University of Toyama)H-Index: 32
view all 7 authors...
The formation of C-F···H-C "hydrogen bonds" has been a controversial subject because, in principle, fluorine is hardly an acceptor for less acidic protons contrasting to the C-F···H-O and C-F···H-N hydrogen bonds. Nevertheless, the interaction is emerging as a powerful implement for confining the torsional rotation in the design of fully coplanar π-conjugated polymers. Heretofore, no evidence of the C-F···H-C interaction has been observed in solutions. We herein disclose comprehensive evidence t...
#1Yu-Wei Su (FCU: Feng Chia University)H-Index: 15
#2Yi-Shan Huang (FCU: Feng Chia University)
Last. Po-Tuan Chen (NTUT: National Taipei University of Technology)
view all 4 authors...
Benzo[1,2-b:4,5-b']dithiophene (BDT) contains electron donating groups and conjugates with acceptor material as a donor-acceptor type conjugated polymer, which can be applied in bulk heterojunction organic photovoltaics due to its high charge carrier mobility. In this study, we used Stille coupling polymerization to synthesize a BDT monomer with thiophene side-chains and copolymerized with dioctyl 2,5-dibromoterephthalate (DTP) to form a 2-D type donor-acceptor conjugated polymer, BDT-DTP. Therm...
#1Li Ding (PKU: Peking University)H-Index: 24
#2Zi-Yuan Wang (PKU: Peking University)H-Index: 5
Last. Jian Pei (PKU: Peking University)H-Index: 74
view all 10 authors...
We developed a rapid method to calculate the average electronic structure properties of large ensembles of conjugated polymer chains sampling their conformational space. This is achieved by using the localized molecular orbital (MO) method to rapidly compute the MOs and their energies for isolated polymer chains and through using a calibration scheme to further correct the obtained energies by comparison with a few accurate calculations. The method is applied to the study of the density of state...
2 CitationsSource
#1Wei Zheng (Nagoya University)
#2Tomoyuki IkaiH-Index: 26
Last. Eiji Yashima (Nagoya University)H-Index: 89
view all 3 authors...
We report the unprecedented synthesis of one-handed helical spiro-conjugated ladder polymers with well-defined primary and secondary structures, in which the spiro-linked dibenzo[ a , h ]anthracene fluorophores are arranged in a one-handed twisting direction, through quantitative and chemoselective acid-promoted intramolecular cyclizations of random-coil precursor polymers composed of chiral 1,1'-spirobiindane and achiral bis[2-(4-alkoxyphenyl)ethynyl]phenylene units. Intense circular dichroism ...
1 CitationsSource
#1Brian J. Eckstein (NU: Northwestern University)H-Index: 5
#2Ferdinand S. Melkonyan (NU: Northwestern University)H-Index: 21
Last. Tobin J. Marks (NU: Northwestern University)H-Index: 179
view all 11 authors...
1 CitationsSource
#1Ze-Fan YaoH-Index: 12
#2Jie-Yu WangH-Index: 43
Last. Jian PeiH-Index: 74
view all 3 authors...
The multi-level microstructure of conjugated polymers is the most critical parameter determining the charge transport property in field-effect transistors (FETs). However, controlling the hierarchical microstructures and the structural evolution remains a significant challenge. In this perspective, we discuss the key aspects of multi-level microstructures of conjugated polymers towards high-performance FETs. We highlight the recent progress in the molecular structures, solution-state aggregation...
9 CitationsSource