Conjugated Polymers: Preparation, Properties and Applications

Topic Information

Dear Colleagues,

Polymers compete with metals as constituents of several materials, being cheapest in preparation and exhibiting more ductility. Synthesis of conjugated polymers allowed preparing semiconducting materials for replacing metals in electronic and optical applications. Conjugated polymers exhibit alternating double bonds and single bonds and several p-orbitals overlapping, with consequent high electron mobility. Light absorption and emission in the range of UV-Visible-Near IR frequencies rendered the compounds objects of several studies concerning potential applications in Photovoltaic, Light Emission Diodes, Bio-Imaging, Hydrogen Photo-production. Conjugated polymers and analysis of their electro-optical properties constitute an active research field due to the needing for materials whose performances are comparable to the metal semiconductors and can replace them. The development of conjugated polymers can also allow applications of semiconductors in new fields, such as electro-optical biomaterials as well as in the treatment of neurodegenerative, inflammation and infectious disease. In this Topic, we intend to collect research work concerning the preparation of conjugated polymers and analysis of their properties.

Dr. Carmine Coluccini
Dr. Paolo Coghi
Topic Editors

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Participating Journals

Journal Name	Impact Factor	CiteScore	Launched Year	First Decision (median)	APC
Polymers polymers	4.7	8.0	2009	14.5 Days	CHF 2700
Nanomaterials nanomaterials	4.4	8.5	2010	13.8 Days	CHF 2900
Molecules molecules	4.2	7.4	1996	15.1 Days	CHF 2700
Chemistry chemistry	2.4	3.2	2019	13.4 Days	CHF 1800
Macromol macromol	-	5.2	2021	20.4 Days	CHF 1000

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Published Papers (11 papers)

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11 pages, 2493 KiB  

Open AccessArticle

Impact of Structural Alterations from Chemical Doping on the Electrical Transport Properties of Conjugated Polymers

by Baiqiao Yue, Xiaoxuan Zhang, Kaiqing Lu, Haibao Ma, Chen Chen and Yue Lin

Polymers 2024, 16(17), 2467; https://doi.org/10.3390/polym16172467 - 30 Aug 2024

Viewed by 678

Abstract

Conjugated polymers (CPs) are widely used as conductive materials in various applications, with their conductive properties adjustable through chemical doping. While doping enhances the thermoelectric properties of CPs due to improved main-chain transport, overdoping can distort the polymer structure, increasing energy disorder and [...] Read more.

Conjugated polymers (CPs) are widely used as conductive materials in various applications, with their conductive properties adjustable through chemical doping. While doping enhances the thermoelectric properties of CPs due to improved main-chain transport, overdoping can distort the polymer structure, increasing energy disorder and impeding intrinsic electrical transport. This study explored how different dopants affect the structural integrity and electrical transport properties of CPs. We found that dopants vary in their impact on CP structure, consequently altering their electrical transport capabilities. Specifically, ferric chloride (FeCl₃)-doped indacenodithiophene-co-benzothiadiazole (IDTBT) shows superior electrical transport properties to triethyloxonium hexachloroantimonate (OA)-doped IDTBT due to enhanced backbone planarity and rigidity, which facilitate carrier transport and lower energetic disorder. These results highlight the critical role of dopant selection in optimizing CPs for advanced applications, suggesting that strategic dopant choices can significantly refine the charge transport characteristics of CPs, paving the way for their industrialization. Full article

(This article belongs to the Topic Conjugated Polymers: Preparation, Properties and Applications)

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10 pages, 2869 KiB  

Open AccessArticle

High-Performance One-Dimensional Sub-5 nm Transistors Based on Poly(p-phenylene ethynylene) Molecular Wires

by Zhilin Chen, Xingyi Tan, Qiang Li, Jing Wan and Gang Xu

Molecules 2024, 29(13), 3207; https://doi.org/10.3390/molecules29133207 - 5 Jul 2024

Viewed by 809

Abstract

Poly(p-phenylene ethynylene) (PPE) molecular wires are one-dimensional materials with distinctive properties and can be applied in electronic devices. Here, the approach called first-principles quantum transport is utilized to investigate the PPE molecular wire field-effect transistor (FET) efficiency limit through the geometry of the [...] Read more.

Poly(p-phenylene ethynylene) (PPE) molecular wires are one-dimensional materials with distinctive properties and can be applied in electronic devices. Here, the approach called first-principles quantum transport is utilized to investigate the PPE molecular wire field-effect transistor (FET) efficiency limit through the geometry of the gate-all-around (GAA) instrument. It is observed that the n-type GAA PPE molecular wire FETs with a suitable gate length (L_g = 5 nm) and underlap (UL = 1, 2, 3 nm) can gratify the on-state current (I_on), power dissipation (PDP), and delay period (τ) concerning the conditions in 2028 to achieve the higher performance (HP) request of the International Roadmap for Device and Systems (IRDS, 2022 version). In contrast, the p-type GAA PPE molecular wire FETs with L_g = 5, 3 nm, and UL of 1, 2, 3 nm could gratify the I_on, PDP, and τ concerning the 2028 needs to achieve the HP request of the IRDS in 2022, while L_g = 5 and UL = 3 nm could meet the I_on and τ concerning the 2028 needs to achieve the LP request of the IRDS in 2022. More importantly, this is the first one-dimensional carbon-based ambipolar FET. Therefore, the GAA PPE molecular wire FETs could be a latent choice to downscale Moore’s law to 3 nm. Full article

(This article belongs to the Topic Conjugated Polymers: Preparation, Properties and Applications)

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20 pages, 7168 KiB  

Open AccessReview

Controlled Surface Textures of Elastomeric Polyurethane Janus Particles: A Comprehensive Review

by Ana Catarina Trindade

Polymers 2024, 16(13), 1835; https://doi.org/10.3390/polym16131835 - 27 Jun 2024

Viewed by 942

Abstract

Colloidal particle research has witnessed significant advancements in the past century, resulting in a plethora of studies, novel applications, and beneficial products. This review article presents a cost-effective and low-tech method for producing Janus elastomeric particles of varied geometries, including planar films, spherical [...] Read more.

Colloidal particle research has witnessed significant advancements in the past century, resulting in a plethora of studies, novel applications, and beneficial products. This review article presents a cost-effective and low-tech method for producing Janus elastomeric particles of varied geometries, including planar films, spherical particles, and cylindrical fibers, utilizing a single elastomeric material and easily accessible chemicals. Different surface textures are attained through strain application or solvent-induced swelling, featuring well-defined wavelengths ranging from sub-microns to millimeters and offering easy adjustability. Such versatility renders these particles potentially invaluable for medical applications, especially in bacterial adhesion studies. The coexistence of “young” regions (smooth, with a small surface area) and “old” regions (wrinkled, with a large surface area) within the same material opens up avenues for biomimetic materials endowed with additional functionalities; for example, a Janus micromanipulator where micro- or nano-sized objects are grasped and transported by an array of wrinkled particles, facilitating precise release at designated locations through wrinkle pattern adjustments. This article underscores the versatility and potential applications of Janus elastomeric particles while highlighting the intriguing prospects of biomimetic materials with controlled surface textures. Full article

(This article belongs to the Topic Conjugated Polymers: Preparation, Properties and Applications)

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30 pages, 6963 KiB  

Open AccessReview

Literature Review on Conjugated Polymers as Light-Sensitive Materials for Photovoltaic and Light-Emitting Devices in Photonic Biomaterial Applications

by Paolo Coghi and Carmine Coluccini

Polymers 2024, 16(10), 1407; https://doi.org/10.3390/polym16101407 - 15 May 2024

Cited by 1 | Viewed by 1244

Abstract

Due to their extended p-orbital delocalization, conjugated polymers absorb light in the range of visible–NIR frequencies. We attempt to exploit this property to create materials that compete with inorganic semiconductors in photovoltaic and light-emitting materials. Beyond competing for applications in photonic devices, organic [...] Read more.

Due to their extended p-orbital delocalization, conjugated polymers absorb light in the range of visible–NIR frequencies. We attempt to exploit this property to create materials that compete with inorganic semiconductors in photovoltaic and light-emitting materials. Beyond competing for applications in photonic devices, organic conjugated compounds, polymers, and small molecules have also been extended to biomedical applications like phototherapy and biodetection. Recent research on conjugated polymers has focused on bioapplications based on the absorbed light energy conversions in electric impulses, chemical energy, heat, and light emission. In this review, we describe the working principles of those photonic devices that have been applied and researched in the field of biomaterials. Full article

(This article belongs to the Topic Conjugated Polymers: Preparation, Properties and Applications)

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18 pages, 4923 KiB  

Open AccessArticle

Chlorpromazine–Polypyrrole Drug Delivery System Tailored for Neurological Application

by Sara Krawczyk, Sylwia Golba, Cristina Neves and João Tedim

Molecules 2024, 29(7), 1531; https://doi.org/10.3390/molecules29071531 - 29 Mar 2024

Cited by 1 | Viewed by 969

Abstract

Nowadays, drug delivery systems (DDSs) are gaining more and more attention. Conducting polymers (CPs) are efficiently used for DDS construction as such systems can be used in therapy. In this research, a well-known CP, polypyrrole (PPy), was synthesized in the presence of the [...] Read more.

Nowadays, drug delivery systems (DDSs) are gaining more and more attention. Conducting polymers (CPs) are efficiently used for DDS construction as such systems can be used in therapy. In this research, a well-known CP, polypyrrole (PPy), was synthesized in the presence of the polysaccharide heparin (HEP) and chlorpromazine (CPZ) using sodium dodecyl sulfate (SDS) as electrolyte on a steel substrate. The obtained results demonstrate the successful incorporation of CPZ and HEP into the polymer matrix, with the deposited films maintaining stable electrochemical parameters across multiple doping/dedoping cycles. Surface roughness, estimated via AFM analysis, revealed a correlation with layer thickness—decreasing for thinner layers and increasing for thicker ones. Moreover, SEM images revealed a change in the morphology of PPy films when PPy is electropolymerized in the presence of CPZ and HEP, while FTIR confirmed the presence of CPZ and HEP within PPy. Due to its lower molecular mass compared to HEP, CPZ was readily integrated into the thin polymer matrix during deposition, with diffusion being unimpeded, as opposed to films with greater thickness. Finally, the resulting system exhibited the ability to release CPZ, enabling a dosing range of 10 mg to 20 mg per day, effectively covering the therapeutic concentration range. Full article

(This article belongs to the Topic Conjugated Polymers: Preparation, Properties and Applications)

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11 pages, 2895 KiB  

Open AccessArticle

Substitution Effect of a Single Nitrogen Atom on π-Electronic Systems of Linear Polycyclic Aromatic Hydrocarbons (PAHs): Theoretically Visualized Coexistence of Mono- and Polycyclic π-Electron Delocalization

by Jong Min Lim, Sangdeok Shim, Hoa Thi Bui, Jimin Kim, Ho-Joong Kim, Yoon Hwa and Sung Cho

Molecules 2024, 29(4), 784; https://doi.org/10.3390/molecules29040784 - 8 Feb 2024

Cited by 1 | Viewed by 1144

Abstract

We theoretically investigated the nitrogen substitution effect on the molecular structure and π-electron delocalization in linear nitrogen-substituted polycyclic aromatic hydrocarbons (N-PAHs). Based on the optimized molecular structures and magnetic field-induced parameters of fused bi- and tricyclic linear N-PAHs, we found that the local [...] Read more.

We theoretically investigated the nitrogen substitution effect on the molecular structure and π-electron delocalization in linear nitrogen-substituted polycyclic aromatic hydrocarbons (N-PAHs). Based on the optimized molecular structures and magnetic field-induced parameters of fused bi- and tricyclic linear N-PAHs, we found that the local π-electron delocalization of subcycles (e.g., mono- and bicyclic constituent moieties) in linear N-PAHs is preserved, despite deviation from ideal structures of parent monocycles. The introduction of a fused five-membered ring with a pyrrolic N atom (N-5MR) in linear N-PAHs significantly perturbs the π-electronic condition of the neighboring fused six-membered ring (6MR). Monocyclic pyrrole exhibits substantial bond length alternations, strongly influencing the π-electronic systems of both the fused N-5MR and 6MR in linear N-PAHs, depending on the location of shared covalent bonds. A fused six-membered ring with a graphitic N atom in an indolizine moiety cannot generate monocyclic π-electron delocalization but instead contributes to the formation of polycyclic π-electron delocalization. This is evidenced by bifurcated diatropic ring currents induced by an external magnetic field. In conclusion, the satisfaction of Hückel’s 4n + 2 rule for both mono- and polycycles is crucial for understanding the overall π-electron delocalization. It is crucial to consider the unique characteristics of the three types of substituted N atoms and the spatial arrangement of 5MR and 6MR in N-PAHs. Full article

(This article belongs to the Topic Conjugated Polymers: Preparation, Properties and Applications)

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13 pages, 2327 KiB  

Open AccessArticle

Synthesis and Photocatalytic Activity of Novel Polycyclopentadithiophene

by Farah Zayanah Ahmad Zulkifli, Moeka Ito, Takahiro Uno and Masataka Kubo

Polymers 2023, 15(20), 4091; https://doi.org/10.3390/polym15204091 - 15 Oct 2023

Viewed by 1233

Abstract

A novel π-conjugated polymer based on cyclopentadithiophene (CPDT) and poly(4,4′]-(((4Hcyclopenta[2,1-b:3,4-b′]dithiophene-4,4-diyl)bis(ethane-2,1-diyl))bis(oxy))bis(4-oxobutanoic acid)) (PCPDT-CO₂H) was prepared as a sparingly soluble material. The generation of hydroxyl radicals from PCPDT-CO₂H in water was confirmed by using coumarin [...] Read more.

A novel π-conjugated polymer based on cyclopentadithiophene (CPDT) and poly(4,4′]-(((4Hcyclopenta[2,1-b:3,4-b′]dithiophene-4,4-diyl)bis(ethane-2,1-diyl))bis(oxy))bis(4-oxobutanoic acid)) (PCPDT-CO₂H) was prepared as a sparingly soluble material. The generation of hydroxyl radicals from PCPDT-CO₂H in water was confirmed by using coumarin as a hydroxyl radical indicator. Furthermore, PCPDT-CO₂H was found to catalyze the oxidative hydroxylation of arylboronic acid and the oxidation of benzaldehyde, indicating that PCPDT-CO₂H can be a promising candidate for metal-free and 100% organic heterogeneous photocatalysts. Full article

(This article belongs to the Topic Conjugated Polymers: Preparation, Properties and Applications)

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16 pages, 3874 KiB  

Open AccessReview

Different Roles between PEDOT:PSS as Counter Electrode and PEDOT:Carrageenan as Electrolyte in Dye-Sensitized Solar Cell Applications: A Systematic Literature Review

by Euis Siti Nurazizah, Annisa Aprilia, Risdiana Risdiana and Lusi Safriani

Polymers 2023, 15(12), 2725; https://doi.org/10.3390/polym15122725 - 18 Jun 2023

Cited by 4 | Viewed by 2181

Abstract

Poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS) has been mostly used as a counter electrode to give a high performance of dye-sensitized solar cell (DSSC). Recently, PEDOT doped by carrageenan, namely PEDOT:Carrageenan, was introduced as a new material to be applied on DSSC as an electrolyte. PEDOT:Carrageenan [...] Read more.

Poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS) has been mostly used as a counter electrode to give a high performance of dye-sensitized solar cell (DSSC). Recently, PEDOT doped by carrageenan, namely PEDOT:Carrageenan, was introduced as a new material to be applied on DSSC as an electrolyte. PEDOT:Carrageenan has a similar synthesis process as PEDOT:PSS, owing to their similar ester sulphate (-SO₃H) groups in both PSS and carrageenan. This review provides an overview of the different roles between PEDOT:PSS as a counter electrode and PEDOT:Carrageenan as an electrolyte for DSSC applications. The synthesis process and characteristics of PEDOT:PSS and PEDOT:Carrageenan were also described in this review. In conclusion, we found that the primary role of PEDOT:PSS as a counter electrode is to transfer electrons back to cell and accelerate redox reaction with its superior electrical conductivity and high electrocatalytic activity. PEDOT:Carrageenan as an electrolyte has not shown the main role for regenerating the dye sensitized at the oxidized state, probably due to its low ionic conductivity. Therefore, PEDOT:Carrageenan still obtained a low performance of DSSC. Additionally, the future perspective and challenges of using PEDOT:Carrageenan as both electrolyte and counter electrode are described in detail. Full article

(This article belongs to the Topic Conjugated Polymers: Preparation, Properties and Applications)

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15 pages, 5542 KiB  

Open AccessArticle

The Pivotal Role of Benzimidazole in Improving the Thermal and Dielectric Performance of Upilex-Type Polyimide

by Meng Lian, Fei Zhao, Jun Liu, Faqin Tong, Lingbin Meng, Yongqi Yang and Feng Zheng

Polymers 2023, 15(10), 2343; https://doi.org/10.3390/polym15102343 - 17 May 2023

Cited by 2 | Viewed by 1697

Abstract

Polyimide (PI) with ultra-high thermal resistance and stability is essential for application as a flexible substrate in electronic devices. Here, the Upilex-type polyimides, which contained flexibly “twisted” 4,4′-oxydianiline (ODA), have achieved various performance improvements via copolymerization with a diamine containing benzimidazole structure. With [...] Read more.

Polyimide (PI) with ultra-high thermal resistance and stability is essential for application as a flexible substrate in electronic devices. Here, the Upilex-type polyimides, which contained flexibly “twisted” 4,4′-oxydianiline (ODA), have achieved various performance improvements via copolymerization with a diamine containing benzimidazole structure. With the rigid benzimidazole-based diamine bearing conjugated heterocyclic moieties and hydrogen bond donors fused into the PI backbone, the benzimidazole-containing PI showed outstanding thermal, mechanical, and dielectric performance. Specifically, the PI containing 50% bis-benzimidazole diamine achieved a 5% decomposition temperature at 554 °C, an excellent high glass transition temperature of 448 °C, and a coefficient of thermal expansion lowered to 16.1 ppm/K. Meanwhile, the tensile strength and modulus of the PI films containing 50% mono-benzimidazole diamine increased to 148.6 MPa and 4.1 GPa, respectively. Due to the synergistic effect of rigid benzimidazole and hinged, flexible ODA, all PI films exhibited an elongation at break above 4.3%. The electrical insulation of the PI films was also improved with a dielectric constant lowered to 1.29. In summary, with appropriate mixing of rigid and flexible moieties in the PI backbone, all the PI films showed superior thermal stability, excellent flexibility, and acceptable electrical insulation. Full article

(This article belongs to the Topic Conjugated Polymers: Preparation, Properties and Applications)

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21 pages, 5006 KiB  

Open AccessArticle

Novel Metallo-Supramolecular Polymers with 1-Thioxophosphole Main-Chain Units and Remarkable Photoinduced Changes in Their Resonance Raman Spectra

by Ivana Šloufová, Tereza Urválková, Muriel Hissler and Jiří Vohlídal

Polymers 2022, 14(23), 5207; https://doi.org/10.3390/polym14235207 - 30 Nov 2022

Viewed by 2085

Abstract

New low-bandgap unimers, with the central thiophene-(1-thioxophosphole)-thiophene (TPT) ring sequence and 2,2′:6′,2″-terpyridin-4′-yl (tpy) end groups connected to the central unit via conjugated linkers of different size, are prepared and assembled with Zn(II) and Fe(II) ions to metallo-supramolecular polymers (MSPs) that are [...] Read more.

New low-bandgap unimers, with the central thiophene-(1-thioxophosphole)-thiophene (TPT) ring sequence and 2,2′:6′,2″-terpyridin-4′-yl (tpy) end groups connected to the central unit via conjugated linkers of different size, are prepared and assembled with Zn(II) and Fe(II) ions to metallo-supramolecular polymers (MSPs) that are studied regarding their properties. The most interesting feature of Zn-MSPs is the luminescence extended deep into the NIR region. Fe-MSPs not only show the metal-to-ligand charge transfer (MLCT) manifested by the MLCT band (an expected feature) but also an as-yet-undescribed remarkable phenomenon: specific damping of the bands of the TPT sequence in the resonance Raman spectra taken from solid Fe-MSPs using the excitation to the MLCT band (532 nm). The damping is highly reversible at the low laser power of 0.1 mW but gradually becomes irreversible as the power reaches ca. 5 mW. The revealed phenomenon is not shown by the same Fe-MSPs in solutions, nor by Fe-MSPs containing no phosphole units. A hypothesis is proposed that explains this phenomenon and its dependence on the irradiation intensity as a result of the interplay of three factors: (i) enhancement of the MLCT process by excitation radiation, (ii) the electron-acceptor character of the 1-thioxophosphole ring, and (iii) morphological changes of the lattice and their dependence on the population of new structures in the lattice. Full article

(This article belongs to the Topic Conjugated Polymers: Preparation, Properties and Applications)

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12 pages, 1825 KiB  

Open AccessArticle

Theoretical Study of Vinyl-Sulfonate Monomers and Their Effect as the Dopants of Polyaniline Dimers

by Isis Rodríguez-Sánchez, Alain S. Conejo-Dávila, Anayansi Estrada-Monje, Alejandro Vega-Rios and Erasto Armando Zaragoza-Contreras

Molecules 2022, 27(19), 6353; https://doi.org/10.3390/molecules27196353 - 26 Sep 2022

Cited by 2 | Viewed by 1662

Abstract

Establishing the structure–property relationships of monomers and polymers via theoretical chemistry is vital for designing new polymer structures with a specific application. Developing bifunctional monomers with selective polymerizable sites is one of the strategies employed to obtain complex polymeric systems. In this work, [...] Read more.

Establishing the structure–property relationships of monomers and polymers via theoretical chemistry is vital for designing new polymer structures with a specific application. Developing bifunctional monomers with selective polymerizable sites is one of the strategies employed to obtain complex polymeric systems. In this work, a theoretical study on anilinium 2-acrylamide-2-methyl-1-propanesulfonate (ani-AMPS) and anilinium 4-styrenesulfonate (ani-SS) monomers and their respective doped polyaniline dimer (PAni-d AMPS or PAni-d SS) was performed. The study focused on understanding the susceptibility of the vinyl group to a radical attack and the conformation changes resulting from the coordinated covalent bond between sulfonate and aniliniun. Applying Density Functional Theory with the B3LYP functional and a basis set of 6 − 31 + G(d,p), the structures of the ani-AMPS, ani-SS, PAni-d AMPS, and PAni-d SS were optimized, and the different chemical descriptors were determined. The simulation showed that the reactivity of the vinyl group in the ani-AMPS is slightly higher. The sulfonate group undergoes a conformational change when bonding with PAni-d AMPS or PAni-d SS compared to its respective bifunctional monomer. Additionally, the electronegativity of PAni-d depends on the dopant’s structure. Thus, the bonded spacer between the vinyl and sulfonate groups (dopant) plays a notable role in the final characteristics of ani-AMPS, ani-SS, PAni-d AMPS, and PAni-d SS. Full article

(This article belongs to the Topic Conjugated Polymers: Preparation, Properties and Applications)

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