bluuebunny/crossref_metadata_2025_split huggingface dataset:
Preparation of Highly-Ordered Tetrabenzorporphyrin Films Controlled by Supramolecular Assemblies and Precursor Approach
Authors: Ueno So , Yamauchi Mitsuaki , Yamada Hiroko 
Published: August 2024

The control of the orientation and packing structures of small organic semiconductor molecules is the important issue for the improvement of charge carrier mobilities of organic field effect transistors. Tetrabenzoporphyrin (BP) is one of the promising p-type organic semiconductors but solubility in organic solvents is very low. We have developed a precursor approach, where a spun-cast film of soluble precursor, tetra-bicyclo[2.2.2]octadiene-fused porphyrin (CP), was heated to obtain BP crystalline film by in-situ retro-Diels–Alder reaction. However, the obtained BP film is a polycrystalline film and the field-effect transistors (FETs) hole mobilities were 10-1~10-2 cm2V-1s-1[1]. Recently, we reported the effect of alkyl substituents at 5,15-positions of BP for the control of the molecular arrangement. The best performance of OFET hole mobility of 5,15-disubstituted BP was 4.1 cm2V-1s-1 [2, 3].
A supramolecular strategy has attracted attentions as the effective method for the control of molecular arrangement in films. We applied the combination of supramolecular assembling method and the precursor approach to prepare well-ordered BP films. 5,15-Bis(p-dodecylamidephenyl)-CP was deposited on the substrate by drop-casting, spin-coating or dip-coating method, followed by the heating to 200 ºC for 10 min to give the corresponding 5,15-bis(p-dodecylamidephenyl)-BP films. The film morphologies of the BP were compared with 5,15-bis(p-dodecyloxyphenyl)-BP, which doesn’t include amide moieties for hydrogen-bonding, using UV-vis absorption spectroscopy, atomic force microscopy (AFM), X-ray diffraction (XRD) analysis, and p-polarized multiple-angle incidence resolution spectrometry (p-MAIRS) to clarify the effect of amide groups. OFET performance of the BPs will be also discussed to clarify the effect of intermolecular hydrogen bonding interaction.
References
[1] H. Yamada*, D. Kuzuhara, M. Suzuki, H. Hayashi, N. Aratani, Synthesis and Morphological Control of Organic Semiconducting Materials using the Precursor Approach, Bull. Chem. Soc. Jpn. 2020, 93, 1234-1267.
[2] K. Takahashi, B. Shan, X. Xu, S. Yang, T. Koganezawa, D. Kuzuhara, N. Aratani, M. Suzuki*, Q. Miao*, H. Yamada*, Engineering Thin Films of a Tetrabenzoporphyrin toward Efficient Charge-Carrier Transport: Selective Formation of a Brickwork Motif. ACS Appl. Mater. Interfaces 2017, 9, 8211-8218.
[3] E. Jeong, T. Ito, K. Takahashi, T. Koganezawa, H. Hayashi, N. Aratani, M. Suzuki*, H. Yamada*, Exploration of alkyl-group effects on the molecular packing of 5,15-disubstituted tetrabenzoporphyrins toward efficient charge-carrier transport. ACS Appl. Mater. Interfaces 2022, 14, 32319-32329.
Novel Functional Organic Chromophores
Authors: Hill Jonathan P. 
Published: August 2024

Porphyrins and other tetrapyrroles are highly suitable for sensing operations based on their synthetic flexibility and chromophore structures where an analyte might interact to stimulate some variation in directly observable optical colour or fluorescence emission modulation. Their chromophore structures also allow access to electronic triplet states, which can be harnessed for the generation of singlet oxygen – a highly reactive species useful for photodynamic action against tumours or microorganisms. Here we discuss the sensing activity of several β-substituted porphyrins1 including not only by the introduction of suitable interacting units but also by the adaptation of non-planar porphyrins for the synthesis of porous structures. The latter are applied for film formation and sensing involving nanomechanical sensors. Selectivity and mechanisms of sensing activity are discussed. We will also introduce new efficient singlet oxygen generating materials based on agglomeration of an oxidized porphyrin chromophore as metal-organic frameworks,2 electron deficient porous polymers, or using resorcinarenes.3 The use of these materials for selective oxidation of organic substrates is demonstrated. Overall, the results demonstrate the efficacy of the chromophore approach to functional materials. The self-assembly properties of porphyrins and nitrogen rich acene compounds, the pyrazinacenes, will also be considered based on contrasting cases of on-surface mobility and immobility, and the introduction of particular functionality influencing the resulting supramolecular structures.
References: 1) M. K. Chahal, A. Liyanage, A. Z. Alsaleh, P. A. Karr, J. P. Hill and Francis D’Souza, Chem. Sci. 12, 4925-4930 (2021), 2) J. Hynek, D. T. Payne, M. K. Chahal, F. Sciortino, Y. Matsushita, L. K. Shrestha, K. Ariga, J. Labuta, Y. Yamauchi and J. P. Hill, Mater. Chem. Today 21, 100534 (2021), 3) C. Bloyet, F. Sciortino,Y. Matsushita, P. A. Karr, A. Liyanage, W. Jevasuwan, N. Fukata, S. Maji, J. Hynek, F. D’Souza, L. K. Shrestha, K. Ariga, T. Yamazaki, N. Shirahata, J. P. Hill and D. T. Payne, J. Am. Chem. Soc. 144, 10830-10843 (2022).
Correlative Microscopy Analysis for Battery Materials
Authors: Trenikhina Yulia , Kelly Stephen T , Tordoff Benjamin , Harris William 
Published: August 2024

Lithium batteries (LB) are in high demand for a diverse range of applications, such as automotive industry, consumer electronics, wearable and medical devices, grid storage, etc. Each application demands a specific set of performance advantages, such as high capacity and/or energy density, long cycle life, superior electrochemical stability. Therefore, there is no one-size-fits-all for a LB chemistry and its form factor. Battery performance advantages rely on optimization of the battery components, including active materials, electrolyte, separator, binder system, and current collectors. For meaningful device optimization, electrochemical battery testing needs to be combined with a deep understanding of the material and device microstructure. Physical and chemical characterization on the material- and electrode-level is needed to establish root-cause relationships with battery performance. Properties of the interfaces between layers of the battery components often define the device characteristics. Critical information is usually buried beneath the surface of a material specimen or encapsulated in a closed-form device. Microstructural defect identification in the battery needs to be followed by a targeted defect study. Different battery form factors and chemistries make it hard to streamline root-cause analysis.
Recently, a commercial focused-ion beam scanning electron microscope was developed with an integrated fs-laser mill attached to the load lock of the microscope, opening the door to new and more powerful analysis approaches in energy materials research. Applications include rapid access to deeply buried structures for high resolution imaging and analytics, large area cross-section preparation, and massive material ablation for sample preparation of structures; e.g. FIB-SEM tomography, TEM, APT, or X-ray nanoCT. Additionally, each of these methods may be correlatively guided by prior imaging, with techniques like 3D X-ray microscopy (XRM), to enable targeted analysis and preparation. The non-destructive nature of 3D XRM makes it an ideal tool for microstructural defect identification in LB. Laser mill allows researchers to combine non-destructive X-ray defect identification with electron microscopy methods for targeted defect characterization. This approach can be used for various battery types and form factors.
By combining the laser mill with 3D X-ray microscopy, this platform enables comprehensive analysis of energy materials at the nanoscale. We illustrate these concepts with application examples, and use cases demonstrating the utility of the approach.
Battery Lifetime Prediction and Degradation Analysis with Machine Learning Method
Authors: Choi Jung-goo , Seo Gyuwon , Lee Jaeyoung 
Published: August 2024

Due to environmental pollution and climate crisis caused by fossil fuels, eco-friendly alternative energy sources are gaining attention. Particularly, electric vehicles (EVs) are being recognized as the next-generation means of transportation. The most crucial technologies in electric vehicles are lithium-ion batteries and Battery Management Systems (BMS). However, the extended lifespan of lithium-ion batteries leads to prolonged assessment periods, making it challenging to measure and improve performance over time. Additionally, the operation of batteries under various conditions makes it difficult to measure state of charge (SOC) and state of health (SOH) in real-time, introducing many variables. With recent advancements in predictive technology through machine learning, accurate predictions can be made without complex physical knowledge, leveraging high-quality data.
In this study, machine learning techniques were applied using charge/discharge data from lithium-ion LiNi0.5Mn0.3Co0.2O2 (NMC532)/graphite pouch cell batteries. The values measured during the initial charge/discharge cycles were converted into variables that could assess battery degradation modes. Machine learning algorithms were then applied, followed by model tuning to reduce overfitting and enhance accuracy. This research contributes to real-time battery management system data using machine learning technology to predict the remaining useful life (RUL) of lithium-ion batteries with high accuracy, using only initial cycles. This approach enhances the efficiency of BMS data in real-world scenarios and contributes to the overall time efficiency of battery research.

Acknowledgement

This research was supported by National R&D Program through the National Research Foundation of Korea (NRF) funded by Ministry of Science and ICT(NRF-2021K1A4A8A01079455).
W(h)Ither Fullerenes in Medicine? Challenges and Opportunities in Industrial Translation
Authors: Rasovic Ilija 
Published: August 2024

The fullerenes—C60 and its derivatives in particular—have been lauded for three decades now as having revolutionary potential for next-generation medical applications. These span therapeutics (e.g. enzyme inhibition and photodynamic therapy for treating cancers) and diagnostics (e.g. improved contrast agents for magnetic resonance imaging). But translating this potential beyond academic research studies and into scaled-up production and clinical practice has proved far more elusive than the much-sought-after widespread industrial adoption of graphene.
In this talk I will first outline why the fullerenes do indeed offer such promise in these clinical application areas, before providing an exploration of many of the intersecting factors that have contributed to making the clinical translation of fullerene-based therapeutics and diagnostics such a seemingly insurmountable barrier up to this point. These factors include:

A uniquely multi-dimensional chemical design space when considering fullerene size and both exohedral and endohedral functionalisation possibilities;

The relationship of the above with understanding functionality and safety in vivo;

Regulatory requirements pertaining to the above;

The presence of unregulated fullerene-based products in the beauty and wellness sector;

The fuzzy borderlands between science and pseudoscience that much of the narrative around fullerenes occupies;

Loss of funding momentum;

Lack of industrial bridges between materials manufacturers and technology developers.

After characterising the state of affairs in this way, I will offer some specific suggestions for hope and opportunity as we move into a world where synthesis and testing bottlenecks can be overcome with the help of artificial intelligence and automation, and increased awareness of the diverse properties of different types of nanomaterials changes the regulatory and industrial landscapes. Thus, I hope to provide a case study of how one family of carbon nanomaterials could finally realise its promise of advancing medicine in the Industry 4.0 era.
Simulating the Effects of Ammonia Crossover and Alternative Ligands in Thermally Regenerative Flow Batteries
Authors: Cross Nicholas R. , Rau Matthew J , Gorski Christopher A. , Logan Bruce E. , Hall Derek M. 
Published: August 2024

There is a significant amount of low-temperature heat (< 100 °C) available globally from various sources such as geothermal energy, industrial processes, and thermal power plants. Electrochemical and membrane-based methods for harnessing this heat are becoming of greater interest due to their ability to utilize the low temperature energy sources and because they can be sized modularly to fit the power, energy, and spatial requirements of the application. The all-aqueous thermally regenerative ammonia battery (Cuaq-TRAB) is a leading technology in the waste heat to electrical power production space due to recent results showing operational power densities of 25 mW cm-2 with an estimated thermal energy efficiency of 7%, outperforming most technologies in this space. Previous research on the Cuaq-TRAB has shown that the battery suffers from the crossover of ammonia through the membrane which adversely impacts battery performance.
To investigate these impacts, we developed a simple numerical model that simulates discharge curves using one fitting parameter to account for parasitic crossover instead of modeling species transport through the membrane. The model was able to replicate experimental data from Cuaq-TRABs with different membrane materials and for multiple applied current densities with < 5% error for average power and energy capacity. Results showed that there is a 20% loss in Cuaq-TRAB energy capacity due to ammonia crossover when compared to a discharge with no parasitic crossover losses. The model was then extended to demonstrate the impact of different changes to the electrolyte chemistry on the resultant power and energy capacities for Cuaq-TRABs. Using this model, we estimate that if chloride was the ligand for the positive electrolyte instead of bromide, it would decrease the power and energy capacity of the battery by 30%. However, considering that an economic analysis showed that chloride is 80% cheaper than bromide, it may be beneficial to consider the use of chloride ligands in this technology despite its worse electrochemical performance.
Advancing Structural Supercapacitors with Hydrated Polymer
Authors: Teymoory Parya , Chang Yu-Che , Shen Caiwei 
Published: August 2024

Structural supercapacitors, capable of bearing mechanical loads while storing electrical energy, hold great promise for enhancing mobile system efficiencies. However, developing practical structural supercapacitors often involves a challenging balance between mechanical and electrochemical performance, particularly in their electrolytes. Traditional research has focused on bi-continuous phase electrolytes (BPEs), which typically comprise high liquid content that weakens mechanical strength, and inert solid phases that hinder ion conduction and block electrode surfaces. Our previous work introduces a novel approach with a hydrated polymer electrolyte, demonstrating enhanced multifunctionality. This electrolyte, derived from controlled hydration of PET-LiClO4, forms a trihydrate (LiClO4∙3H2O) structure, where water molecules bond with ions without forming a liquid phase, thereby improving ion mobility while maintaining the base polymer's mechanical properties. This new design also promotes better electrochemical interfaces with electrodes, a significant advancement over traditional BPEs.
In this study, we further enhance the performance and processability of such hydrated polymer electrolytes by incorporating polylactic acid (PLA) as the base polymer and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) as the salt. The electrolyte, prepared through solution casting and subsequent controlled hydration, consistently remains an amorphous solid solution in both dry and hydrated states, as confirmed by DSC, XRD, and FTIR analyses. Our tests on ionic conductivity and mechanical properties reveal that adding water to the polymer electrolyte substantially increases ionic conductivity while retaining mechanical properties. A specific composition demonstrated a remarkable increase in ionic conductivity coupled with superior toughness surpassing the base polymer. Furthermore, we successfully fabricated and tested structural supercapacitor devices made of composites of carbon fibers and these new electrolytes. The prototypes presented enhanced toughness with significant energy storage performance, demonstrating their vast application potential due to their outstanding multifunctionality.
Exploring New Carbon Allotropes and Nanographenes on Surfaces
Authors: Gottfried Michael 
Published: August 2024

The quest for planar sp2-hybridized carbon allotropes other than graphene has stimulated substantial research efforts because of their predicted unique mechanical, electronic, and transport properties. However, the syntheses of these nonbenzenoid networks remain challenging due to the lack of reliable protocols for generating nonhexagonal rings. We have developed various on-surface synthesis strategies by which straight polymer chains are linked to form the nonbenzenoid carbon networks. In this way, we synthesized biphenylene network, a new carbon allotrope with 4-6-8-membered rings, which is metallic already at very small dimensions. Similarly, we generated phagraphene nanoribbons, which are based on 5-6-7-membered rings.
Acenes are another interesting class of carbon materials that have fascinated chemists and physicists due to their potential for use in organic electronic applications. We show the synthesis of tridecacene (13ac) and pentadecacene (15ac), the longest acenes known to date, via multistep single-molecule manipulation of suitable precursor molecules on Au(111). We find antiferromagnetic open-shell ground state electron configurations for both acenes. 15ac shows a low-bias spin-excitation feature, indicating a singlet-triplet gap of around 124 meV. Investigation of 15ac complexes with up to 6 gold atoms suggest considerable multiradical contributions to the electronic ground state of 15ac.
Altering the electronic and magnetic properties of carbon-based nanomaterials can also be achieved by doping with heteroatoms. We present an access to a variety of nitrogen-containing 0D and 1D carbon nanostructures including planar and curved cycloarenes with different cavities as well as N-doped graphene nanoribbons.
On-Surface Synthesis of 2D Polymers at the Liquid-Solid Interface
Authors: De Feyter Steven 
Published: August 2024

Unraveling the structure and dynamics of the formation of covalent and non-covalent organic-based 2D crystalline materials is key to controlling the quality of these materials, such as the defect density and their size. Understanding these characteristics is important for controlling their properties. This contribution highlights our efforts in using scanning probe microscopy, particularly scanning tunneling microscopy (STM), to visualize the structure and dynamics of substrate-supported metal-organic frameworks (sMOFs) and substrate-supported covalent organic frameworks (sCOFs) at the liquid-solid interface.
We will focus on the growth of covalent organic frameworks, primarily based on boroxine chemistry, and reveal both qualitative and quantitative details of the nucleation-elongation processes in real-time and under ambient conditions. Sequential data analysis enables the observation of the amorphous-to-crystalline transition, the time-dependent evolution of nuclei, the existence of 'non-classical' crystallization pathways, and, importantly, the experimental determination of essential crystallization parameters with excellent accuracy, including critical nucleus size, nucleation rate, and growth rate. Other aspects that will be addressed include sCOFs and chirality, as well as the formation of multilayered sCOFs.
Additionally, we demonstrate that in specific cases, the electric field between the STM tip and the substrate can induce, on demand, the polymerization or depolymerization process.
Exploring Order/Disorder Molecular Networks on Metal Surfaces
Authors: Lu Jiayi , Zheng Fengru , Jiang Hao , Zhu Zhiwen , Yan Yuyi , Nieckarz Damian , Szabelski Paweł , Sun Qiang 
Published: August 2024

Materials featuring disordered structures often exhibit unique properties. Metal-organic frameworks (MOFs) are a class of hybrid materials composed of metal nodes and coordinating organic linkers[1]. Recently, there has been growing interests in MOFs with structural disorder, and the investigations of amorphous structures on surfaces[2]. Herein, we demonstrate a bottom-up method to construct molecular networks on metal surfaces with order-disorder transition by preparing two-component samples with different stoichiometric ratios of two organic molecule linkers sharing the same symmetry but differing in size[3]. We investigate the topological and electronic structures of the order/disorder molecular networks by scanning tunneling microscopy (STM) and scanning tunneling spectroscopy (STS) under ultra-high vacuum (UHV). The results may advance our understanding of the formation mechanism and electronic behaviors characteristic of monolayer molecular networks with structural disorders, holding the potential to catalyze advancements in the design and application of new amorphous MOF materials with intriguing properties.
[1] L. Dong, et al., Progress in Surface Science, 91, 101–135 (2016).
[2] J. Fonseca, et al., Journal of Materials Chemistry A, 9.17, 10562-10611 (2021).
[3] J. Lu, et al., ACS Nano, 17, 20, 20194–20202 (2023).
Gem-Dibromovinylenes: Highly Versatile Systems for On-Surface Synthesis
Authors: Martin Nazario 
Published: August 2024

The advent of the so-called On-Surface synthesis represents a new scenario where testing new reaction conditions affording disruptive materials impossible to be obtained by conventional synthetic chemistry. In this regard, we have reported an unprecedented chemical reaction from tetrabromo-p-quinodimethanes (TBQs) which, by heating on gold surface, has allowed to obtain a variety of new 1D π-conjugated polymers,[1] some of them exhibiting a quasimetallic behavior.[2]
In this presentation, new designed organic molecules endowed with gem-dibromovinylene units have been synthesized with the aim of broadening the scope of this highly reactive functional group to other on-surface chemical reactions.[3] Thus, new different polymers or molecular systems will be presented and discussed.[4]

References

[1] A. Sánchez-Grande, et al., "On-surface synthesis of ethynylene bridged anthracene polymers", Angew.
Chem. Int. Ed., 2019, 58, 6559-6563.
[2] Cirera, B., et al., “Tailoring topological order and π-conjugation to engineer quasi-metallic polymers”. Nat. Nanotechnol.
2020, 15, 437–443.
[3] Sánchez-Grande, et al., "Surface-assisted Synthesis of N-substituted π-Conjugated Polymers" Adv. Sci., 2022, - advs.202200407R1
[4] E. Pérez-Elvira, et al., "Generating Antiaromaticity: Thermally-selective Skeletal Rearrangements at Interfaces", Nat. Synth., 2023, NATSYNTH-22121246B.