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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 37 records · Page 2
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Exceptional Electron-Rich Heteroaromatic Pentacycle for Ultralow Band Gap Conjugated Polymers and Photothermal Therapy

Stable redox-active conjugated molecules with exceptional electron-donating abilities are key components for the design and synthesis of ultralow band gap conjugated polymers. While hallmark electron-rich examples such as pentacene derivatives have been thoroughly explored, their poor air stability has hampered their broad incorporation into conjugated polymers for practical applications. Herein, we describe the synthesis of the electron-rich, fused pentacyclic pyrazino[2,3-b:5,6-b’]diindolizine (PDIz) motif and detail its optical and redox behavior. The PDIz ring system exhibits a lower oxidation potential and a reduced optical band gap than the isoelectronic pentacene while retaining greater air stability in both solution and the solid state. The enhanced stability and electron density, together with readily installed solubilizing groups and polymerization handles, allow for the use of the PDIz motif in the synthesis of a series of conjugated polymers with band gaps as small as 0.71 eV. Importantly; the tunable absorbance throughout the biologically relevant near-infrared I and II regions enables the use of these PDIz-based polymers as efficient photothermal therapeutic reagents for laser ablation of cancer cells.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Triplet Management at Ligand-Perovskite Interface to Enhanced Photovoltaics Performance

Aromatic organic molecules are widely used as passivators in perovskite solar cells (PSCs). Efforts have been devoted to improving the energy alignments, band edge states, and defect passivation functionalities. However, potential energy loss through triplet states in such conjugated molecules has not been investigated in the past. Here, we report the observation of charge transfer from FAPbI 3 to the triplet state of a pyrene (Pyr)-based cationic ligand. Such a potential loss channel can be suppressed via delicate triplet management in polycyclic aromatic compounds. Interestingly, a subtle structural modification from Pyr to the triphenylene (TP) core gave rise to shallower triplets that prohibit electron transfer from perovskites. This strategy has led to TP-passivated PSCs achieving an enhanced power conversion efficiency (PCE) of 24.69% from 23.10% in Pyr-passivated counterparts. Moreover, the devices retained above 80% initial PCE after 4000 h of light soaking, which likely benefited from the reduced triplet electron trapping at the ligand-perovskite interface.

14 SOLAR ENERGY↗
DOE OSTI2023

Electron Spin Polarization and Rectification Driven by Chiral Perylene Diimide-Based Nanodonuts

The chirality-induced spin selectivity (CISS) effect allows thin-film layers of chiral conjugated molecules to function as spin filters at ambient temperature. Through solvent-modulated dropcasting of chiral l- and d-perylene diimide (PDI) monomeric building blocks, two types of aggregate morphologies, nanofibers and nanodonuts, may be realized. Spin-diode behavior is evidenced in the nanodonut structures. Stacked PDI units, which form the conjugated core of these nanostructures, dominate the nanodonut–Au electrode contact; in contrast, the AFM tip contacts largely the high-resistance solubilizing alkyl chains of the chiral monomers that form these nanodonuts. Current–voltage responses of the nanodonuts, measured by magnetic conductive AFM (mC-AFM), demonstrate substantial spin polarizations as well as spin current rectification ratios (>10) that exceed the magnitudes of those determined to date for other chiral nanoscale systems. Furthermore, these results underscore the potential for chiral nanostructures, featuring asymmetric molecular junctions, to enable CISS-based nanoscale spin current rectifiers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Hydrogen-Bond-Promoted Planar Conformation, Crystallinity, and Charge Transport in Semiconducting Diazaisoindigo Derivatives

Conformational control of π-conjugated molecules using intramolecular noncovalent bonds represents a promising strategy to tailor the solid-state molecular packing and electronic properties of these materials. Here, we report the design and synthesis of two model compounds featuring intramolecular hydrogen bonds formed between a center diazaisoindigo unit (the acceptor) and flanking indole units (the donor). Computational and experimental investigations show that these hydrogen bonds enthalpically stabilize the coplanar molecular conformation by over 10 kcal/mol. The formation of these hydrogen bonds is also slightly favorable in terms of entropy, ensuring high temperature stability of the planar conformation. In this work, thermal annealing of thin films of these compounds imparts high crystallinity and orientation in the solid state, while the non-hydrogen bond control only gave an amorphous solid. Field-effect transistor devices fabricated from these thin films exhibit hole mobilities up to 0.270 cm 2 V -1 s -1 , in contrast to the lack of measurable charge carrier mobility for the non-hydrogen bond control. This work demonstrates an efficient synthetic strategy to incorporate robust intramolecular hydrogen bonds into conjugated π-systems and elucidates the mechanism on how such hydrogen bonds promote the desired molecular conformation, solid-state packing, and electronic performances of conjugated organic materials.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Tailoring the Weight of Surface and Intralayer Edge States to Control LUMO Energies

Abstract The energies of the frontier molecular orbitals determine the optoelectronic properties in organic films, which are crucial for their application, and strongly depend on the morphology and supramolecular structure. The impact of the latter two properties on the electronic energy levels relies primarily on nearest‐neighbor interactions, which are difficult to study due to their nanoscale nature and heterogeneity. Here, an automated method is presented for fabricating thin films with a tailored ratio of surface to bulk sites and a controlled extension of domain edges, both of which are used to control nearest‐neighbor interactions. This method uses a Langmuir–Schaefer‐type rolling transfer of Langmuir layers (rtLL) to minimize flow during the deposition of rigid Langmuir layers composed of π‐conjugated molecules. Using UV–vis absorption spectroscopy, atomic force microscopy, and transmission electron microscopy, it is shown that the rtLL method advances the deposition of multi‐Langmuir layers and enables the production of films with defined morphology. The variation in nearest‐neighbor interactions is thus achieved and the resulting systematically tuned lowest unoccupied molecular orbital (LUMO) energies (determined via square‐wave voltammetry) enable the establishment of a model that functionally relates the LUMO energies to a morphological descriptor, allowing for the prediction of the range of accessible LUMO energies.

36 MATERIALS SCIENCE↗
DOE OSTI2024

“Off‐Label Use” of the Siderophore Enterobactin Enables Targeted Imaging of Cancer with Radioactive Ti (IV)

Abstract The development of inert, biocompatible chelation methods is required to harness the emerging positron emitting radionuclide 45 Ti for radiopharmaceutical applications. Herein, we evaluate the Ti (IV) ‐coordination chemistry of four catechol‐based, hexacoordinate chelators using synthetic, structural, computational, and radiochemical approaches. The siderophore enterobactin (Ent) and its synthetic mimic TREN‐CAM readily form mononuclear Ti (IV) species in aqueous solution at neutral pH. Radiolabeling studies reveal that Ent and TREN‐CAM form mononuclear complexes with the short‐lived, positron‐emitting radionuclide 45 Ti (IV) , and do not transchelate to plasma proteins in vitro and exhibit rapid renal clearance in naïve mice. These features guide efforts to target the 45 Ti isotope to prostate cancer tissue through the design, synthesis, and evaluation of Ent‐DUPA, a small molecule conjugate composed of a prostate specific membrane antigen (PSMA) targeting peptide and a monofunctionalized Ent scaffold. The [ 45 Ti][Ti(Ent‐DUPA)] 2− complex forms readily at room temperature. In a tumor xenograft model in mice, selective tumor tissue accumulation (8±5 %, n =5), and low off‐target uptake in other organs is observed. Overall, this work demonstrates targeted imaging with 45 Ti (IV) , provides a foundation for advancing the application of 45 Ti in nuclear medicine, and reveals that Ent can be repurposed as a 45 Ti‐complexing cargo for targeted nuclear imaging applications.

Koller, Angus J.↗
DOE OSTI2024

“Off‐Label Use” of the Siderophore Enterobactin Enables Targeted Imaging of Cancer with Radioactive Ti (IV)

The development of inert, biocompatible chelation methods is required to harness the emerging positron emitting radionuclide 45 Ti for radiopharmaceutical applications. Herein, we evaluate the Ti (IV) -coordination chemistry of four catechol-based, hexacoordinate chelators using synthetic, structural, computational, and radiochemical approaches. The siderophore enterobactin (Ent) and its synthetic mimic TREN-CAM readily form mononuclear Ti (IV) species in aqueous solution at neutral pH. Radiolabeling studies reveal that Ent and TREN-CAM form mononuclear complexes with the short-lived, positron-emitting radionuclide 45 Ti (IV) , and do not transchelate to plasma proteins in vitro and exhibit rapid renal clearance in naïve mice. These features guide efforts to target the 45 Ti isotope to prostate cancer tissue through the design, synthesis, and evaluation of Ent-DUPA, a small molecule conjugate composed of a prostate specific membrane antigen (PSMA) targeting peptide and a monofunctionalized Ent scaffold. Additionally, the [ 45 Ti][Ti(Ent-DUPA)] 2− complex forms readily at room temperature. In a tumor xenograft model in mice, selective tumor tissue accumulation (8±5 %, n=5), and low off-target uptake in other organs is observed. Overall, this work demonstrates targeted imaging with 45 Ti (IV) , provides a foundation for advancing the application of 45 Ti in nuclear medicine, and reveals that Ent can be repurposed as a 45 Ti-complexing cargo for targeted nuclear imaging applications.

62 RADIOLOGY AND NUCLEAR MEDICINE↗
DOE OSTI2025

Truncating 2D Framework Materials Down to a Single Pore: Synthetic Approaches and Opportunities

Here, in this Accounts article, we summarize our recent work on truncating conjugated two-dimensional framework materials down to a single pore, or a single macrocycle. Conjugated 2D architectures have emerged as one of the most synthetically adaptable motifs for coupling semiconductivity and porosity in metal–organic frameworks (MOFs) and covalent organic frameworks (COFs). However, despite their prevalence, 2D architectures have several limitations. In particular, the strong interlayer π–π stacking can limit both processability and the accessibility of internal active sites. We have found that simple macrocycles preserve key aspects of 2D framework structure and function, including porosity and out-of-plane electrical conductivity, while providing improved processability, surface tunability, and mass transport properties. In this article, we first describe our synthetic approach and general design considerations. Specifically, we show how ditopic analogues of the tritopic ligands commonly found in the synthesis of 2D MOFs and COFs can be used to achieve a diverse library of conjugated macrocycles that resemble fragments of semiconducting frameworks in both form and function. The length of the peripheral side chains, the size of the aromatic core, and the solubility of intermediates are all key variables in favoring selective macrocycle formation over undesired linear polymers and oligomers. Next, we highlight the unique advantages that macrocycles provide, including improved processability, atomically precise surface tunability, and greater active site accessibility. In particular, the identity of the peripheral side chains dramatically impacts both solubility and colloidal stability as well as crystal size and morphology. We further show how the solution processability and nanoscale dimensions of macrocycles can simplify electronic device fabrication and improve electrochemical performance. Finally, we end with a forward-looking discussion on how macrocycles offer a unique bridge between conjugated molecules and extended frameworks, enabling new application areas and fundamental science.

charge transport↗
DOE OSTI2021

Role of Polycyclic Aromatic Alkylammonium Cations in Tuning the Electronic Properties and Band Alignment of Two-Dimensional Hybrid Perovskite Semiconductors

Two-dimensional hybrid organic–inorganic perovskites (HOIPs) have recently drawn intense attention as potential photovoltaic materials. However, n = 1 two-dimensional (2D) HOIPs face the challenge of low conductivity between the inorganic layers, leading to unsatisfactory device performance. Interestingly, 2D HOIPs employing π-conjugated molecules as organic moieties show energy and charge transfers between organic and inorganic layers, indicating potentially efficient carrier transport for photovoltaic applications. Nevertheless, the development of 2D HOIP-based solar cells especially utilizing polycyclic aromatic alkylammonium as cations is in its infancy. Herein, we investigated the electronic structure and band alignment of a series of n = 1 2D Ruddlesden–Popper (RP) phase HOIPs containing different polycyclic aromatic groups and alkyl chains, based on density functional theory calculations. We find that the polycyclic aromatic group plays an important role in controlling the functionality of 2D HOIPs by directly modifying band-edge states, and the band alignment at the organic–inorganic interface can be designed to promote either exciton trapping or dissociation for light-emitting or photovoltaic applications, respectively.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Efficient Intermolecular Charge Transport in π-Stacked Pyridinium Dimers Using Cucurbit[8]uril Supramolecular Complexes

Intermolecular charge transport through π-conjugated molecules plays an essential role in biochemical redox processes and energy storage applications. In this work, we observe highly efficient intermolecular charge transport upon dimerization of pyridinium molecules in the cavity of a synthetic host (cucurbit[8]uril, CB[8]). Stable, homoternary complexes are formed between pyridinium molecules and CB[8] with high binding affinity, resulting in an offset stacked geometry of two pyridiniums inside the host cavity. The charge transport properties of free and dimerized pyridiniums are characterized using a scanning tunneling microscope-break junction (STM-BJ) technique. Our results show that π-stacked pyridinium dimers exhibit comparable molecular conductance to isolated, single pyridinium molecules, despite a longer transport pathway and a switch from intra- to intermolecular charge transport. Control experiments using a CB[8] homologue (cucurbit[7]uril, CB[7]) show that the synthetic host primarily serves to facilitate dimer formation and plays a minimal role on molecular conductance. Molecular modeling using density functional theory (DFT) reveals that pyridinium molecules are planarized upon dimerization inside the host cavity, which facilitates charge transport. In addition, the π-stacked pyridinium dimers possess large intermolecular LUMO–LUMO couplings, leading to enhanced intermolecular charge transport. Altogether, this work demonstrates that supramolecular assembly can be used to control intermolecular charge transport in π-stacked molecules.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

π covalency in the halogen bond

Halogen bonds are a highly directional class of intermolecular interactions widely employed in chemistry and chemical biology. This linear interaction is commonly viewed to be analogous to the hydrogen bond because hydrogen bonding models also intuitively describe the σ-symmetric component of halogen bonding. The possibility of π-covalency in a halogen bond is not contemplated in any known models. Here we present evidence of π-covalency being operative in halogen bonds formed between chloride and halogenated triphenylamine-based radical cations. We reach this conclusion through computational analysis of chlorine K-edge X-ray absorption spectra recorded on these halogen bonded pairs. In light of this result, we contend that halogen bonding is better described by analogy to metal coordination bonds rather than hydrogen bonds. Our revised description of the halogen bond suggests that these interactions could be employed to influence the electronic properties of conjugated molecules in unique ways.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Nanoribbons or weakly connected acenes? The influence of pyrene insertion on linearly extended ring systems

Derived from the lateral fusion of benzene rings, acenes are a class of π-conjugated molecules containing a single aromatic sextet, where system size is inversely correlated with chemical stability. In the pursuit of creating graphene nanoribbons/nanowires, several extended-ring structures have been synthesized through linear combinations of azaacenes and pyrene. Importantly, these extended systems demonstrate enhanced chemical stability and allow for the construction of macromolecular-sized structures. In this report we present a combined quantum-chemical and experimental study to reveal the cost of these improved characteristics in fully carbon-based systems. The results clearly show that pyrene moieties inserted among acene units do not result in long acene-like structures, rather the pyrene-inserted acene is, electronically, a series of (nearly) isolated acenes. The origin of pyrene's electronic blocking effect and implications on oxidized and photoexcited states of these extended-ring systems are detailed. The results of this investigation definitively show that coupling pyrene in an orthogonal orientation (through the 4, 5/9, 10 positions or e/l faces) to acenes should be eschewed if nanographene-/nanowire-like structures are desired.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Advanced Electron Microscopy of Nanophased Synthetic Polymers and Soft Complexes for Energy and Medicine Applications

After decades of developments, electron microscopy has become a powerful and irreplaceable tool in understanding the ionic, electrical, mechanical, chemical, and other functional performances of next-generation polymers and soft complexes. The recent progress in electron microscopy of nanostructured polymers and soft assemblies is important for applications in many different fields, including, but not limited to, mesoporous and nanoporous materials, absorbents, membranes, solid electrolytes, battery electrodes, ion- and electron-transporting materials, organic semiconductors, soft robotics, optoelectronic devices, biomass, soft magnetic materials, and pharmaceutical drug design. For synthetic polymers and soft complexes, there are four main characteristics that differentiate them from their inorganic or biomacromolecular counterparts in electron microscopy studies: (1) lower contrast, (2) abundance of light elements, (3) polydispersity or nanomorphological variations, and (4) large changes induced by electron beams. Since 2011, the Center for Nanophase Materials Sciences (CNMS) at Oak Ridge National Laboratory has been working with numerous facility users on nanostructured polymer composites, block copolymers, polymer brushes, conjugated molecules, organic–inorganic hybrid nanomaterials, organic–inorganic interfaces, organic crystals, and other soft complexes. This review crystalizes some of the essential challenges, successes, failures, and techniques during the process in the past ten years. It also presents some outlooks and future expectations on the basis of these works at the intersection of electron microscopy, soft matter, and artificial intelligence. Machine learning is expected to automate and facilitate image processing and information extraction of polymer and soft hybrid nanostructures in aspects such as dose-controlled imaging and structure analysis.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Optimizing the self-assembly of conjugated polymers and small molecules through structurally programmed non-covalent control

Organic conjugated polymers and oligomers are key electronic materials for applications such as transistors, photovoltaics, and light emitting devices due to their potential for solution processability, mechanical flexibility, and precise structure-based tuning compared to inorganic materials. In dilute environments, the optoelectronic properties of conjugated polymers are largely governed by their constitutional structure and, to a lesser degree, their solution-state intramolecular configuration. In the solid state, intramolecular conformation and intermolecular electronic coupling impact these properties substantially, especially in relation to device performance. Therefore, an increasingly important area of research concerning conjugated materials is developing design strategies aimed at optimizing the solid-state packing for electronic applications. Programming solid-state packing arrangements through discrete non-covalent interactions is an emerging strategy within the context of conjugated polymers. This review focuses on the use of the two most prevalent discrete and directional interactions used to dictate the self-assembly of conjugated polymers and oligomers—hydrogen bonds and chalcogen bonds. Further, we also discuss how these design motifs can imbue conjugated materials with appealing physical properties while simultaneously retaining or improving electronic capabilities.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Water-Surface Drag Coating: A New Route Toward High-Quality Conjugated Small-Molecule Thin Films with Enhanced Charge Transport Properties

Electronic properties of organic semiconductor (OSC) thin films are largely determined by their morphologies and crystallinities. However, solution-processed conjugated small-molecule OSC thin films usually exhibit abundant grain boundaries and impure grain orientations because of complex fluid dynamics during solution coating. Here, a novel methodology, water-surface drag coating, is demonstrated to fabricate high-quality OSC thin films with greatly enhanced charge transport properties. This method utilizes the water surface to alter the evaporation dynamics of solution to enlarge the grain size, and a unique drag-coating process to achieve the unidirectional growth of organic crystals. Furthermore, using 2,8-difluoro-5,11-bis(triethylsilylethynyl)anthradithiophene (Dif-TES-ADT) as an example, thin films with millimeter-sized single-crystal domains and pure crystallographic orientations are achieved, revealing a significant enhancement (4.7 times) of carrier mobility. More importantly, the resulting film can be directly transferred onto any desired flexible substrates, and flexible transistors based on the Dif-TES-ADT thin films show a mobility as high as 16.1 cm 2 V -1 s -1 , which represents the highest mobility value for the flexible transistors reported thus far. The method is general for the growth of various high-quality OSC thin films, thus opening up opportunities for high-performance organic flexible electronics.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Bulky Cation-Modified Interfaces for Thermally Stable Lead Halide Perovskite Solar Cells

Charged conjugated organic molecules offer promising prospects for reducing nonradiative recombination at interfaces in perovskite solar cells, while protecting the active layer from moisture. However, several studies have shown that the heat induced diffusion of these cations leads to irreversible solar cell degradation. Passivation molecules for perovskite can reconstruct the film surface into lower-dimensional phases when exposed to thermal stress, impeding charge extraction and affecting the photoconversion efficiency (PCE) of devices. In this work, we study how molecular interactions between passivation molecules and 3D CsFAPbI 3 perovskite impact stability and charge extraction at the perovskite/hole transport layer interfaces. Two model π- conjugated molecules are studied: 2-([2,2′-bithiophen]-5-yl)ethan-1-aminium iodide (2TI) and 2-(3‴,4′-dimethyl-[2,2′:5′,2″:5″,2‴- quaterthiophen]-5-yl)ethan-1-ammonium iodide (4TmI). We demonstrate that the speed of surface layer reconstruction under thermal stress can be controlled by the cation size and correlate these structural changes with the solar cell performance and stability. Devices treated with 2TI and 4TmI achieve PCEs over 21% and maintain their performance under thermal stress. Our findings demonstrate that thermal stability in PSCs can be achieved via the design engineering of passivation agents, offering a blueprint for developing next-generation passivation molecules.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Conjugation effect of amine molecules in non-aqueous Mg redox flow batteries

Nonaqueous magnesium redox flow batteries (Mg RFBs) are attractive for low-cost, high-energy-density and long-cycle-life stationary energy storage applications. However, state-of-the-art cathode redox-active molecules suffer from low solubility and low redox potential. Herein, we screened a range of cathode redox-active molecules and identified amine molecules as optimal to couple with the Mg anode. The properties of amine derivatives and their performances were collected to establish the correlation between molecular structures and electrochemical performances. The redox potential and solubility of these amine molecules were influenced by the π-conjugated and non-conjugated structures of amine derivatives. Density functional theory (DFT) simulations and the inverse aromatic fluctuation index (FLU −1 ) verified that conjugation had an important role in stabilizing the molecule and increasing its redox potential. Notably, tris[4-(diethylamino)phenyl]amine (TDPA) achieved the highest theoretical energy density (∼120 Wh L −1 ) due to its high solubility (∼0.9 M) and voltage (∼2.5 V vs. Mg/Mg 2+ ). We also demonstrated that ether solvents were crucial for stable, high-solubility catholytes, while bulk anions did not affect the redox potential of these p-type molecules. In a Mg-amine RFB configuration, the battery delivered 2.50 V, a specific discharge capacity of 106.5 mAh g −1 , an initial coulombic efficiency of 90.74%, and a capacity retention of 93.88% after 150 cycles.

Qin, Yunan [University of Utah, Salt Lake City, UT↗
DOE OSTI2025

Pressure-Induced Stacking of Rhodamine 6G Molecules

Extended conjugation of molecular π systems are of great significance for solar cells and organic light-emitting diodes as these can serve as new light absorbing and emitting chromophores. This research demonstrates the potential of using pressure and solvent environment to create larger assemblies of molecular π-conjugated systems. Here, we selected rhodamine 6G (Rh6G) to study the pressure-induced stacking of molecules in three different solvents: methanol (MeOH), isopropanol (IPA), and 16:3:1 mixture of methanol: ethanol: water (MEW). Absorption, emission, and fluorescence lifetime were studied at pressures up to 11.38 GPa. We found that pressure-induced stacking mechanisms can present solvent dependence: high pressures tend to create emissive Haggregates in MeOH and MEW, but excimers in IPA. This work guides and demonstrates routes to stacking of organic molecules using high pressures and provides fundamental insights into the formation of extended conjugation π systems.

Johnson, Kade [Univ. of Texas at San Antonio, TX (↗