Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Antiaromaticity gain increases the potential for n-type charge transport in hydrogen-bonded ?-conjugated cores.

ABSTRACT: Density functional theory computations suggest that formally non-aromatic organic dyes, like diketopyrrolopyrrole, naphthodipyrrolidone, indigo, and isoindigo, show increased [4n] ?-antiaromatic character and decreased LUMO orbital energies upon hydrogen bonding, making them suitable molecular candidates for applications in n-type organic field effect transistors.

SUBMITTER: Wen Z

PROVIDER: S-EPMC7046090 | biostudies-literature | 2020 Feb

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Antiaromaticity gain increases the potential for n-type charge transport in hydrogen-bonded π-conjugated cores.

Wen Zhili Z Wu Judy I-Chia JI

Chemical communications (Cambridge, England) 20200201 13

Density functional theory computations suggest that formally non-aromatic organic dyes, like diketopyrrolopyrrole, naphthodipyrrolidone, indigo, and isoindigo, show increased [4n] π-antiaromatic character and decreased LUMO orbital energies upon hydrogen bonding, making them suitable molecular candidates for applications in n-type organic field effect transistors. ...[more]

PMID: 31961352

Similar Datasets

Controlling Charge Transport in Molecular Wires through Transannular <i>π-π</i> Interaction.

Project description:This paper describes the influence of the transannular π-π interaction in controlling the carrier transport in molecular wires by employing the STM break junction technique. Five pentaphenylene-based molecular wires that contained [2.2]paracyclophane-1,9-dienes (PCD) as the building block were prepared as model compounds. Functional substituents with different electronic properties, ranging from strong acceptors to strong donors, were attached to the top parallel aromatic ring and used as a gate. It was found that the carrier transport features of these molecular wires, such as single-molecule conductance and a charge-tunneling barrier, can be systematically controlled through the transannular π-π interaction.

| S-EPMC9654154 | biostudies-literature

Stable room temperature ferroelectricity in hydrogen-bonded supramolecular assemblies of ambipolar π-systems.

Project description:This article reports H-bonding driven supramolecular polymerization of naphthalimide (A)-thiophene (D)-naphthalimide (A) (AD n A, n = 1-4) conjugated ambipolar π-systems and its remarkable impact on room temperature ferroelectricity. Electrochemical studies confirm the ambipolar nature of these AD n A molecules with the HOMO-LUMO gap varying between 2.05 and 2.29 eV. Electron density mapping from ESP calculations reveals intra-molecular charge separation as typically observed in ambipolar systems. In the aggregated state, AD1A and AD2A exhibit bathochromically shifted absorption bands while AD3A and AD4A show typical H-aggregation with a hypsochromic shift. Polarization vs. electric field (P-E) measurements reveal stable room temperature ferroelectricity for these supramolecular assemblies, most prominent for the AD2A system, with a Curie temperature (T c) ≈ 361 K and saturation polarization (P s) of ∼2 μC cm-2 at a rather low coercive field of ∼2 kV cm-1. Control molecules, lacking either the ambipolar chromophore or the amide functionality, do not show any ferroelectricity, vindicating the present molecular and supramolecular design. Computational studies enable structural optimization of the stacked oligomer(s) of AD2A molecules and reveal a significant increase in the macro-dipole moment (in the range of 10-12 Debye) going from the monomer to the oligomer(s), which provides the rationale for the origin of ferroelectricity in these supramolecular polymers.

| S-EPMC8768847 | biostudies-literature

Green synthesis of stable hybrid biocatalyst using a hydrogen-bonded, π-π-stacking supramolecular assembly for electrochemical immunosensor.

Project description:Rational integration of native enzymes and nanoscaffold is an efficient means to access robust biocatalyst, yet remains on-going challenges due to the trade-off between fragile enzymes and harsh assembling conditions. Here, we report a supramolecular strategy enabling the in situ fusion of fragile enzymes into a robust porous crystal. A c2-symmetric pyrene tecton with four formic acid arms is utilized as the building block to engineer this hybrid biocatalyst. The decorated formic acid arms afford the pyrene tectons high dispersibility in minute amount of organic solvent, and permit the hydrogen-bonded linkage of discrete pyrene tectons to an extended supramolecular network around an enzyme in almost organic solvent-free aqueous solution. This hybrid biocatalyst is covered by long-range ordered pore channels, which can serve as the gating to sieve the catalytic substrate and thus enhance the biocatalytic selectivity. Given the structural integration, a supramolecular biocatalyst-based electrochemical immunosensor is developed, enabling the pg/mL detection of cancer biomarker.

| S-EPMC10282088 | biostudies-literature

Monolayer nanosheets formed by liquid exfoliation of charge-assisted hydrogen-bonded frameworks.

Project description:Hydrogen-bonded organic frameworks (HOFs) are a diverse and tunable class of materials, but their potential as free-standing two-dimensional nanomaterials has yet to be explored. Here we report the self-assembly of two layered hydrogen-bonded frameworks based on strong, charge-assisted hydrogen-bonding between carboxylate and amidinium groups. Ultrasound-assisted liquid exfoliation of both materials readily produces monolayer hydrogen-bonded organic nanosheets (HONs) with micron-sized lateral dimensions. The HONs show remarkable stability and maintain their extended crystallinity and monolayer structures even after being suspended in water at 80 °C for three days. These systems also exhibit efficient fluorescence quenching of an organic dye in organic solvents, superior to the quenching ability of the bulk frameworks. We anticipate that this approach will provide a route towards a diverse new family of molecular two-dimensional materials.

| S-EPMC8179369 | biostudies-literature

High-mobility, trap-free charge transport in conjugated polymer diodes.

Project description:Charge transport in conjugated polymer semiconductors has traditionally been thought to be limited to a low-mobility regime by pronounced energetic disorder. Much progress has recently been made in advancing carrier mobilities in field-effect transistors through developing low-disorder conjugated polymers. However, in diodes these polymers have to date not shown much improved mobilities, presumably reflecting the fact that in diodes lower carrier concentrations are available to fill up residual tail states in the density of states. Here, we show that the bulk charge transport in low-disorder polymers is limited by water-induced trap states and that their concentration can be dramatically reduced through incorporating small molecular additives into the polymer film. Upon incorporation of the additives we achieve space-charge limited current characteristics that resemble molecular single crystals such as rubrene with high, trap-free SCLC mobilities up to 0.2 cm2/Vs and a width of the residual tail state distribution comparable to kBT.

| S-EPMC6509340 | biostudies-literature

Charge-Assisted Anion-π Interaction and Hydrogen Bonding Involving Alkylpyridinium Cations.

Project description:Competition and cooperation of charge-assisted anion-π interactions and hydrogen bonding were explored in the solid state and in solutions of 1-ethyl-4-carbomethoxypyridinium iodide, the compound utilized by Kosower to calculate solvent polarity Z-indices. X-ray structural analysis of this salt revealed multiple short contacts of iodide anions with hydrogen atoms and aromatic rings of pyridinium cations. Geometric characteristics, quantum theory of atoms in molecules (QTAIM), and noncovalent interaction (NCI) analysis of these contacts indicated comparable interaction energies of the anion-π and hydrogen bonding between iodide and pyridinium cation. 1H NMR (indicating the presence of the hydrogen-bonded complexes) and UV-vis measurements (which were consistent with the formation of anion-π associations) pointed out that both these supramolecular interactions also coexist in solutions. The comparable interaction energies (ΔE) of these modes were confirmed by the DFT computations. Also, while the variations of ΔE with the dielectric constant of the solvents for the complexes of iodide with the neutral π-acceptors were related to the increase of the effective radii of hydrogen- or anion-π bonded iodides, the changes in ΔE for the complexes with pyridinium followed interaction energies between two unit charges. However, the distinction of the bonding in hydrogen-bonded and anion-π complexes of iodide with pyridinium led to a switch of their relative energies with an increase of the polarity of the medium.

| S-EPMC11500369 | biostudies-literature

Simultaneously Achieving Fast Intramolecular Charge Transfer and Mass Transport in Holey D-π-A Organic Conjugated Polymers for Highly Efficient Photocatalytic Pollutant Degradation.

Project description:Simultaneously realizing efficient intramolecular charge transfer and mass transport in metal-free polymer photocatalysts is critical but challenging for environmental remediation. Herein, we develop a simple strategy to construct holey polymeric carbon nitride (PCN)-based donor-π-acceptor organic conjugated polymers via copolymerizing urea with 5-bromo-2-thiophenecarboxaldehyde (PCN-5B2T D-π-A OCPs). The resultant PCN-5B2T D-π-A OCPs extended the π-conjugate structure and introduced abundant micro-, meso-, and macro-pores, which greatly promoted intramolecular charge transfer, light absorption, and mass transport and thus significantly enhanced the photocatalytic performance in pollutant degradation. The apparent rate constant of the optimized PCN-5B2T D-π-A OCP for 2-mercaptobenzothiazole (2-MBT) removal is ∼10 times higher than that of the pure PCN. Density functional theory calculations reveal that the photogenerated electrons in PCN-5B2T D-π-A OCPs are much easier to transfer from the donor tertiary amine group to the benzene π-bridge and then to the acceptor imine group, while 2-MBT is more easily adsorbed on π-bridge and reacts with the photogenerated holes. A Fukui function calculation on the intermediates of 2-MBT predicted the real-time changing of actual reaction sites during the entire degradation process. Additionally, computational fluid dynamics further verified the rapid mass transport in holey PCN-5B2T D-π-A OCPs. These results demonstrate a novel concept toward highly efficient photocatalysis for environmental remediation by improving both intramolecular charge transfer and mass transport.

| S-EPMC10206595 | biostudies-literature

Delayed Blue Fluorescence via Upper-Triplet State Crossing from C-C Bonded Donor-Acceptor Charge Transfer Molecules with Azatriangulene Cores.

Project description:We report the synthesis and structural and photophysical characterization of two series of molecules with functionalized azatriangulene electron donor cores and three pendant electron acceptor units. The presented donor and acceptor units are joined by C-C bonds, instead of the usual C-heteroatom bonds often found in thermally activated delayed fluorescence (TADF) emitters. The effects of the donor-acceptor strength and donor-acceptor dihedral angle on the emission properties are assessed. The data establish that the singlet-triplet energy gap is >0.3 eV and that delayed emission is present in only specific host matrices, irrespective of host polarity. Specific host behavior is atypical of many TADF materials, and we suggest the delayed emission in this work does not occur by a conventional vibronically coupled TADF mechanism, as the ΔE ST value is too large. Detailed photophysical analysis and supporting density functional theory calculations suggest that some presented azatriangulene molecules emit via an upper-triplet state crossing mechanism. This work highlights that several different mechanisms can be responsible for delayed emission, often with highly similar photophysics. Detailed photophysical analysis is required to establish which delayed emission mechanism is occurring. Our results also highlight a clear future direction toward vibronically coupled C-C bonded TADF materials.

| S-EPMC7011764 | biostudies-literature

Ultrafast polarization control by terahertz fields via π-electron wavefunction changes in hydrogen-bonded molecular ferroelectrics.

Project description:Rapid polarization control by an electric field in ferroelectrics is important to realize high-frequency modulation of light, which has potential applications in optical communications. To achieve this, a key strategy is to use an electronic part of ferroelectric polarization. A hydrogen-bonded molecular ferroelectric, croconic acid, is a good candidate, since π-electron polarization within each molecule is theoretically predicted to play a significant role in the ferroelectric-state formation, as well as the proton displacements. Here, we show that a sub-picosecond polarization modulation is possible in croconic acid using a terahertz pulse. The terahertz-pulse-pump second-harmonic-generation-probe and optical-reflectivity-probe spectroscopy reveal that the amplitude of polarization modulation reaches 10% via the electric-field-induced modifications of π-electron wavefunctions. Moreover, the measurement of electric-field-induced changes in the infrared molecular vibrational spectrum elucidates that the contribution of proton displacements to the polarization modulation is negligibly small. These results demonstrate the electronic nature of polarization in hydrogen-bonded molecular ferroelectrics. The ultrafast polarization control via π-electron systems observed in croconic acid is expected to be possible in many other hydrogen-bonded molecular ferroelectrics and utilized for future high-speed optical-modulation devices.

| S-EPMC6177455 | biostudies-literature

Charge Transport in Conjugated and Saturated Hydrocarbons: Comparing Ballistic and Cotunneling Contributions.

Project description:The comparison between electrical transport in CnH2n+2S2 alkane and CnHn+2S2 alkene (n = 4, 6, 8, 10) is studied by using a generalized Breit-Wigner approach and considering coherent transport mechanisms and eventual changes in the state of charge (i.e., cotunneling processes) for both molecules. In general, the conductance of alkanes tends to be smaller than that of similar-sized alkenes. However, cotunneling processes have an important participation in the overall transport in the case of alkanes but not for the alkene family. The progressive changes in both the eigenenergies of the relevant frontier molecular orbitals of the charged species and their spatial localization play decisive roles in the observed differences. While the molecular orbitals of the charged species of the conjugated molecules are hardly affected by the applied voltage, their saturated counterparts are quite sensitive to the external field. With this, successive avoided-crossing events between the molecular orbitals of the single-charged alkane molecules can lead to the appearance of nonballistic conduction channels that make no negligible contributions to the molecular transport.

| S-EPMC10911760 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

Tweets

OmicsDI Databases

PRIDE
PeptideAtlas
MassIVE
JPOST Repository
Physiome Model Repository

EGA
EVA
ENA
LINCS
PAXDB
Cell Collective

MetaboLights
Metabolomics Workbench
MetabolomeExpress
GNPS
BioModels
FAIRDOMHub

ArrayExpress
dbGaP
ExpressionAtlas
GEO
NODE

Information

Databases
Help
API
Contact us
Code on GitHub
Terms of use
Submit Data