Single cycloparaphenylene molecule devices: Achieving large conductance modulation via tuning radial π-conjugation.
Ontology highlight
ABSTRACT:
SUBMITTER: Lv Y
PROVIDER: S-EPMC8694625 | biostudies-literature |
REPOSITORIES: biostudies-literature
Similar Datasets
Project description:Nature has developed supramolecular constructs to deliver outstanding charge-transport capabilities using metalloporphyrin-based supramolecular arrays. Herein we incorporate simple, naturally inspired supramolecular interactions via the axial complexation of metalloporphyrins into the formation of a single-molecule wire in a nanoscale gap. Small structural changes in the axial coordinating linkers result in dramatic changes in the transport properties of the metalloporphyrin-based wire. The increased flexibility of a pyridine-4-yl-methanethiol ligand due to an extra methyl group, as compared to a more rigid 4-pyridinethiol linker, allows the pyridine-4-yl-methanethiol ligand to adopt an unexpected highly conductive stacked structure between the two junction electrodes and the metalloporphyrin ring. DFT calculations reveal a molecular junction structure composed of a shifted stack of the two pyridinic linkers and the metalloporphyrin ring. In contrast, the more rigid 4-mercaptopyridine ligand presents a more classical lifted octahedral coordination of the metalloporphyrin metal center, leading to a longer electron pathway of lower conductance. This works opens to supramolecular electronics, a concept already exploited in natural organisms.
| S-EPMC7590179 | biostudies-literature
Project description:Herein, single-molecule conductance studies of TBT1-TBT6 which entails 1,4-dithienylbenzene as the backbone and SMe groups as the anchoring units, with the scanning tunneling microscope break junction (STM-BJ) technique, are reported. The molecular conductance of TBT1 with intramolecular O•••S noncovalent interactions is enhanced by about one order of magnitude in comparison to their analogue TBT2 (which contains alkyl instead of alkoxy chains). By replacing the methoxy groups in TBT1 with extending alkoxy chains in TBT3, TBT4, and TBT5, the molecular backbones become twisted and as a consequence the single-molecule conductance decreases gradually, showing that the intramolecular O•••S noncovalent interaction is influenced by the structural features of alkoxy chains. More importantly, the single-molecule conductance of TBT3, TBT4, and TBT5 can be boosted by increasing the electric field applied to the molecular junctions. Remarkably, the conductance of TBT3, TBT4, and TBT5 can be reversibly modulated due to the conformational changes between twisted and planar ones by varying the electric field. These results demonstrate that molecules with intramolecular O•••S noncovalent interactions have the potential for in situ control of the electrical properties of molecular-scale devices.
| S-EPMC9189668 | biostudies-literature
Project description:Here we present a molecular architecture that can reversibly change the geometric conformation of its π-system backbone via irradiation with two different wavelengths. The proposed 'molecular actuator' consists of a photoswitchable azobenzene orthogonally connected to a π-conjugated bithiophene by both direct and aliphatic linker-assisted bonding. Upon exposure to 350 nm light, the trans azobenzene moiety isomerizes to its cis form, causing the bithiophene to assume a semiplanar anti conformation (extended π-conjugation). Exposure to 254 nm light promotes the isomerization of the azobenzene unit back to its initial extended trans conformation, thus forcing the bithiophene fragment to twist out of coplanarity (restricted π-conjugation). The molecular conformation of the bithiophene was characterized using steady-state UV-vis and nuclear magnetic resonance spectroscopy, as well as ab initio computations. The proposed molecular design could be envisaged as a π-conjugation modulator, which has potential to be incorporated into extended linear π-systems, i.e. via the terminal α-thiophene positions, and used to tune their optical and electronic properties.
| S-EPMC5365055 | biostudies-literature
Project description:Silicene is an exciting two-dimensional material that shares many of graphene's electronic properties, but differs in its structural buckling. This buckling allows opening a bandgap in silicene through the application of a perpendicular electric field. Here we show that this buckling also enables highly effective modulation of silicene's conductance by means of an in-plane electric field applied through silicene side gates, which can be realized concurrently within the same silicene monolayer. We illustrate this by using silicene to implement Self-Switching Diodes (SSDs), which are two-dimensional field effect nanorectifiers realized within a single silicene monolayer. Our quantum simulation results show that the atomically-thin silicene SSDs, with sub-10?nm dimensions, achieve a current rectification ratio that exceeds 200, without the need for doping, representing a 30?fold enhancement over graphene SSDs. We attribute this enhancement to a bandgap opening due to the in-plane electric field, as a consequence of silicene's buckling. Our results suggest that silicene is a promising material for the realization of planar field effect devices.
| S-EPMC4594042 | biostudies-literature
Project description:π-Conjugated donor (D)-acceptor (A) copolymers have been extensively studied as organic photovoltaic (OPV) donors yet remain largely unexplored in organic thermoelectrics (OTEs) despite their outstanding mechanical bendability, solution processability and flexible molecular design. Importantly, they feature high Seebeck coefficient (S) that are desirable in room-temperature wearable application scenarios under small temperature gradients. In this work, the authors have systematically investigated a series of D-A semiconducting copolymers possessing various electron-deficient A-units (e.g., BDD, TT, DPP) towards efficient OTEs. Upon p-type ferric chloride (FeCl3 ) doping, the relationship between the thermoelectric characteristics and the electron-withdrawing ability of A-unit is largely elucidated. It is revealed that a strong D-A nature tends to induce an energetic disorder along the π-backbone, leading to an enlarged separation of the transport and Fermi levels, and consequently an increase of S. Meanwhile, the highly electron-deficient A-unit would impair electron transfer from D-unit to p-type dopants, thus decreasing the doping efficiency and electrical conductivity (σ). Ultimately, the peak power factor (PF) at room-temperature is obtained as high as 105.5 µW m-1 K-2 with an outstanding S of 247 µV K-1 in a paradigm OPV donor PBDB-T, which holds great potential in wearable electronics driven by a small temperature gradient.
| S-EPMC8811840 | biostudies-literature
Project description:We describe the synthesis and single-molecule electrical transport properties of a molecular wire containing a π-extended tetrathiafulvalene (exTTF) group and its charge-transfer complex with F4TCNQ. We form single-molecule junctions using the in situ break junction technique using a homebuilt scanning tunneling microscope with a range of conductance between 10 G0 down to 10(-7) G0. Within this range we do not observe a clear conductance signature of the neutral parent molecule, suggesting either that its conductance is too low or that it does not form a stable junction. Conversely, we do find a clear conductance signature in the experiments carried out on the charge-transfer complex. Due to the fact we expected this species to have a higher conductance than the neutral molecule, we believe this supports the idea that the conductance of the neutral molecule is very low, below our measurement sensitivity. This idea is further supported by theoretical calculations. To the best of our knowledge, these are the first reported single-molecule conductance measurements on a molecular charge-transfer species.
| S-EPMC4505095 | biostudies-literature
Project description:Small-molecule probes emitting in the second near-infrared window (NIR-II) are attracting great attention because of their deep-tissue imaging ability. However, developing NIR-II fluorogenic (off-on) probes with good water solubility remains a great challenge due to the lack of a facile approach. Herein we first report the combination of changeable π-conjugation and hydrophilic groups as an effective strategy for developing water-soluble NIR-II fluorogenic probes. With the strategy, new water-soluble NIR-II fluorophores are prepared, among which NIR-II-F2 and NIR-II-F3 show superior stability and bright fluorescence in aqueous media, and are thus used to design two water-soluble NIR-II fluorogenic probes for leucine aminopeptidase (LAP). The excellent performance in real aqueous bio-environments is demonstrated by imaging mouse vasculatures and organs with NIR-II-F2, and LAP in drug-induced liver injury mice with one of the enzymatic probes; however, water-insoluble dyes cannot achieve such in vivo imaging under the same conditions. Our strategy may be helpful for further developing water-soluble organic NIR-II fluorogenic probes for in vivo imaging of other analytes.
| S-EPMC10016431 | biostudies-literature
Project description:Conflicting reports in the literature have raised the question whether radial extracorporeal shock wave therapy (rESWT) devices and vibrating massage devices have similar energy signatures and, hence, cause similar bioeffects in treated tissues.We used laser fiber optic probe hydrophone (FOPH) measurements, high-speed imaging and x-ray film analysis to compare fundamental elements of the energy signatures of two rESWT devices (Swiss DolorClast; Electro Medical Systems, Nyon, Switzerland; D-Actor 200; Storz Medical, Tägerwillen, Switzerland) and a vibrating massage device (Vibracare; G5/General Physiotherapy, Inc., Earth City, MO, USA). To assert potential bioeffects of these treatment modalities we investigated the influence of rESWT and vibrating massage devices on locomotion ability of Caenorhabditis elegans (C. elegans) worms.FOPH measurements demonstrated that both rESWT devices generated acoustic waves with comparable pressure and energy flux density. Furthermore, both rESWT devices generated cavitation as evidenced by high-speed imaging and caused mechanical damage on the surface of x-ray film. The vibrating massage device did not show any of these characteristics. Moreover, locomotion ability of C. elegans was statistically significantly impaired after exposure to radial extracorporeal shock waves but was unaffected after exposure of worms to the vibrating massage device.The results of the present study indicate that both energy signature and bioeffects of rESWT devices are fundamentally different from those of vibrating massage devices.Prior ESWT studies have shown that tissues treated with sufficient quantities of acoustic sound waves undergo cavitation build-up, mechanotransduction, and ultimately, a biological alteration that "kick-starts" the healing response. Due to their different treatment indications and contra-indications rESWT devices cannot be equated to vibrating massage devices and should be used with due caution in clinical practice.
| S-EPMC4625004 | biostudies-literature
Project description:We report time-dependent density functional theory calculations of the vertical excitation energies for the singlet states of three-coordinate 5H-dibenzoborole (DBB) derivatives and four-coordinate 5-fluoro-5H-dibenzoborole ion (FDBB) derivatives. These molecules show remarkable hypsochromic (blue) shifts in their fluorescence spectra and bathochromic (red) shifts in their absorption spectra when the bridging boron atoms change their coordination number from three to four. We constructed a series of derivatives of DBB and FDBB and studied how the energies of the electronic excitations change. The states with prominent oscillator strength in all of the DBB and FDBB derivatives show similar shifts of their excitation energies upon coordination. The three-coordinate DBB derivative 5-(2,4,6-triisopropylphenyl)-2,8-dimethoxy-3,7-bis[p-(N,N-diphenylamino)phenyl]-5H-dibenzo[d,b]borole has an intense absorption at 3.25 eV, which shifts in the four-coordinate FDBB derivative 5-fluro-5-(2,4,6-triisopropylphenyl)-2,8-dimethoxy-3,7-bis[p-(N,N-dip henylamino)phenyl]-5H-dibenzo[d,b]borole ion to 3.17 eV. The experimental absorption peaks are 3.43 and 3.31 eV, respectively. In addition, we investigated and analyzed the nature of these electronic excitations using attachment/detachment density plots, with which we characterized the changes in electron density that arose from the excitations.
| S-EPMC2562313 | biostudies-literature
Project description:In contrast with conventional single-molecule junctions, in which the current flows parallel to the long axis or plane of a molecule, we investigate the transport properties of M(II)-5,15-diphenylporphyrin (M-DPP) single-molecule junctions (M=Co, Ni, Cu, or Zn divalent metal ions), in which the current flows perpendicular to the plane of the porphyrin. Novel STM-based conductance measurements combined with quantum transport calculations demonstrate that current-perpendicular-to-the-plane (CPP) junctions have three-orders-of-magnitude higher electrical conductances than their current-in-plane (CIP) counterparts, ranging from 2.10-2 G0 for Ni-DPP up to 8.10-2 G0 for Zn-DPP. The metal ion in the center of the DPP skeletons is strongly coordinated with the nitrogens of the pyridyl coated electrodes, with a binding energy that is sensitive to the choice of metal ion. We find that the binding energies of Zn-DPP and Co-DPP are significantly higher than those of Ni-DPP and Cu-DPP. Therefore when combined with its higher conductance, we identify Zn-DPP as the favoured candidate for high-conductance CPP single-molecule devices.
| S-EPMC5116753 | biostudies-literature