Three site molecular orbital controlled single-molecule rectifiers based on perpendicularly linked porphyrin–imide dyads

Nanoscale ◽  
2019 ◽  
Vol 11 (47) ◽  
pp. 22724-22729 ◽  
Author(s):  
Murni Handayani ◽  
Hirofumi Tanaka ◽  
Shinichi Katayose ◽  
Tatsuhiko Ohto ◽  
Zhijin Chen ◽  
...  
Keyword(s):  
Molecular Orbital ◽  
Single Molecule ◽  
Central Metal ◽  
Rectification Ratio ◽  
Metal Porphyrin

Single-molecule rectifiers with perpendicularly connected metal porphyrin–imide dyads showed high rectification ratio, which could be tuned by the central metal inside the porphyrin. The features can be explained with a three sight model.

scholarly journals Single-molecule functionality in electronic components based on orbital resonances

2020 ◽  
Vol 22 (23) ◽  
pp. 12849-12866
Author(s):  
Mickael L. Perrin ◽  
Rienk Eelkema ◽  
Jos Thijssen ◽  
Ferdinand C. Grozema ◽  
Herre S. J. van der Zant
Keyword(s):  
Molecular Orbital ◽  
Single Molecule ◽  
Resonant Tunneling ◽  
Resonant Tunneling Diode ◽  
Electronic Components ◽  
Tunneling Diode ◽  
Orbital Resonances

A gateable single-molecule diode and resonant tunneling diode are realized using molecular orbital engineering in multi-site molecules.

scholarly journals Design of an efficient coherent multi-site single-molecule rectifier

2017 ◽  
Vol 19 (43) ◽  
pp. 29187-29194 ◽  
Author(s):  
Mickael L. Perrin ◽  
Matthijs Doelman ◽  
Rienk Eelkema ◽  
Herre S. J. van der Zant
Keyword(s):  
Single Molecule ◽  
Rectification Ratio

We propose the design of a multi-site single-molecule diode with a rectification ratio exceeding a million.

MOLECULAR-SCALE ORGANIC ELECTROLUMINESCENCE FROM TUNNEL JUNCTIONS

2006 ◽  
Vol 13 (02n03) ◽  
pp. 143-147 ◽  
Author(s):  
Z. C. DONG ◽  
X. L. GUO ◽  
Y. WAKAYAMA ◽  
J. G. HOU
Keyword(s):  
Molecular Orbital ◽  
Single Molecule ◽  
Scanning Tunneling ◽  
Hot Electron ◽  
Organic Electroluminescence ◽  
Hot Electron Injection ◽  
New Information ◽  
Molecular Scale ◽  
Molecular Fluorescence ◽  
Lowest Unoccupied Molecular Orbital

We report the generation and detection of bipolar organic electroluminescence of porphyrin molecules from a nanoscale junction in an ultrahigh vacuum scanning tunneling microscope (STM). Clear molecular fluorescence from porphyrin molecules near metal substrates has been realized through highly localized electrical excitation of molecules in proximity to a sharp tip apex. The molecular origin of the luminescence, arising from the highest occupied molecular orbital–lowest unoccupied molecular orbital (HOMO–LUMO) radiative transitions of neutral molecules, is clearly established by the observed well-defined vibrationally resolved fluorescence spectra that match perfectly with conventional photoluminescence data from molecular thin films. The molecules fluoresce at low onset voltages for both bias polarities, presenting an example of bipolar organic electroluminescence at the nanoscale. Such bipolar operation suggests a double-barrier model for electron transport, with hot electron injection into unoccupied states of molecules in both polarities. The optical behavior of molecules in the tunnel junction is also found sensitive to the electronic properties of molecules and energy level alignment at the interface. These results offer new information to the optoelectronic behavior of molecules in a nanoscopic environment and may open up new routes to the development of single-molecule science and molecular scale electronics.

scholarly journals Theoretical Study on Electronic Structural Properties of Catalytically Reactive Metalloporphyrin Intermediates

Catalysts ◽  
2020 ◽  
Vol 10 (2) ◽  
pp. 224 ◽  
Author(s):  
Meijuan Cao ◽  
Aijing Gao ◽  
Yuanyuan Liu ◽  
Yang Zhou ◽  
Zhicheng Sun ◽  
...  
Keyword(s):  
Structural Properties ◽  
Density Functional ◽  
Structural Changes ◽  
Ground States ◽  
Density Functional Theory Method ◽  
Decisive Role ◽  
Chemical Oxidation ◽  
Relative Energy ◽  
Central Metal ◽  
Metal Porphyrin

Metalloporphyrins have attracted great attention in the potential application of biomimetic catalysis. Especially, they were widely investigated as green catalysts in the chemical oxidation of various hydrocarbons through the catalytic activation of molecular oxygen. The structural properties of active central metal ions were reported to play a decisive role in catalytic activity. However, those delicate structural changes are difficult to be experimentally captured or elucidated in detail. Herein, we explored the electronic structural properties of metalloporphyrins (metal porphyrin (PMII, PMIIICl)) and their corresponding catalytically active intermediates (metal(III)-peroxo(PMIII-O2), metal(III)-hydroperoxo(PMIII-OH), and metal(IV)-oxo(PMIV=O), (M=Fe, Mn, and Co)) through the density functional theory method. The ground states of these intermediates were determined based on the assessment of relative energy and the corresponding geometric structures of ground states also further confirmed the stability of energy. Furthermore, our analyses of Mulliken charges and frontier molecular orbitals revealed the potential catalytic behavior of reactive metalloporphyrin intermediates.

Single molecule level studies of reversible ligand binding to metal porphyrins at the solution/solid interface

2020 ◽  
Vol 24 (08) ◽  
pp. 993-1002 ◽  
Author(s):  
Ursula Mazur ◽  
K. W. Hipps
Keyword(s):  
Ligand Binding ◽  
Single Molecule ◽  
Quantitative Information ◽  
Scanning Tunneling ◽  
Tunneling Microscopy ◽  
Metal Porphyrin ◽  
Single Molecule Level ◽  
Solid Interface ◽  
Metal Porphyrins ◽  
Exogenous Ligands

Ligands bind reversibly to metal porphyrins in processes such as molecular recognition, electron transport and catalysis. These chemically relevant processes are ubiquitous in biology and are important in technological applications. In this article, we focus on the current advances in ligand binding to metal porphyrin receptors noncovalently bound at the solution/solid interface. In particular, we restrict ourselves to studies at the single molecule level. Dynamics of the binding/dissociation process can be monitored by scanning tunneling microscopy (STM) and can yield both qualitative and quantitative information about ligand binding affinity and the energetics that define a particular ligation reaction. Molecular and time dependent imaging can establish whether the process under study is at equilibrium. Ligand-concentration-dependent studies have been used to determine adsorption isotherms and thermodynamic data for processes occurring at the solution/solid interface. In several binding reactions, the solid support acted as an electron-donating fifth coordination site, thereby significantly changing the metal porphyrin receptor’s affinity for exogenous ligands. Supporting calculations provide insight into the metalloporphyrin/support and ligand–metalloporphyrin/support interactions and their energetics.

scholarly journals Current–voltage characteristics of single-molecule diarylethene junctions measured with adjustable gold electrodes in solution

2012 ◽  
Vol 3 ◽  
pp. 798-808 ◽  
Author(s):  
Bernd M Briechle ◽  
Youngsang Kim ◽  
Philipp Ehrenreich ◽  
Artur Erbe ◽  
Dmytro Sysoiev ◽  
...  
Keyword(s):  
Transport Properties ◽  
Molecular Orbital ◽  
Single Molecule ◽  
Cyano Group ◽  
Electrical Contact ◽  
Gold Electrodes ◽  
Liquid Environment ◽  
Current Voltage ◽  
End Groups ◽  
Current Voltage Characteristics

We report on an experimental analysis of the charge transport through sulfur-free photochromic molecular junctions. The conductance of individual molecules contacted with gold electrodes and the current–voltage characteristics of these junctions are measured in a mechanically controlled break-junction system at room temperature and in liquid environment. We compare the transport properties of a series of molecules, labeled TSC, MN, and 4Py, with the same switching core but varying side-arms and end-groups designed for providing the mechanical and electrical contact to the gold electrodes. We perform a detailed analysis of the transport properties of TSC in its open and closed states. We find rather broad distributions of conductance values in both states. The analysis, based on the assumption that the current is carried by a single dominating molecular orbital, reveals distinct differences between both states. We discuss the appearance of diode-like behavior for the particular species 4Py that features end-groups, which preferentially couple to the metal electrode by physisorption. We show that the energetic position of the molecular orbital varies as a function of the transmission. Finally, we show for the species MN that the use of two cyano end-groups on each side considerably enhances the coupling strength compared to the typical behavior of a single cyano group.

scholarly journals Self-Assembly of Covalently Linked Porphyrin Dimers at the Solid–Liquid Interface

Molecules ◽  
2019 ◽  
Vol 24 (16) ◽  
pp. 3018 ◽  
Author(s):  
Thomas Habets ◽  
Dennis Lensen ◽  
Sylvia Speller ◽  
Johannes A.A.W. Elemans
Keyword(s):  
Single Molecule ◽  
Self Assembly ◽  
Liquid Interface ◽  
Scanning Tunneling ◽  
Tunneling Microscopy ◽  
Metal Porphyrin ◽  
Metal Centers ◽  
Solid Liquid Interface ◽  
Solid Liquid ◽  
Porphyrin Dimers

The synthesis and surface self-assembly behavior of two types of metal-porphyrin dimers is described. The first dimer type consists of two porphyrins linked via a rigid conjugated spacer, and the second type has an alkyne linker, which allows rotation of the porphyrin moieties with respect to each other. The conjugated dimers were equipped with two copper or two manganese centers, while the flexible dimers allowed a modular built-up that also made the incorporation of two different metal centers possible. The self-assembly of the new porphyrin dimers at a solid–liquid interface was investigated at the single-molecule scale using scanning tunneling microscopy (STM). All dimers formed monolayers, of which the stability and the internal degree of ordering of the molecules depended on the metal centers in the porphyrins. While in all monolayers the dimers were oriented coplanar with respect to the underlying surface (‘face-on’), the flexible dimer containing a manganese and a copper center could be induced, via the application of a voltage pulse in the STM setup, to self-assemble into monolayers in which the porphyrin dimers adopted a non-common perpendicular (‘edge-on’) geometry with respect to the surface.

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