Naturally Degradable Photonic Devices with Transient Function by Heterostructured Waxy-Sublimating and Water-Soluble Materials.

Combined dry-wet transient materials and devices are introduced, which are based on water-dissolvable dye-doped polymers layered onto nonpolar cyclic hydrocarbon sublimating substrates. Light-emitting heterostructures showing amplified spontaneous emission are obtained on transient elements and used as illumination sources for speckle-free, full-field imaging, and transient optical labels are realized that incorporate QR-codes with stably encoded information. The transient behavior is also studied at the microscopic scale, highlighting the real-time evolution of material domains in the sublimating compound. Finally, the exhausted components are fully soluble in water thus being naturally degradable. This technology opens new and versatile routes for environmental sensing, storage conditions monitoring, and organic photonics.

Spin-crossover complex on Au(111): structural and electronic differences between mono- and multilayers.

Submono-, mono- and multilayers of the Fe(II) spin-crossover (SCO) complex [Fe(bpz)2 (phen)] (bpz=dihydrobis(pyrazolyl)borate, phen=1,10-phenanthroline) have beenprepared by vacuum deposition on Au(111) substrates and investigated with near edge X-ray absorption fine structure (NEXAFS) spectroscopy and scanning tunneling microscopy (STM). As evidenced by NEXAFS, molecules of the second layer exhibit a thermal spin crossover transition, although with a more gradual characteristics than in the bulk. For mono- and submonolayers of [Fe(bpz)2 (phen)] deposited on Au(111) substrates at room temperature both NEXAFS and STM indicate a dissociation of [Fe(bpz)2 (phen)] on Au(111) into four-coordinate complexes, [Fe(bpz)2 ], and phen molecules. Keeping the gold substrate at elevated temperatures ordered monolayers of intact molecules of [Fe(bpz)2 (phen)] are formed which can be spin-switched by electron-induced excited spin-state trapping (ELIESST).

Toward Quantum-dot Cellular Automata units: thiolated-carbazole linked bisferrocenes.

Quantum-dot Cellular Automata (QCA) exploit quantum confinement, tunneling and electrostatic interaction for transistorless digital computing. Implementation at the molecular scale requires carefully tailored units which must obey several structural and functional constraints, ranging from the capability to confine charge efficiently on different 'quantum-dot centers'-in order to sharply encode the Boolean states-up to the possibility of having their state blanked out upon application of an external signal. In addition, the molecular units must preserve their geometry in the solid state, to interact electrostatically in a controlled way. Here, we present a novel class of organometallic molecules, 6-3,6-bis(1-ethylferrocen)-9H-carbazol-9-yl-6-hexan-1-thiols, which are engineered to satisfy all such crucial requirements at once, as confirmed by electrochemistry and scanning tunneling microscopy measurements, and first principles density functional calculations.

Electronic decoupling of a cyclophane from a metal surface.

Electronic self-decoupling of an organic chromophore from a metal substrate is achieved using a naphtalenediimide cyclophane to spatially separate one chromophore unit of the cyclophane from the substrate. Observations of vibronic excitations in scanning tunneling spectra demonstrate the success of this approach. These excitations contribute a significant part of the tunneling current and give rise to clear structure in scanning tunneling microscope images. We suggest that this approach may be extended to implement molecular functions at metal surfaces.

Single azopyridine-substituted porphyrin molecules for configurational and electronic switching.

A new azopyridine functionalized Ni-porphyrin was synthesized as a model compound for deposition and switch on surfaces. Two geometrically and electronically different states of single molecules on Au(111) were found by scanning tunneling microscopy/spectroscopy and analyzed with density functional calculations.

Rectification in supramolecular zinc porphyrin/fulleropyrrolidine dyads self-organized on gold(111).

Self-assembled donor/acceptor dyads are of current interest as they are biomimetic to the natural photosynthetic conversion system. Herein, we present an ultrahigh-vacuum scanning tunneling microscopy and scanning tunneling spectroscopy (UHV-STM/STS) study of ex situ self-assembled supramolecular dyads consisting of fulleropyrrolidines (PyC(2)C(60)) axially ligated to zinc(II) tetraphenylporphyrin (ZnTPP), self organized on a 4-aminothiophenol (4-ATP) self-assembled monolayer on gold(111). These dyads show both bias-polarity-dependent apparent height in STM images and highly rectifying behavior in tunneling spectroscopy. First-principles density functional theory calculations clarify the conformational and electronic properties of the 4-ATP/ZnTPP/PyC(2)C(60) system. Interestingly, we find easier tunneling for electrons moving from the acceptor side of the dyads to the donor side, in the inverse-rectifying sense with respect to previously reported molecular rectifiers. Such behavior cannot be explained as an elastic resonant tunneling process, but it can by using a model based on the Aviram-Ratner mechanism.

Zinc porphyrin-driven assembly of gold nanofingers.

Nanofingers of gold covered by porphyrins are prepared by a combination of atomic manipulation and surface self-organization. A submonolayer of zinc(II) 5,10,15,20-tetrakis(4-tert-butylphenyl)-porphyrin (ZnTBPP) axially ligated to a self-assembled monolayer of 4-aminothiophenol (4-ATP) on Au(111) is prepared and studied using a combination of ultrahigh vacuum techniques. Under the electric field produced by the STM tip, the relatively weakly bound Au surface atoms along the discommensuration lines become mobile due to the strong bond to 4-ATP, while the tendency of the porphyrins towards self-assembly result in a collective motion of gold clusters. The clusters diffuse onto the surface following well-defined pathways along the [112] direction and then reach the step edges where they assembled, thus forming nanofingers. First-principles density functional theory calculations demonstrate the reduction of the binding energies between the surface gold clusters and the substrate induced by adsorption of thiols. Scanning tunneling microscopy images show assemblies across three adjacent discommensuration lines of the Au(111)-(22 x square root 3) reconstruction, which collectively diffuse along these lines to form islands nucleated at step edges.

X-ray excited visible luminescence spectroscopy of organic materials using a portable optical spectrometer.

The use of a portable video telescope, mounted externally to a beamline endstation, to obtain synchrotron-radiation-excited visible luminescence, is described. Real-time video monitoring permits simple and quick alignment, and allows a visual record of the luminescence experiment. The telescope is fibre-optic-coupled to an optical spectrometer. Examples are given of X-ray excited optical spectroscopy from organic materials for light-emitting-diode applications.

Self-assembled monolayers of cobalt(II)- (4-tert-butylphenyl)-porphyrins: the influence of the electronic dipole on scanning tunneling microscopy images.

Self-assembled monolayers (SAMs) of cobalt(II) 5,10,15,20-tetrakis(4-tert-butylphenyl)-porphyrin, a promising material for optical, photoelectrochemical, and chemical sensor applications, were prepared on Au(111) via axial ligation to 4-aminothiophenol, and studied by several surface science techniques. Scanning tunneling microscopy (STM) and spectroscopy (STS) measurements showed the apparent topology of the Au(111) herringbone structure reconstruction, but with bias-dependent contrast images and asymmetric I/V characteristics. Photoelectron spectroscopy confirmed the presence of metalloporphyrins on the surface, whereas near-edge X-ray absorption (NEXAFS) measurements revealed that the porphyrin ring was tilted by about 70 degrees with respect to the surface plane. The above effects are ascribed to the presence of oriented molecular dipole layers between the metal and the organic material as confirmed by a comparison with first-principles density-functional theory calculations. The measured bias-dependent STM profiles have been reproduced by a simple monodimensional tunneling model.