Formation and Thermal Stability of Ordered Self-Assembled Monolayers by the Adsorption of Amide-Containing Alkanethiols on Au(111).

We examined the surface structure, binding conditions, electrochemical behavior, and thermal stability of self-assembled monolayers (SAMs) on Au(111) formed by N-(2-mercaptoethyl)heptanamide (MEHA) containing an amide group in an inner alkyl chain using scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS), and cyclic voltammetry (CV) to understand the effects of an internal amide group as a function of deposition time. The STM study clearly showed that the structural transitions of MEHA SAMs on Au(111) occurred from the liquid phase to the formation of a closely packed and well-ordered ß-phase via a loosely packed α-phase as an intermediate phase, depending on the deposition time. XPS measurements showed that the relative peak intensities of chemisorbed sulfur against Au 4f for MEHA SAMs formed after deposition for 1 min, 10 min, and 1 h were calculated to be 0.0022, 0.0068, and 0.0070, respectively. Based on the STM and XPS results, it is expected that the formation of a well-ordered ß-phase is due to an increased adsorption of chemisorbed sulfur and the structural rearrangement of molecular backbones to maximize lateral interactions resulting from a longer deposition period of 1 h. CV measurements showed a significant difference in the electrochemical behavior of MEHA and decanethiol (DT) SAMs as a result of the presence of an internal amide group in the MEHA SAMs. Herein, we report the first high-resolution STM image of well-ordered MEHA SAMs on Au(111) with a (3 × 2√3) superlattice (ß-phase). We also found that amide-containing MEHA SAMs were thermally much more stable than DT SAMs due to the formation of internal hydrogen networks in MEHA SAMs. Our molecular-scale STM results provide new insight into the growth process, surface structure, and thermal stability of amide-containing alkanethiols on Au(111).

Thermally Driven Structural Order of Oligo(Ethylene Glycol)-Terminated Alkanethiol Monolayers on Au(111) Prepared by Vapor Deposition.

To probe the effects of deposition temperature on the formation and structural order of self-assembled monolayers (SAMs) on Au(111) prepared by vapor deposition of 2-(2-methoxyethoxy)ethanethiol (CH3O(CH2)2O(CH2)2SH, EG2) for 24 h, we examined the surface structure and electrochemical behavior of the resulting EG2 SAMs using scanning tunneling microscopy (STM) and cyclic voltammetry (CV). STM observations clearly revealed that EG2 SAMs vapor-deposited on Au(111) at 298 K were composed of a disordered phase on the entire Au surface, whereas those formed at 323 K showed improved structural order, showing a mixed phase of ordered and disordered phases. Moreover, at 348 K, uniform and highly ordered EG2 SAMs on Au(111) were formed with a (2 × 3√3) packing structure. CV measurements showed sharp reductive desorption (RD) peaks at -0.818, -0.861, and -0.880 V for EG2 SAM-modified Au electrodes formed at 298, 323, and 348 K, respectively. More negative potential shifts of RD peaks with increasing deposition temperature are attributed to an increase in van der Waals interactions between EG2 molecular backbones resulting from the improved structural quality of EG2 SAMs. Our results obtained herein provide new insights into the formation and thermally driven structural order of oligo(ethylene glycol)-terminated SAMs vapor-deposited on Au(111).

Stimulus-Responsive Tubular Conjugated Polymer 2D Nanosheets.

Creation of new two-dimensional (2D) architectures has attracted significant attention in the field of self-assembly for structural diversity and new functionalization. Although numerous 2D polymer nanosheets have been reported, 2D nanosheets with tubular channels have been unexplored. Herein, we describe a new strategy for the fabrication of stimulus-responsive conjugated polymer 2D nanosheets with hollow cavities. Amphiphilic macrocyclic diacetylenes self-assembled in an aqueous solution in a columnar manner to afford bilayered 2D nanosheets with intrinsically tubular nanochannels. UV-induced polymerization resulted in the generation of blue-colored tubular conjugated polydiacetylene 2D nanosheets. Immobilization of gold nanoparticles, fluorescence labeling with FRET phenomenon and colorimetric DNA sensing were demonstrated with these new 2D nanosheets. In addition, the free NH2 containing polymerized 2D nanosheet was utilized for conductivity behavior and grafting on graphene oxide (GO).

Solvent- and Light-Sensitive AIEE-Active Azo Dye: From Spherical to 1D and 2D Assemblies.

Fluorescent molecular assembly systems provide an exciting platform for creating stimuli-responsive nano- and microstructured materials with optical, electronic, and sensing functions. To understand the relationship between (i) the plausible molecular structures preferentially adopted depending on the solvent polarity (such as N,N-dimethylformamide [DMF], tetrahydrofuran [THF], and toluene), (ii) the resulting spectroscopic features, and (iii) self-assembled nano-, micro-, and macrostructures, we chose a sterically crowded triangular azo dye (3Bu) composed of a polar molecular core and three peripheral biphenyl wings. The chromophore changed the solution color from yellow to pink-red depending on the solvent polarity. In a yellow DMF solution, a considerable amount of the twisted azo form could be kept stable with the help of favorable intermolecular interactions with the solvent molecules. By varying the concentration of the DMF solution, the morphology of self-assembled structures was transformed from nanoparticles to micrometer-sized one-dimensional (1D) structures such as sticks and fibers. In a pink-red toluene solution, the periphery of the central ring became more planar. The resulting significant amount of the keto-hydrazone tautomer grew into micro- and millimeter-sized 1D structures. Interestingly, when THF-H2O (1:1) mixtures were stored at a low temperature, elongated fibers were stacked sideways and eventually developed into anisotropic two-dimensional (2D) sheets. Notably, subsequent exposure of visible-light-irradiated sphere samples to solvent vapor resulted in reversible fluorescence off↔on switching accompanied by morphological restoration. These findings suggest that rational selection of organic dyes, solvents, and light is important for developing reusable fluorescent materials.

Light-directed trapping of metastable intermediates in a self-assembly process.

Self-assembly is a dynamic process that often takes place through a stepwise pathway involving formation of kinetically favored metastable intermediates prior to generation of a thermodynamically preferred supramolecular framework. Although trapping intermediates in these pathways can provide significant information about both their nature and the overall self-assembly process, it is a challenging venture without altering temperature, concentrations, chemical compositions and morphologies. Herein, we report a highly efficient and potentially general method for "trapping" metastable intermediates in self-assembly processes that is based on a photopolymerization strategy. By employing a chiral perylene-diimide possessing a diacetylene containing an alkyl chain, we demonstrated that the metastable intermediates, including nanoribbons, nanocoils and nanohelices, can be effectively trapped by using UV promoted polymerization before they form thermodynamic tubular structures. The strategy developed in this study should be applicable to naturally and synthetically abundant alkyl chain containing self-assembling systems.

Growth Processes and Reductive Desorption Behaviors of 4-Fluorobenzenethiol Self-Assembled Monolayers on Au(111).

Growth processes and electrochemical behaviors of 4-fluorobenzenethiol (4-FBT) self-assembled monolayers (SAMs) on Au(111) prepared by vapor deposition at 323 K were examined using scanning tunneling microscopy (STM) and cyclic voltammetry (CV). STM imaging revealed that 4-FBT SAMs at the initial growth stage (deposition for 1 min) were mainly composed of bright molecular aggregates and liquid-like disordered phase. After longer deposition for 3 min, 4-FBT SAMs had three distinct surface features: a few molecular aggregates, small ordered domains, and disordered phase. These small ordered domains with sizes ranging from 5 to 10 nm had a (4× âˆš3)R30° packing structure. As deposition time increased to 24 h, long-range ordered domains larger than 40 nm were formed on Au(111) surfaces. From this STM study, we demonstrate that phase transitions of 4-FBT SAMs on Au(111) occur from molecular aggregates to large ordered domains via formation of small ordered domains as deposition time increases. CV measurements showed reductive desorption peaks for 4-FBT SAMs in the range of -638~-648 mV regardless of SAM morphology, suggesting that S-Au binding strength of 4-FBT SAMs on Au electrodes is a dominant factor for electrochemical stability.

Displacement Processes of 1-Adamanetanethiol Self-Assembled Monolayers on Au(111) by 1-Hexanethiol.

Displacement processes of pre-adsorbed 1-admanetanethiol (ADT) self-assembled monolayers (SAMs) on Au(111) by 1-hexanethiol (HT) at room temperature were investigated by scanning tunneling microscopy (STM) and cyclic voltammetry (CV). Molecular-scale STM imaging clearly revealed that phase transitions from the (7 × 7) phase for ADT SAMs to the c(4 × 2) phase for HT SAMs via intermediate phase including bright aggregated islands and disordered phase. Moreover, it was found that ADT SAMs were completely displaced by HT molecules with a short hexyl chain within an hour. The CV measurements showed that cathodic peaks for SAM-modified Au(111) electrodes as a function of displacement time were varied with the structural change of displaced SAMs. Our results provide new insight into understanding the displacement processes of ADT SAMs on Au(111) by HT.

Well-Ordered Domains of 4-Fluorobenzenethiol Self-Assembled Monolayers on Au(111) Guided by a Displacement Reaction.

Displacement processes of pre-covered cyclohexanethiol (CHT) self-assembled monolayers (SAMs) by 4-fluorobenzenethiol (4-FBT) on Au(111) were examined as a function of displacement time by scanning tunneling microscopy (STM) and water static contact angle (CA) measurements. STM imaging revealed that the adsorption of 4-FBT on Au(111) in a 1 mM ethanol solution at room temperature for 24 h generated disordered SAMs, whereas well-ordered 4-FBT SAMs with a (4√6 × âˆš3)R5° packing structure were formed over the entire Au(111) surfaces via the displacement of pre-covered CHT SAMs by 4-FBT molecules. The CA measurements also showed that CA values increase with increasing displacement time, reflecting that the displacement reaction took place and the resulting SAMs had greater hydrophobicity compared with CHT SAMs. In this study, we found that the displacement technique using CHT SAMs as a molecular template is very useful in obtaining 4-FBT SAMs with a high degree of structural order and large ordered domains.