Dynamic double lattice of 1-adamantaneselenolate self-assembled monolayers on Au{111}.

We report a complex, dynamic double lattice for 1-adamantaneselenolate monolayers on Au{111}. Two lattices coexist, revealing two different binding modes for selenols on gold: molecules at bridge sites have lower conductance than molecules at three-fold hollow sites. The monolayer is dynamic, with molecules switching reversibly between the two site-dependent conductance states. Monolayer dynamics enable adsorbed molecules to reorganize according to the underlying gold electronic structure over long distances, which facilitates emergence of the self-organized rows of dimers. The low-conductance molecules assume a (7 × 7) all-bridge configuration, similar to the analogous 1-adamantanethiolate monolayers on Au{111}. The high-conductance molecules self-organize upon mild annealing into distinctive rows of dimers with long-range order, described by a (6√5 × 6√5)R15° unit cell.

Liquid-phase epitaxy of multicomponent layer-based porous coordination polymer thin films of [M(L)(P)0.5] type: importance of deposition sequence on the oriented growth.

The progressive liquid-phase layer-by-layer (LbL) growth of anisotropic multicomponent layer-based porous coordination polymers (PCPs) of the general formula [M(L)(P)(0.5)] (M: Cu(2+), Zn(2+); L: dicarboxylate linker; P: dinitrogen pillar ligand) was investigated by using either pyridyl- or carboxyl-terminated self-assembled monolayers (SAMs) on gold substrates as templates. It was found that the deposition of smooth, highly crystalline, and oriented multilayer films of these PCPs depends on the conditions at the early growth cycles. In the case of a two-step process with an equimolar mixture of L and P, growth along the [001] direction is strongly preferred. However, employing a three-step scheme with full separation of all components allows deposition along the [100] direction on carboxyl-terminated SAMs. Interestingly, the growth of additional layers on top of previously grown oriented seeding layers proved to be insensitive to the particular growth scheme and full retention of the initial orientation, either along the [001] or [100] direction, was observed. This homo- and heteroepitaxial LbL growth allows full control over the orientation and the layer sequence, including introduction of functionalized linkers and pillars.

Controlling interpenetration in metal-organic frameworks by liquid-phase epitaxy.

Metal-organic frameworks (MOFs) are highly porous materials generally consisting of two building elements: inorganic coupling units and organic linkers. These frameworks offer an enormous porosity, which can be used to store large amounts of gases and, as demonstrated in more recent applications, makes these compounds suitable for drug release. The huge sizes of the pores inside MOFs, however, also give rise to a fundamental complication, namely the formation of sublattices occupying the same space. This interpenetration greatly reduces the pore size and thus the available space within the MOF structure. We demonstrate here that the formation of the second, interpenetrated framework can be suppressed by using liquid-phase epitaxy on an organic template. This success demonstrates the potential of the step-by-step method to synthesize new classes of MOFs not accessible by conventional solvothermal methods.

Self-assembled monolayers of aromatic omega-aminothiols on gold: surface chemistry and reactivity.

Amino-terminated self-assembled monolayers on gold substrates were studied by X-ray photoelectron spectroscopy (XPS), near-edge X-ray absorption fine structure (NEXAFS) measurements, and atomic force microscopy (AFM). Two different omega-amino-4,4'-terphenyl substituted alkanethiols of the general structure H(2)N-(C(6)H(4))(3)-(CH(2))(n)-SH (ATPn) were used: 2-(4''-amino-1,1':4',1''-terphenyl-4-yl)ethane-1-thiol (n = 2, ATP2) and 3-(4''-amino-1,1':4',1''-terphenyl-4-yl)propane-1-thiol (n = 3, ATP3). Moreover, the addressability of amino groups within the films was investigated by chemical derivatization of ATPn SAMs with 3,5-bis(trifluoromethyl)phenyl isothiocyanate (ITC) forming fluorinated thiourea ATPn-F films. Evaluation of high-resolution C 1s and N 1s XPS data revealed successful derivatization of at least 50% of surface amino species. Furthermore, it could be demonstrated by angle-resolved NEXAFS spectroscopy that chemical derivatization with ITC has no noticeable influence on the preferential upright orientation of the molecules in the SAMs.

A divergent synthesis of oligoarylalkanethiols with Lewis-basic N-donor termini.

Araliphatic thiols are key molecules for the formation of self-assembled monolayers with high long-range order. If these monolayers shall act as bases for the attachment of other molecules, the respective thiols need to carry suitable functional groups, such as the amino or the pyridine group. Due to their Lewis-basicity, these groups are not compatible with the thiol group under most reaction conditions. Here, an entry into this versatile class of compounds is presented, by using fundamental building blocks in which the thiol groups are protected as triisopropylsilyl sulfides making them compatible with many reagents including Grignard reagents and palladium catalysts. With this strategy at hand, six thiols with bi- and terphenyl backbones, one to three methylene groups, and amino or pyridine head groups became accessible in short reaction sequences.

Relative stability of thiol and selenol based SAMs on Au(111) - exchange experiments.

Two fully analogue homologue series of thiol and selenol based aromatic self-assembled monolayers (SAMs) on Au(111) in the form of CH(3)-(C(6)H(4))(2)-(CH(2))(n)-S-Au(111) (BPnS/Au(111), n = 2-6) and CH(3)-(C(6)H(4))(2)-(CH(2))(n)-Se-Au(111) (BPnSe/Au(111), n = 2-6), respectively, have been used to elucidate the relative stability of the S-Au(111) and Se-Au(111) bonding by monitoring their exchange by alkanethiol and alkaneselenol molecules from their respective solutions. The exchange process was monitored using infrared reflection absorption spectroscopy (IRRAS). Two main results obtained by these study are: (1) the selenium-based BPnSe/Au(111) series is significantly more stable than their sulfur analogues; (2) a clear odd-even effect exists for the stability of both BPnS/Au(111) and BPnSe/Au(111) SAMs towards exchange processes with the even-numbered systems being less stable. The results obtained are discussed in view of previously reported microscopic and spectroscopic data of the same SAMs addressing the issue of the relative stability of S-Au(111) and Se-Au(111) bonding, which is an important factor for the rational design of SAMs.

Self-assembled monolayers of perfluoroterphenyl-substituted alkanethiols: specific characteristics and odd-even effects.

Self-assembled monolayers (SAMs) formed by perfluoroterphenyl-substituted alkanethiols (C(6)F(5)-C(6)F(4)-C(6)F(4)-(CH(2))(n)-SH, FTPn) with variable length of the aliphatic linker (n = 2 and 3) were prepared on (111) Au and Ag and characterized by a combination of several complementary spectroscopic and microscopic techniques. A specific feature of these systems is the helical conformation of the FTP moieties, which, along with the high electronegativity of fluorine, distinguishes them from the analogous non-fluorinated systems and makes them attractive for different applications. The SAMs were found to be well-defined, highly ordered, and densely packed, which suggests a perfect correlation between the orientations and, in particular, twists of the FTP helices in the adjacent molecules. Significantly, the SAM exhibited pronounced odd-even effects, i.e. a dependence of the molecular orientation and packing density on the length of the aliphatic linker in the target molecules, with parity of n being the decisive parameter and the direction of the effects on Au opposite to that on Ag. The presence of the odd-even effects in the FTPn system brings new aspects into the discussion about the origin and mechanism of these phenomena. Specifically, the helical conformation of the FTP moieties in the dense phase excludes a variation of the intramolecular torsion and molecular twist as the mechanism behind the odd-even effects.

Structural characterization of self-assembled monolayers of pyridine-terminated thiolates on gold.

Self-assembled monolayers (SAMs) fabricated on Au(111) substrates from a homologous series of pyridine-terminated organothiols have been investigated using ultra high vacuum infrared reflection adsorption spectroscopy (UHV-IRRAS), X-ray photoelectron spectroscopy (XPS), scanning tunnelling microscopy (STM) and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. A total of 4 different pyridine-based organothiols have been investigated, consisting of a pyridine unit, one or two phenyl units, a spacer of between one and three methylene units and, finally, a thiol unit. For all pyridine-terminated thiols the immersion of Au-substrates in the corresponding ethanolic solutions was found to result in the formation of highly ordered and densely packed SAMs. For an even number of the methylene spacers between the SH group and the aromatic moieties, the SAM unit-cell is rather large, (5sq.rt(3) x 3)rect, whereas in case of an odd number of methylene units a smaller unit cell is adopted, (2sq.rt(3) x sq.rt(3))R30 degrees. The tilt angle of the molecules amounts to 15 degrees . In contrast to expectation, the pyridine-terminated organic surfaces exposed by the corresponding SAMs showed a surprisingly strong resistance with regard to protonation.

Mobility of charge carriers in self-assembled monolayers.

We present a new approach to study charge transport within 2D layers of organic semi-conductors (OSCs) using atomic force microscopy (AFM)-based lithography applied to self-assembled monolayers (SAMs), fabricated from appropriate organothiols. The extent of lateral charge transport was investigated by insulating pre-defined patches within OSC-based SAMs with regions of insulating SAM made from large band gap alkanethiolates. The new method is demonstrated using a phenyl-linked anthracenethiolate (PAT), 4-(anthracene-2-ylethynyl)benzyl thiolate. I-V characteristics of differently shaped PAT-islands were measured using the AFM tip as a top electrode. We were able to determine a relationship between island size and electrical conductivity, and from this dependence, we could obtain information on the lateral charge transport and charge carrier mobility within the thin OSC layers. Our study demonstrates that AFM nanografting of appropriately functionalized OSC molecules provides a suitable method to determine intrinsic mobilities of charge carriers in OSC thin films. In particular, this method is rather insensitive with regard to influence of grain boundaries and other defects, which hamper the application of conventional methods for the determination of mobilities in macroscopic samples.

Triptycene-terminated thiolate and selenolate monolayers on Au(111).

To study the implications of highly space-demanding organic moieties on the properties of self-assembled monolayers (SAMs), triptycyl thiolates and selenolates with and without methylene spacers on Au(111) surfaces were comprehensively studied using ultra-high vacuum infrared reflection absorption spectroscopy, X-ray photoelectron spectroscopy, near-edge X-ray absorption fine structure spectroscopy and thermal desorption spectroscopy. Due to packing effects, the molecules in all monolayers are substantially tilted. In the presence of a methylene spacer the tilt is slightly less pronounced. The selenolate monolayers exhibit smaller defect densities and therefore are more densely packed than their thiolate analogues. The Se-Au binding energy in the investigated SAMs was found to be higher than the S-Au binding energy.