ADSORPTION-INDUCED CHIRAL SAMs CHAPTER SURFACE-ADSORPTION INDUCED CHIRAL SELF-ASSEMBLED MONOLAYERS OF HEXAALKYL HEXAPHENYLBENZENE (HHB) ON HIGHLY ORIENTED PYROLYTIC GRAPHITE (HOPG) 6.1 Motivation Since the separation of the sodium ammonium salt of racemic tartaric acid in enantiomorphous crystals by Pasteur 150 years ago [1], the concept of chirality has become an important research subject in chemistry. Chiral structures can be formed not only from pure chiral molecules but also by the asymmetric assembly of the molecules. In the two-dimensional realm, potential applications such as enatio-selective heterogeneous catalysts [2, 3], nanometer scale patterning, development of molecular electronic devices, and chemical sensors have drawn much interest in the study of chiral structures on surfaces [2-25]. Depositing chiral molecules on the surface is a typical way of generating a chiral surface [3-5], such as (R,R)-tartaric acid have been successfully used as surface modifiers in enantioselective heterogeneous catalysis [3, 4]. At the supramolecular level, chiral structures may be formed by asymmetric assembly. For example, racemic mixtures of certain chiral molecules spontaneously separate on the surface to form chiral domains [6-9]. Hydrogen bonded chains [4, 11] have been reported to show chiral structures on the surface. Studies of surface-adsorption induced chirality revealed that the interaction between the substrate and adsorbate plays a key role in inducing structural 92 ADSORPTION-INDUCED CHIRAL SAMs changes and the symmetry breaking which results in chirality [9, 12, 17, 21-25]. The development of the scanning probe techniques especially scanning tunneling microscopy (STM) and atomic force microscopy (AFM) made it possible to locally probe monolayers at atomic resolution. Spontaneous breaking of chiral symmetry by achiral molecules in a Langmuir-Blodgett (LB) film was determined by Viswanathan et al. with AFM [9]. Separation of achiral molecules into lattices with chiral packing [9] and separation of chiral phases of chiral organic molecules in LB films have been observed by AFM [26]. Chiral liquid crystals have also been investigated with STM and found to form domains that exhibit two-dimensional chirality [27]. Supramolecular clusters of 1-nitronaphthalene on gold have been observed to aggregate in 2D domains that are mirror images of each other [28]. In this chapter we present an STM study at the liquid-solid interface of hexaalkyl hexaphenylbenzenes (HHB) physisorbed onto a graphite surface. Chemical Structure of HHB This is an example of the formation of an asymmetric structure on the surface, which involves the supramolecular assembly through van der Waals’ forces. The molecule 93 ADSORPTION-INDUCED CHIRAL SAMs used in this experiment is hexaalkyl hexaphenylbenzene (HHB) - a precursor of the polycyclic aromatic hydrocarbons (PAHs) with peripheral substituents. PAHs can self-assemble into columnar mesophases [29] which are well suited materials for the study of one-dimensional transport processes such as electrical conductivity [30] and photoconductivity [31] along the columnar axis. Research toward electronics on the scale of individual molecules can be performed by investigating highly ordered monomolecular adsorbate layers of HHBs. Using the STM, single molecules in these two-dimensional patterns can be visualized with submolecular resolution. At the same time, information on their electronic properties can be obtained. 6.2 STM Results 6.2.1 STM Images of HHB Fig 6.1 STM image of a monolayer of HHB on HOPG surfaces (100nm100nm, Vbias=100mV, Iset=150pA) 94 ADSORPTION-INDUCED CHIRAL SAMs Fig 6.1 displays the STM current image of a monolayer of HHB physisorbed at the interface between organic solution and the basal plane of HOPG. It shows the monolayer is right beside the step on the HOPG (bright part at the right-top corner). The conductivity of the graphite is better than the organic monolayers therefore the step becomes the brightest part in the STM current image. Each bright dot within the SAMs corresponds to one physisorbed HHB molecule. The angle AOB=89±1, which is almost a right angle. Section analysis of OA and OB (Fig 6.2) shows that the neighbouring molecules are apart by distance of 3.910.08nm along direction OA and 2.970.06nm along direction OB respectively. In another words, the unit cell of the HHB monolayers is a rectangle with two sides at 3.910.08nm and 2.970.06nm respectively. 95 ADSORPTION-INDUCED CHIRAL SAMs Fig 6.2 Section analysis of HHB monolayer. A: Section analysis of OA in Fig 6.2. The distance containing 21 neighbouring molecules is 78.1nm. B: Section analysis of OB in Fig 6.2. The distance containing 21 neighbouring molecules is 59.4nm. 6.2.2 Chiral SAMs High resolution STM images of the HHB monolayers reveal the arrangement of molecules within the monolayers. In Fig 6.3 the aromatic part of the HHB molecule – the benzene rings appeared as brightest part in the STM image. The aliphatic dodecyl groups appeared as dark part and could barely be observed. Although the atomic resolution was not achieved, the shape of the bright part was able to help us to determine the configuration of the HHB molecules on HOPG surfaces. The bright part exhibited three ‘legs’, two pointing upwards and one pointing downwards. These 96 ADSORPTION-INDUCED CHIRAL SAMs three ‘legs’ were assigned to the three carbazole groups. The molecular models of HHB with benzene rings highlighted fit into the STM image very well. N N N Fig 6.3 Left: High resolution image of HHB monolayers: Bright hexagons represent the benzene ring of HHB. Right: the molecular configuration of HHB (L-HHB) in monolayers. (Vbias = 100mV, and Iset = 150pA) The STM results showed that within that scanned area HHB molecule had only one configuration: two carbazole groups on top and one carbazole group at the left bottom, which we called it left-HHB (L-HHB). Its mirror image configuration with two carbazole groups on top and one carbazole group at the right bottom (R-HHB) was not observed within this scanned area. Therefore the monolayers were formed by L-HHB and could be considered as chiral monolayers. Another STM images captured in other region was shown in Fig 6.4. The resolution of this image is lower comparing to Fig 6.3, especially for molecules at the boundary, because they had higher mobility than the molecules at the center of the monolayers. In each molecule, top half was brighter than rest part of molecule so it stood for two carbazole groups. The 97 ADSORPTION-INDUCED CHIRAL SAMs brightness of bottom half is uneven, with right part being more intensive. This suggested the molecule HHB’s configuration was mirror image of L-HHB, that is, R-HHB. The monolayer formed by R-HHB was also a chiral monolayer. Measurements of R-HHB monolayers and L-HHB showed that both unit cells were rectangles with two sides at 3.900.80nm and 2.950.60nm. N N N Fig 6.4 Left: High resolution image of HHB monolayers: Bright hexagons represent the benzene ring of HHB. Right: the molecular configuration of HHB (R-HHB) in monolayers. (Vbias = 100mV, and Iset = 150pA) 6.3.3 Symmetry Transformation of SAMs We regularly observed these two sets of domains with a reproducible small angle relationship between the sets of 14.01.0 (Fig 6.5). 98 ADSORPTION-INDUCED CHIRAL SAMs Fig 6.5 Top: STM image of two types of SAMs arrangement and their boundary. Bottom: The surface plot of the STM image (current profile). The height of each pinnacle is proportional to the magnitude of current. (Vbias = 100mV, and Iset = 150pA) In the high-resolution image in Figure 6.5 the phenyl groups of molecule HBB appear as regions of highest intensity, consistent with the occupied frontier orbitals being localized on these sites. The contrast in STM images of organic molecules has often been successfully compared to the frontier orbitals, either the HOMO or LUMO, according to the polarity of the applied potential. In the STM images of HBB, the aliphatic groups are harder to identify than the aromatic groups. The differences between the left part and the right part of Figure 6.6 cannot be a consequence of 99 ADSORPTION-INDUCED CHIRAL SAMs instrumental technique since they are from the same image. After using spectrum 2D function to remove the noise, the differences between the left part and the right part are apparent as shown in Fig 6.6: (i) the alignment of the individual molecules within the rows and (ii) different ‘internal’ structure of the molecules. Further studies of the SAMs showed that the unit cell on the right hand side is rectangular with two sides at a=4.000.08nm and b=2.950.06nm. On the contrary, the unit cell on the left hand side is rhombic with two sides at c=4.100.08nm, d=3.020.06nm respectively and angle =761. It was observed that at the center bottom of the Fig 6.5 (highlighted by black circle) the object did not match well with the neighbouring HHB molecules. A surface plot of that region revealed that the tunneling current within the black circle was higher than over the remaining part of the monolayers. It is however difficult to determine the nature of the object directly from the STM image. Fig 6.6 STM image of two types of SAMs arrangement and their boundary. Data was treated with Spectrum 2D function. (Vbias = 100mV, and Iset = 150pA) 100 ADSORPTION-INDUCED CHIRAL SAMs 6.3 Discussion 6.3.1 STM Images of HHB A large area scan of the HHB monolayers showed the monolayers started at the steps of the HOPG surfaces (Fig 6.1). The molecules near the step are not as bright as the molecules at the center of SAMs, but this is an artifact due to the hysteresis effect of the STM when the tip moves across the steps. These bright dot arrays show that the HHB molecules are localized firmly on the HOPG surfaces. On the contrary, in Fig 6.7 the molecules at the boundary are not as clear as the molecules at the center of the SAMs because of their higher mobility. That suggests the steps assist the stabilization of the molecules on the surface, which makes them the favorite physisorption sites on the HOPG surfaces. Fig 6.7 STM images of SAMs formed by HHB without presence of steps (Vbias=100mV, Iset=50pA) Furthermore, the SAMs formed not by the side of the steps are usually small in lateral size (Fig 6.7) because the molecules at the SAMs’ boundary can easily move 101 ADSORPTION-INDUCED CHIRAL SAMs away from the monolayers. The presence of rectangular unit cell of the monolayers indicated that the structure and symmetry of the monolayers are mainly determined by the interaction between the adsorbates rather than the substrate/adsorbates interactions, since the arrangement of the unit cell not follow the orientation of the graphite surface lattice. 6.3.2 Chiral SAMs In general, HHB is not planar, and its point group is being assigned as Ci. This group consists of only element E and hence does not contain an improper-rotation axis. Therefore the molecule HHB is chiral. It was found that HHB was quite flat in STM image, especially the aromatic moieties, allowing us to simplify HHB molecular structure. The illustration of the physisorption process was shown in Fig 6.9, where the HHB molecule is represented by a chiral center with three different attachments A, B and C, which are not within the same plane. Fig 6.8 Illustration of physisorption of HHB molecule onto HOPG surfaces 102 ADSORPTION-INDUCED CHIRAL SAMs The physisorption process can be considered as an addition reaction between the HHB and graphite surface, although no covalent bonds were formed. The resulting products or the physisorbed molecules were shown in and when graphite attacked HHB through route (L-HHB) and (R-HHB), respectively. As discussed in chapter and chapter 5, the configurations of the adsorbates on the surface must be in such way to maximize the intermolecular interaction between them. Similar to the system in Chapter 4, the resulting monolayers are the thermodynamically stable products of the physisorption process. In both L-HHB monolayers and R-HHB monolayers, the molecules have to orientate in the same direction as the adsorbates physisorbed at an early stage. Therefore the phase-separated chiral monolayers will form on the achiral surfaces. The proposed addition reaction mechanism is similar to the second step of an SN1 reaction. If the adsorbate has one side being blocked by bulky groups, the probability for graphite attacking from the blocked site will be much lower than from the unblocked site. In other words, the more open face of the adsorbates has a stronger affinity towards the substrates. Based on the discussion, we may be able to synthesize desired chiral monolayers simply by blocking one side of the adsorbates using bulky groups. 6.3.3 Symmetry Transformation of SAMs The shape of the unit cell of the HHB varied as shown in Fig 6.6 while the orientation of the HHB did not change with it. The plane group of the unit cell 103 ADSORPTION-INDUCED CHIRAL SAMs transformed from pg to p1 [32]. Detailed studies showed that the appearances of HBB under STM are different for molecules on the left hand side and right hand side of the boundary (in black, Fig 6.7). The observation strongly suggested the ‘internal’ structures of molecules were different within these two regions, although only near atomic resolution was achieved during STM studies. It was also noticed that at the boundary (Fig 6.6) there was a region with higher tunneling current. This region could possibly be: a) overlap or mismatching of the adsorbates; b) surface defects; c) impurities. It is quite difficult to identify the object directly from the STM results. The sharp rise in current suggests it is more likely the surface defects as the graphite has larger conductivity. On the other hand, the unit cell of SAMs is a rectangle with two sides at a=4.000.08nm and b=2.950.06nm, while the graphite has an in-plane lattice constant of 2.46Å and a rhombic unit cell with angle equals to 60°. The mismatch between the monolayers and substrate can possibly lead to transformation of SAMs unit cell. Therefore the change of the symmetry group of SAMs unit cell was possibly caused by i) the presence of the unknown object; ii) incommensurate lattice constant between the graphite and SAMs. The monolayers conformation was sensitive to the substrate structure. 104 ADSORPTION-INDUCED CHIRAL SAMs 6.4 Conclusion An ordered monolayer formed from the hexaalkyl hexaphenylbenzene (HHB) on an HOPG substrate is imaged by STM. Analysis of the STM images shows that the molecules form chiral monolayers on the HOPG surfaces. The chirality of the SAMs is due to the different binding sites that the adsorbates can have upon physisorption onto HOPG. The existence of phase separated chiral monolayers also indicated the physisorbed monolayers were the thermodynamically stable products of self-assembly process. Formation of desired chiral surface is made possible using the self-assembled technique. 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Res. 2007, 40, 287. 108 [...]... open face of the adsorbates has a stronger affinity towards the substrates Based on the discussion, we may be able to synthesize desired chiral monolayers simply by blocking one side of the adsorbates using bulky groups 6. 3.3 Symmetry Transformation of SAMs The shape of the unit cell of the HHB varied as shown in Fig 6. 6 while the orientation of the HHB did not change with it The plane group of the unit... upon physisorption onto HOPG The existence of phase separated chiral monolayers also indicated the physisorbed monolayers were the thermodynamically stable products of self- assembly process Formation of desired chiral surface is made possible using the self- assembled technique Meanwhile, we noticed that the monolayers unit cell was transformed within certain regions, possibly due to the presence of. ..ADSORPTION-INDUCED CHIRAL SAMs away from the monolayers The presence of rectangular unit cell of the monolayers indicated that the structure and symmetry of the monolayers are mainly determined by the interaction between the adsorbates rather than the substrate/adsorbates interactions, since the arrangement of the unit cell do not follow the orientation of the graphite surface lattice 6. 3.2 Chiral... a=4.000.08nm and b=2.950.06nm, while the graphite has an in-plane lattice constant of 2. 46 and a rhombic unit cell with angle equals to 60 ° The mismatch between the monolayers and substrate can possibly lead to transformation of SAMs unit cell Therefore the change of the symmetry group of SAMs unit cell was possibly caused by i) the presence of the unknown object; ii) incommensurate lattice constant between... lattice constant between the graphite and SAMs The monolayers conformation was sensitive to the substrate structure 104 ADSORPTION-INDUCED CHIRAL SAMs 6. 4 Conclusion An ordered monolayer formed from the hexaalkyl hexaphenylbenzene (HHB) on an HOPG substrate is imaged by STM Analysis of the STM images shows that the molecules form chiral monolayers on the HOPG surfaces The chirality of the SAMs is due to the... attachments A, B and C, which are not within the same plane Fig 6. 8 Illustration of physisorption of HHB molecule onto HOPG surfaces 102 ADSORPTION-INDUCED CHIRAL SAMs The physisorption process can be considered as an addition reaction between the HHB and graphite surface, although no covalent bonds were formed The resulting products or the physisorbed molecules were shown in 1 and 2 when graphite attacked... ADSORPTION-INDUCED CHIRAL SAMs transformed from pg to p1 [32] Detailed studies showed that the appearances of HBB under STM are different for molecules on the left hand side and right hand side of the boundary (in black, Fig 6. 7) The observation strongly suggested the ‘internal’ structures of molecules were different within these two regions, although only near atomic resolution was achieved during STM studies. .. through route 1 (L-HHB) and 2 (R-HHB), respectively As discussed in chapter 4 and chapter 5, the configurations of the adsorbates on the surface must be in such way to maximize the intermolecular interaction between them Similar to the system in Chapter 4, the resulting monolayers are the thermodynamically stable products of the physisorption process In both L-HHB monolayers and R-HHB monolayers, the molecules... HHB is not planar, and its point group is being assigned as Ci This group consists of only element E and hence does not contain an improper-rotation axis Therefore the molecule HHB is chiral It was found that HHB was quite flat in STM image, especially the aromatic moieties, allowing us to simplify HHB molecular structure The illustration of the physisorption process was shown in Fig 6. 9, where the HHB... the molecules have to orientate in the same direction as the adsorbates physisorbed at an early stage Therefore the phase-separated chiral monolayers will form on the achiral surfaces The proposed addition reaction mechanism is similar to the second step of an SN1 reaction If the adsorbate has one side being blocked by bulky groups, the probability for graphite attacking from the blocked site will be . 3.900.80nm and 2.950 .60 nm. N N N Fig 6. 4 Left: High resolution image of HHB monolayers: Bright hexagons represent the benzene ring of HHB. Right: the molecular configuration of HHB (R-HHB) in monolayers. . Fig 6. 3 Left: High resolution image of HHB monolayers: Bright hexagons represent the benzene ring of HHB. Right: the molecular configuration of HHB (L-HHB) in monolayers. (V bias = 100mV, and. ADSORPTION-INDUCED CHIRAL SAMs CHAPTER 6 SURFACE-ADSORPTION INDUCED CHIRAL SELF-ASSEMBLED MONOLAYERS OF HEXAALKYL HEXAPHENYLBENZENE (HHB) ON HIGHLY ORIENTED PYROLYTIC GRAPHITE (HOPG) 6. 1 Motivation