• Bulletin of the Korean Chemical Society
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• v.34 no.5
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• pp.1383-1387
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• 2013

The surface structure and electrochemical behavior of self-assembled monolayers (SAMs) prepared from benzenethiol (BT), cyclohexanethiol (CHT), and cyclopentanethiol (CPT) on Au(111) surface were examined by scanning tunneling microscopy (STM) and cyclic voltammetry (CV) to understand the influence of thiol molecular backbone structure on the formation and reductive desorption behavior of SAMs. STM imaging showed that BT and CPT SAMs on Au(111) surface formed at room temperature were mainly composed of disordered domains, whereas CHT SAMs were composed of well-ordered domains with three orientations. From these STM results, we suggest that molecule-substrate interaction is a key parameter for determining the structural order and disorder of simple aromatic and alicyclic thiol SAMs on Au(111). In addition, the reductive desorption peak potential for BT SAMs with aromatic rings was observed at a less negative potential of -566 mV compared to CHT SAMs (-779 mV) or CPT SAMs (-775 mV) with aliphatic cyclic rings. This reductive desorption behavior for BT SAMs is due to the presence of p-orbitals on the aromatic rings, which promote facile electron transfer from the Au electrode to BT as compared to CHT and CPT. We also confirmed that the reductive desorption behavior for simple alicyclic thiol SAMs such as CHT and CPT SAMs on Au electrodes was not significantly influenced by the degree of structural order.

• Bulletin of the Korean Chemical Society
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• v.30 no.10
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• pp.2381-2386
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• 2009

The tetrakis(thio)-substituted-1,4-benzoquinone products 4a-e, 6, 7, and the mono(alkoxy)-tris(thio)-substituted-1,4- benzoquinone products 5a-e and 8a-e were synthesized from the reactions of p-chloranil with some thiols and mixture of two different thiol compounds in alcohol in the presence of $Na_2CO_3$ at room temperature. The structures of the novel S,S,S,S- and S,S,S,O- substituted products, which were obtained by the reactions of p-chloranil as a starting compound with n-propanethiol, n-pentanethiol, n-decanethiol, n-dodecanethiol, 2-methyl-2-propanethiol, and mixture of n-decanethiol and n-cyclohexanethiol as S-nucleophiles, were characterized by spectroscopic methods.

• Proceedings of the Korean Vacuum Society Conference
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• 2011.02a
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• pp.26-26
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• 2011

Self-assembled monolayers (SAMs) prepared by sulfur-containing organic molecules on metal surfaces have drawn much attention for more than two decades because of their technological applications in wetting, chemical and biosensors, molecular recognition, nanolithography, and molecular electronics. In this talk, we will present self-assembly mechanism and two-dimensional (2D) structures of various organic thiol SAMs on Au(111), which are mainly demonstrated by molecular-scale scanning tunneling microscopy (STM) observation. In addition, we will provide some idea how to control 2D molecular arrangements of organic SAMs. For instance, the formation and surface structure of pentafluorobenzenethiols (PFBT) self-assembled monolayers (SAMs) on Au(111) formed from various experimental conditions were examined by means of STM. Although it is well known that PFBT molecules on metal surfaces do not form ordered SAMs, we clearly revealed for the first time that adsorption of PFBT on Au(111) at $75^{\circ}C$ for 2 h yields long-range, well-ordered self-assembled monolayers having a $(2{\times}5\sqrt{13})R30^{\circ}$ superlattice. Benzenethiols (BT) SAMs on gold usually have disordered phases, however, we have clearly demonstrated that the displacement of preadsorbed cyclohexanethiol self-assembled monolayers (SAMs) on Au(111) by BT molecules can be a successful approach to obtain BT SAMs with long-range ordered domains. Our results will provide new insight into controlling the structural order of BT or PFBT SAMs, which will be very useful in precisely tailoring the interface properties of metal surfaces in electronic devices.