7th Symposium on Soft Chemistry toward
Functional Materials
グローバルCOE シンポジウム「低温合成法による新機能性材料の創製（第７回）」(Kyoto University Global COE Program "Integrated Materials Science”)
Date: March 4, 2009
Place: Katsura Campus Room A2-303 (Kyoto University, Japan)
10:35 Opening Remarks: Hiroshi Kageyama (Graduate School of Science, Kyoto University)[Chair] Takeshi Abe (Graduate School of Engineering, Kyoto University)
10:40 “Functional Self Assembled Monolayers: Assembly of Donor – Spacer –Acceptor
Molecules on Gold Surfaces”
Srinivasan Sampath (Department of Inorganic and Physical Chemistry, Indian
Institute of Science, India)
11:40 “Mono-molecular Layers Covalently Bonded to Silicon Formed through a
Photochemical Reaction at Room Temperatures”
Hikaru Sano（Graduate School of Engineering, Kyoto University）(12:00 - 13:30 Lunch)[Chair] Kazuyoshi Kanamori (Graduate School of Science, Kyoto University)
13:30 “Function-integrated Hybrid Materials Fabricated via the Molecular AssemblyTechnique”
Kiyofumi Katagiri (Graduate School of Engineering, Nagoya University)
14:20 “Fabrication of Hybridized Porous Coordination Framework Crystals”
Shuhei Furukawa (Institute for Integrated Cell-Material Sciences, Kyoto University;
ERATO Kitagawa Integrated Pores Project, JST)
(15:10 - 15:30 Coffee Break)[Chair] Hiroshi Kageyama (Graduate School of Science, Kyoto University)
15:30 “Low Temperature Topochemical Methods for the Construction of Metal-Anion
Layers within Receptive Perovskite Hosts”
John B. Wiley (Department of Chemistry, University of New Orleans, USA)
16:30 “Inorganic-Organic Hybrids Based on Layered Compounds: Preparation andApplication”
Yoshiyuki Sugahara (Faculty of Science and Engineering, Waseda University)
17:20

Closing Remarks: Takeshi Abe (Graduate School of Engineering, Kyoto University)

Functional Self-Assembled Monolayers: Assembly of Donor Spacer - Acceptor Molecules on Gold Surfaces
Department of Inorganic and Physical Chemistry,
Indian Institute of Science, Bangalore, India
S Sampath
Chemical modification of surfaces has been a major area of research in interfacial
electrochemistry. As part of our on-going research program, we have been involved inunderstanding the interfacial properties of modified surfaces / new materials and liquid /solid electrolytes. The materials that we are presently interested in, are self-assembled
monolayers / LB film modified surfaces, exfoliated graphite / graphene oxide,
nanobimetallic particles, and molten electrolytes.
The present talk will highlight some of our research work on organic thin films on
conducting surfaces with special emphasis on(a) assembly of donor - s spacer - acceptor molecules for molecular rectification andintra / intermolecular electron transfer;(b) assembly of zein protein on surfaces of controlled wettability and its orientation(c) understanding water structure near a hydrophobic surface and(d) orientation dependent catalysis.
Some of our research work in the areas of SAMs and briefly, the assembly of graphene
oxide will be discussed in the present lecture.

Mono-molecular Layers Covalently Bonded to Silicon Formed througha Photochemical Reaction at Room Temperatures
Hikaru Sano
Department of Materials Science and Engineering, Kyoto University, Kyoto 606-8501, Japanhikarusano@t01.mbox.media.kyoto-u.ac.jp
Background:
Unsaturated hydrocarbons such as
1-alkene are known to react with a hydrogen-terminatedsilicon (Si) through a thermal or UV light excitation,
resulting in the formation of a self-assembled
monolayer (SAM) directly attached to the Si surface
without an intermediate oxide layer (Figure 1).
Besides thermal and UV light excitation processes, aprocess utilizing visible light has been reported.[1] Thismethod may cause less damage to organic molecules soFigure 1. Unsaturated hydrocarbons
that this process is more attractive. Nevertheless, thesuch as 1-alkene are known to react withvisible light excitation process for SAM formation has
hydrogen-terminated silicon surface
not been elucidated in detail. In the present study, wethrough thermal or photo excitation ofhave investigated the SAM formation behavior fromthe substrate.
1-hexadeceneonhydrogen-terminatedSi(111)(H-Si(111)) surfaces under irradiation with visible lightat room temperature.
Experimental: A H-Si(111) sample surface immersed in neat 1-hexadecene liquid was irradiatedwith a Xe lamp through a band-pass filter (300 nm, 400 nm, 550 nm, 700 nm, FWHM ≈ 10 nm) for 2– 32 hours at room temperature. Chemical and physical properties of the resulting samples werecharacterized by water contact angle measurements, X-ray photoelectron spectroscopy (XPS),
ellipsometry, and atomic force microscopy (AFM).
Results and discussion: Results of water contact
angles, carbon contents obtained from XPS
quantitative analysis and ellipsometric thicknessesof each sample indicate that the irradiated light witheach wavelength certainly promoted the SAM
formation and that the reaction rate become fasteras the irradiation wavelength shortened. Most
importantly AFM images obtained on theSAM-covered samples have similar topographic
images to that on H-Si(111) with terraces andmono-atomic steps, indicating that mono-molecularlayers with high uniformity are formed on theH-Si(111) surface (Figure 2).
Since UV/Vis
spectroscopy showed that 1-hexadecene molecules
do not absorb light with wavelengths between 300
and 800 nm, the irradiated light was considered toexcite the Si substrate itself. In addition, theoptical absorption coefficient of single crystal Si at
300 nm is about 770 times larger than that at 700
Figure 2.
Topographic images of thenm. Therefore, the generation of a hole/electron
samples (a) before and after irradiation withpair with an excitation photon is plausible as rate(b) 400, (c) 550 and (d) 700 nm incontrolling step of the whole reaction between
wavelength for 32 h.
H-Si(111) surface and 1-alkane.
References:[1] Q. -Y. Sun, L. C. P. M. de Smet, B. van Lagen, M. Giesberts, P. C. Thuene, J. van Engelenburg,
F. A. de Wolf, H. Zuilhof, and E. J. R. Sudhölter, J. Am. Chem. Soc., 127, 2514 (2005).

Function-integrated Hybrid Materials Fabricated
via the Molecular Assembly Technique
Kiyofumi Katagiri
Department of Applied Chemistry, Graduate School of Engineering, Nagoya University
Furo-cho, Chikusa-ku, Nagoya 464-8603, Japan.
*E-mail: katagiri@apchem.nagoya-u.ac.jp
Researches on organic-inorganic hybrid materials have been continuously attracted much attention from thecommunity of materials science. At the incunabulum stage, these materials were obtained by mixing inorganic
precursors with organic polymers, using organically modified metal alkoxides, or doping functional molecules into
the inorganic gels. However, it is not easy to control the nanostructure of hybrid materials by these techniques. In
the past decade, a number of nanostructured materials have been developed with the evolution of supramolecularscience. At the current stage, the technique of molecular assembly is an important strategy to control structure andfunctions of hybrid materials. Functions of organic and inorganic components are conjugated in these nanohybrids
and novel properties generated by integration of their functions are expected. Here, the several approaches offunction-integrated hybrid materials fabricated via the molecular assembly technique are introduced.
1) “Cerasome” as a lipid bilayer vesicle with siloxane surface
Lipid bilayer vesicles, known as liposomes, have been studied not only for cell membrane models also for drug
carriers, and substrates of molecular devices. However, the morphology of liposome is not stable since it forms by
weak molecular interaction. In 1999, “cerasome” was developed by sol-gel reaction and self-assembly oforganoalkoxysilanes which have analogous structure with bilayer forming lipids [1]. The cerasomes have highmorphological stability compared to conventional liposomes due to their inorganic frameworks on the surface.
Furthermore, the hierarchically multicellar assembly of cerasomes on the substrate was achieved by layer-by-layer
assembly of oppositely charged cerasomes [2].
2) External stimuli responsive hybrid hollow capsules prepared via layer-by-layer assembly
One of the most suitable methods to fabricate microcapsules is the layer-by-layer (LbL) assembly technique [3].
The process consists of the successive deposition of oppositely charged polyelectrolytes on colloidal particles,
followed by removal of the core. Now a number of efforts are devoted for the development of “smart capsules”
with stimuli-responsive behavior. We have developed stimuli-responsive hybrid microcapsules, comprisingpolyelectrolyte multilayers coated with lipid bilayers and metal oxides, such as TiO2 and Fe3O4, via the LbL
colloid-templating technique and the solution process for inorganic materials synthesis. The encapsulated
molecules can be released on demand by the external field irradiation due to the changes of molecular permeabilityof hollow shells [4].
[1] (a) K. Katagiri et al., Chem. Lett., 661 (1999). (b) K. Katagiri et al., Chem. Eur. J., 13, 5272-5281 (2007).
[2] K. Katagiri et al., J. Am. Chem. Soc., 124, 7892 (2002).
[3] K. Katagiri et al., Soft Matter, 2, 18-23 (2006).
[4] K. Katagiri et al., Chem. Mater., 21, 195-197 (2009).

Fabrication of Hybridized Porous Coordination Framework Crystals
Shuhei Furukawa
ERATO Kitagawa Integrated Pores Project, JST & Institute for Integrated Cell‐MaterialSciences, Kyoto University
Well‐designed metal–organic hybrid porous materials—so‐called porous coordination polymers (PCPs) or
metal–organic frameworks (MOFs)—can be made from an assembly of organic linkers with metal ions.
This class of materials was recently recognized as an intriguing class of crystalline nanoporous materials
for gas sorption, separation, and catalysis because their framework topologies and pore sizes can be
designed for selective guest accommodation, and the functionality of the pore surfaces directly
influences the interaction with guest molecules.
Porous properties such as gas sorption and guest molecule accommodation should also
correlate with the interfacial structure of porous materials because guest molecules (adsorbates) firstencounter the surface of porous materials. Hence, the affinity of porous materials for guest molecules
can be tuned by modifying the surface structure. There has been no report to directly modify the surfaceof PCP crystals, even though functionalization of PCP outer surfaces is a great challenge but a promising
methodology not only for modification of the porous properties but also for the addition of a new
function to the PCP without changing the characteristic features of the PCP crystal itself, resulting in thefabrication of multi‐functional PCPs. Here we show the novel approaches to modify the surfaces of PCP
crystals.
One way to decorate the crystal surfaces of a PCP is to hybridize the core PCP crystal withanother shell crystal by epitaxial growth at a single crystal level, thus creating core/shell type PCP
hetero‐epitaxial crystals. Such a lattice match promises pore connections at the interface between
crystals, where the modified crystal structure should influence the mobility or diffusion of adsorbates.
The first example of core/shell type PCP single crystals was synthesized by epitaxial growth, andmoreover the structural relationship between the shell and the core was determined using surface X‐ray
diffraction analysis.
The other approach is to hybridize PCP crystals with other functional organic molecules. Theligand exchange reaction of functional organic molecules with organic linkers that terminate the surfacesof PCP crystals allows us to form the self‐assembled monolayers (SAMs) on PCP crystals. Moreover, thein‐situ ligand exchange reaction led to the fabrication of nanosized rod‐like PCP crystal. The detailmechanism of crystal growth in nanometer scale was unveiled by the time‐course measurement oftransmission electron microscopy (TEM).

Low Temperature Topochemical Methods for the Construction of Metal-Anion Layers
within Perovskite Hosts
Elisha A. Josepha, Jong Lak Choi, Xiao Zhang, Liliana Viciu, Thomas A. Kodenkandath,and John B. Wiley*
Department of Chemistry and the Advanced Materials Research Institute
University of New Orleans, New Orleans, LA 70148
Low temperature (< 500 °C) topochemical reactions can be an effective way of manipulating
the structure and valence of receptive host compounds. Our group is working to develop
multistep strategies based on ion exchange and/or intercalation methods for the construction ofmetal-anion layers within receptive hosts. Previously we have shown that transition-metal-halide
layers can be inserted by ion exchange into Dion-Jacobson-type layered perovskites resulting in
new oxyhalides such as (MCl)LaNb2O7 (M = V, Cr, Mn, Fe, Co, Cu). Building on thischemistry, we examined the reductive intercalation of (CuCl)LaNb2O7. This reaction resulted in
the new compounds (AxCl)LaNb2O7 (A = Li, Na) with expulsion of copper metal. Subsequent
workup of the lithium product resulted in (Li2Cl)LaNb2O7. This compound retains the doubleperovskite layers of the host, but now contains tetrahedrally-coordinated lithium cations(LiO2Cl2) where two alkali-metal layers are separated by a single halide layer.
In an effort to expand this chemistry to larger alkali metals, an alternate strategy based onsequential intercalation reactions has also been investigated. Here a combination of reductive
and oxidative intercalations was performed on Dion-Jacobson-type layered perovskites:

A0Cl2

This approach has lead to the formation of similarly layered alkali-halide compounds,(A2Cl)LaNb2O7 (A = Rb, Cs). Here too, two alkali-metal layers form in the interlayer, but due tothe larger sizes of the cations, cubic coordination is favored (AO4Cl4).
More recent studies have examined intercalation chemistry with Ruddlesden-Popper layered
perovskites, following the examples of Greaves and coworkers.1 Here oxidative intercalation
can be carried. In addition to preparing the already reported Greaves oxyfluoride compounds,
we have made some new oxychlorides. Currently we are looking to carryout reductive
intercalation in these systems to probe whether alkali-halide arrays can also be formed in thesehost materials as well.
1. See for example: Li, R.K.; Greaves, C. Phys. Rev. B 2000, 62, 3811.

Inorganic-organic Hybrids Based on Layered Compounds:Preparation and Applications
Yoshiyuki Sugahara
Department of Applied Chemistry, School of Advanced Science and Engineering,
Waseda University
Inorganic-organic hybrids attract increasing attention, and the use of inorganic
nano-building blocks is one of promising preparation methods for these hybrids. It is wellknown that some inorganic layered compounds, which consist of stacked nano-sheets,
can accommodate organic compounds between nano-sheets, leading to the formation oftwo-dimensional ordered inorganic-organic hybrids. A large number of layered
compounds are known to form intercalation compounds with rather weak interfacialinteractions, such as ionic bonds, acid-base interactions, and hydrogen bonds. Typicalhost inorganic layered compounds are clay minerals (for example montmorillonite andkaolinite), protonated forms of layered transition metal oxides and ion-exchangeable
layered perovskites. It is also possible to bind organic groups via graft reactions wheninterlayer surfaces possess reactivities. Ion-exchangeable layered perovskites undergo
this type of reactions and layered transition metal oxyhalides (MOX, M is typically Feand Ti) are also well-known host inorganic layered compounds for grafting reactions.
Resultant inorganic-organic hybrids can be utilized in several applications, if guest
species are functional. For example, the nano-sheets with grafted polyoxyethylene chainscanfurther

accommodate

LiClO4andthus

exhibitedionic

conductivity.

Inorganic-organic hybrids can also be converted into nano-structured inorganic materials.
The conversion of n-alkylamine-H2W2O7•xH2O hybrids into WO3 nano-plates is a recent
example.