1 July 2014, Dublin, Ireland

5th Joint CSJ-RSC
Symposium on
Supramolecular Chemistry

Programme
Book
Registered charity number 207890

Welcome address
Dear Colleagues
Welcome to the fifth in our series of Joint Chemical Society of Japan (CSJ) and Royal Society of Chemistry (RSC)
symposia. This symposium is one of the activities jointly organized following the signing in 2010 of a five year
International Cooperation Agreement between the CSJ and the RSC and we hope it will be another successful
and memorable CSJ-RSC activity that will facilitate and foster collaborations and friendships. We are delighted
to have this opportunity to organize this meeting in partnership with the CSJ and thank Mr Nobuyuki Kawashima,
CSJ Executive Director and Professor Takashi Uemura from Kyoto University for all their help and support tomake this event possible.
The Royal Society of Chemistry is the world’s leading chemistry community, advancing excellence in thechemical sciences. With over 49,000 members and a knowledge business that spans the globe, we are theUK’s professional body for chemical scientists, supporting and representing our members and bringing together
chemical scientists from all over the world.
A not-for-profit organization with a heritage that spans 170 years, we have an ambitious international vision for the
future. Around the world, we invest in educating future generations of scientists. We raise and maintain standards.
We partner with industry and academia, promoting collaboration and innovation. We advise government on policy.
And we promote the talent, information and ideas that lead to great advances in science.
In a complex and changing world, chemistry and the chemical sciences are essential. They are vital in our
everyday lives and will be vital in helping the world respond to some of its biggest challenges. We’re working toshape the future of the chemical sciences – for the benefit of science and humanity.
The RSC is also pleased to have the opportunity to work more closely with the Japanese chemical science
community through Dr Hiromitsu Urakami, our Representative for Japan, who is based full-time in our office inTokyo. This office is located in the CSJ building in Tokyo and we are very grateful to the CSJ for all their help andadvice in establishing this office.
Each of the speakers in this symposium is an international expert in the area of supramolecular chemistry.
We hope that the presentations will stimulate the exchange of ideas and experiences between all participants.
We thank each of the speakers and all the participants for their contributions to this symposium.
Once again a very warm welcome to what promises to be an exciting scientific event. We hope that the
symposium will provide a springboard for future activities and that it will foster new research collaborations. We
look forward to continuing our close partnership with the CSJ with more joint CSJ-RSC activities in the future.

Professor Lesley Yellowlees CBEPresident
Royal Society of Chemistry2

Welcome address
Dear Colleagues,
In 2007, the Chemical Society of Japan (CSJ) began holding joint symposia with the Royal Society of Chemistry(RSC) as a part of its efforts to promote international exchange. The symposia were held alternatingly in Japanand in the United Kingdom in 2007, 2008, 2010, and 2012. Now CSJ and its 30,000 members are delighted
to hold the fifth joint symposium in Dublin, Ireland, in conjunction with the 13th International Symposium on
Advancing the Chemical Sciences (ISACS13).
The world is now confronting global-scale challenges in environment, resource, energy, food, and water, among
others, resulting from the population growth and human activities. Given that it is practically impossible for any
single nation to find solutions for these issues, all countries must cooperate in creating innovations based on
science and technology. As CSJ President, I believe that chemistry is a key to such innovations where chemists
can play significant roles. As one of the main action plans for 2014, therefore, CSJ is enhancing collaboration withthe chemistry-related societies around the world.
CSJ and RSC have already begun increasingly close collaboration in recent years as reflected in our International
Cooperation Agreement established in 2010. More specifically, for example, the two societies started working
together to improve chemistry-related capabilities in both countries by exchanging research findings at the two
symposia in London, with leading researchers presenting Japanese and European technological innovations
in chemistry, particularly the areas of green and life-related innovations: The first symposium in March 2013 onlithium-ion batteries and the second in March 2014 on peptide drugs.
Supramolecular chemistry, the topic of the 2014 joint symposium, is a highly advanced interdisciplinary fieldthat covers the chemical, physical and biological properties and functions of supramolecules, complex chemicalmaterials formed through specific intermolecular interaction beyond individual molecules. Recently we havebeen witnessing rapid advances in various research areas related to supramolecular chemistry, thus leading to adiverse range of materials that exhibit electrical conductivity, luminescence, self-healing, catalysis, and separation
functions, among many others. The development of applications of these materials is generating considerable
excitement.
To this fifth symposium, six distinguished scientists in the area of supramolecular chemistry are invited to present
their research results and to exchange information and ideas:
Dr. Thomas Bennett, University of Cambridge

Dr. Wolfgang Schmitt, University of Dublin, Trinity College

Dr. Kim Jelfs, Imperial College London

Dr Yoshinori Takashima, Osaka University

Dr. Rie Makiura, Osaka Prefecture University

Dr. Takashi Uemura, Kyoto University

I hope that this joint symposium will contribute to accelerating the research in supramolecular chemistry andrelated domains and also to strengthening the ties between the chemistry communities in the United Kingdom &Ireland, and Japan as represented by RSC and CSJ.

Dr. Sadayuki Sakakibara
President
The Chemical Society of Japan3

5th Joint CSJ-RSC Symposium on Supramolecular Chemistry
Chartered Accountants House, Dublin
Tuesday 1st July, 2014
Time

Event

13.30

Introduction and welcome
Nobuyuki Kawashima, CEO, Chemical Society of Japan, Japan
Robert Parker, CEO, Royal Society of Chemistry, UK

13:50

Stimuli responsive and self-healing supramolecular materials through host and guest
interactions
Yoshinori Takashima, Osaka University, Japan

14:20

Amorphous metal-organic frameworks: Structure, properties and applications
Thomas D Bennett, University of Cambridge, UK

14:50

Surface nanotectonics of metal-organic frameworks at air/liquid interfaces
Rie Makiura, Osaka Prefecture University, Japan

15:20

Coffee break

15:50

Molecular prediction of porous organic molecules
Kim E Jelfs, Imperial College London, UK

16:20

Polymer chemistry in coordination nanochannels
Takashi Uemura, Kyoto University, Japan

16:50

Supramolecular approaches to nanoscopic coordination cages, clusters and highsurface area coordination networks
Wolfgang Schmitt, University of Dublin, Ireland

17.20

Closing remarks
Lesley Yellowlees, President, Royal Society of Chemistry, UK
Close

4

Chair
Sarah Thomas
Royal Society ofChemistry, UK

Chair
Takashi Uemura
Kyoto University,
Japan

Chair
Thomas D Bennett
University ofCambridge, UK

ChairSarah Thomas,
Royal Society ofChemistry, UK

Notes5

Thomas Douglas Bennett
University of Cambridge, UK
Tdb35@cam.ac.uk
Thomas D. Bennett was born in South Shields, UK (1986).He read the Natural Sciences Tripos at the Universityof Cambridge, specializing in Chemistry, where he undertook research on the synthesis of ‘light’ metal-organic
frameworks under Dr. Paul T. Wood.After moving to the Department of Materials Science and Metallurgy, hecompleted a PhD on the thermo-mechanical Properties of Zeolitic Imidazolate Frameworks, under Professor
Anthony Cheetham. In 2009 he was awarded an honorary research fellowship at the Ras Al Khaimah center foradvanced materials (RAK-CAM), and in 2012 he won the Panalytical prize for an outstanding contribution to X-ray
diffraction.Thomas was elected as a Research Fellow at Trinity Hall, University of Cambridge in 2013.He currently
focuses on the synthesis, structure, properties and applications of amorphous hybrid frameworks, alongside theformation of hybrid glasses.

6

Amorphous metal-organic frameworks: Structure, properties
and applications
Thomas Douglas Bennett
University of Cambridge, UKA small but growing number of cases of MOFs lacking the long-range order characteristic of crystalline
structures are steadily capturing scientific interest (though they remain woefully under represented), despite thephenomenon being known in inorganic zeolites.The majority of work has been performed on a sub-family of
MOFs called zeolitic imidazolate frameworks (ZIFs), which consist of tetrahedral metal centers (typically Zn2+ orCo2+), connected by Imidazolate-type (C3H3N2-) organic ligands in zeolitic topologies.Recently, we discovered that
ZIFs could be amorphized by ball-milling and heating, and that the resultant amorphous material has a similar
topology to that of silica glass.1 Similarly, they can also be amorphized by pressure, though there is considerable
debate about the reversibility of the process.

	
  Amorphous MOFs, whilst significantly harder to characterise, are more mechanically stable than their well-known
crystalline counterparts.They also offer routes to functional glass materials, through melting of functionalised
parent frameworks (incoporating lanthanide ions or chiral ligands).Some of these glasses have been shown to be
topologically ‘perfect’ with fragilities lower than that of aSiO2.Recently, we have shown that the release in-vitro of
ibuprofen and caffeine stored within ZIF-8 can be tailored by ball-milling inducing collapse of the framework, whilst
I2 has also been irreversible captured using similar methodology.2
References
1.	Bennett, T. D.; Goodwin, A. L.; Dove, M. T.; Keen, D. A.; Tucker, M. G.; Barney, E. R.; Soper, A. K.; Bithell, E. G.; Tan,
J. C.; Cheetham, A. K. Structure and Properties of an Amorphous Metal-Organic Framework. Phys Rev Lett 2010, 104.
2.	Bennett, T. D.; Saines, P. J.; Keen, D. A.; Tan, J. C.; Cheetham, A. K. Ball-Milling-Induced Amorphization of Zeolitic
Imidazolate Frameworks (ZIFs) for the Irreversible Trapping of Iodine. Chem-Eur J 2013, 19, 7049-7055.

7

Kim Jelfs
Imperial College London, UK
k.jelfs@imperial.ac.uk
Since October 2013 I have held a Royal Society University Research Fellowship (URF) at Imperial College
London, where I am now establishing my own independent research group. My fellowship is entitled “Directing thesynthesis of functional molecular materials”. I completed my PhD in Computational Chemistry at UCL, working on
the development and application of modelling to understand zeolite crystal growth and was awarded the Ramsay
Medal for the best completing PhD student. I subsequently became a visiting researcher at the Universitat
de Barcelona for 6 months, working with Prof. Stefan Bromley on the prediction of silicate cluster formation,
before moving to the University of Liverpool, working as a PDRA across the experimental groups of Profs. Matt
Rosseinsky and Andy Cooper. I focused upon modelling porous materials, with my expertise spanning zeolites,
metal-organic frameworks, polymers and porous molecular materials. Research highlights over my career thus
far include high impact publications in Nature, Nature Chemistry, Angewandte Chemie and JACS. In several of
my publications to date I have been the sole computational author, providing both insight and predictions for theexperimental research.

8

Molecular prediction of porous organic molecules
Kim E. Jelfsa*, Ming Liub and Andrew I. CooperbaDepartment of Chemistry, Imperial College London, UKb
Department of Chemistry, University of Liverpool, UK

The modular assembly of discrete, intrinsically porous organic molecules is an alternative to forming porous
materials through extended networks that are chemically bonded in 3-dimensions.1 These modular materials canhave advantages, such as being easily processable,2 co-crystallisation allowing property tuning3 and their greater
mobility facilitating stimuli-response behaviour, such as “on”/“off” porosity switching.4 From a computational
perspective, it has been shown that crystal structure prediction techniques can rationalise the observed
polymorphs3 and we have used molecular dynamics simulations to explain observed sorbate selectivity.4,5 Morerecently, we have been developing an approach towards in silico design of new porous molecular materials withdesired structures and properties. This automates the assembly and screening of hypothetical molecules from alibrary of precursors. The first goal is to predict the conformation of the molecule that will be formed. It is crucial
to test whether the molecule will be “shape persistent”, keeping an internal void in the absence of solvent, as wehave previously spent months synthesising large molecules that collapse upon desolvation. The second goal is
to correctly predict which molecule will form from a pair of precursors – e.g. will a [2+3], [4+6], [6+9] or [8+12]
reaction occur? We have demonstrated the successful prediction of an odd-even effect for a series of alkane
diamines (a).6 Further, we can predict how post-synthetic modification can engineer shape-persistence and acidand base-resistance (b), as well as using computational predictions to engineer novel shaped molecules and to
perform rapid computational screening to predict properties for hypothetical molecules (c).

Figure: a) Size and structure prediction of an odd-even alkane chain effect; b) Predictions of post-synthetic modification routes
to engineer shape persistence; c) Predictions of promising synthetic targets for new topologies and functions.

References
1.
2.
3.
4.
5.
6.

Nat. Mater., 2009, 8, 973.
J. Am. Chem. Soc. 2012, 134, 588.
Nature 2011, 474, 367.
Angew. Chem. Int. Ed. 2010, 50 (3), 749.
Nature Chem., 2013, 5, 276.
J. Am. Chem. Soc. 2013, 135, 9307.

9

Rie Makiura
Osaka Prefecture University, Japanr-makiura@21c.osakafu-u.ac.jp
Rie Makiura graduated from the University of Tsukuba in 2002 (MSc, Chemistry). Following an extended spell asa Researcher at the Frontier Device Research Center of SEIKO EPSON Cooperation in Nagano (2002 - 2007)
where she worked on the development of organic electronic (OLED, TFT) devices and thin film all-solid batteries,
she returned to academia as an Assistant Professor at the Department of Chemistry, Kyushu University (2007 2010). She was awarded her D.Sc. degree from Kyushu University in 2010. In April 2010, she was appointed asa tenure-track Lecturer at the Nanoscience and Nanotechnology Research Center, Osaka Prefecture University.
She was also appointed as a PRESTO (Precursory Research for Embryonic Science and Technology) researcher,
the Japan Science and Technology (JST) agency in 2012. She received the 2013 Award for Outstanding Young
Women Chemists by the Chemical Society of Japan and the 2014 Young Scientists’ Prize of the Commendationfor Science and Technology by the Minister of Education, Culture, Sports, Science and Technology, Japan. Her
research focus is currently on the rational design and construction of functional surface/interface nanostructures.

10Surface	
  nanotectonics	
  of	
  metal-­‐organic	
  frameworks	
  at	
  air/liquid	
  Interfaces	
  
	
  

Rie	
  Makiura1,2	
  	
  Surface nanotectonics
of metal-organic frameworks at1	
  Nanoscience	
  and	  Nanotechnology	
  Research	
  C
enter,	
  Osaka	  Prefecture	
  University,	  1-­‐
air/liquidinterfaces

	
  

2	
  Gakuen-­‐cho,	
  Naka-­‐ku,	
  Sakai,	
  Osaka	
  599-­‐8570	
  JAPAN,	
  2	
  JST-­‐PRESTO	  
Rie Makiura1,2
Email	  :	  r-­‐makiura@21c.osakafu-­‐u.ac.jp	
  
1
HP	
  :	
  http://www.nanosq.21c.osakafu-­‐u.ac.jp/ttsl_lab/r_makiura/index.html	
  Nanoscience and Nanotechnology Research Center, Osaka Prefecture University,

1-2 Gakuen-cho, Naka-ku, Sakai, Osaka 599-8570 JAPAN2
JST-PRESTO,
Email: r-makiura@21c.osakafu-u.ac.jp
Development	
   of	
   rational	
   methods	
  for	
   creating	
  ordered	
   structures	
   with	  HP:
http://www.nanosq.21c.osakafu-u.ac.jp/ttsl_lab/r_makiura/index.html
nanometer	
   scale	
   precision	
   is	
   one	   of	
   the	   central	
   issues	
   in	
   the	   nanoscience	
   and	  Intensity (arb. units)

nanotechnology	
  fields.	
   Molecular	
   based	
   nanoassemblies	
   are	   of	
   great	   interest	  Development of rational methods for creating ordered structures with nanometer scale precision is one of the
because	   of	
   their	  of	
   structures	
  and	
   facile	
   functionalization.	
  
have	
  
central rich	
  issuesvariety	
  in the nanoscienceand nanotechnology
fields. Molecular basedWe	
  nanoassemblies
are of greatinterest
becauseperfect	  of their richvariety of structures and facile
functionalization.
We have succeeded to assemble
succeeded	
   to	
  assemble	
  preferentially-­‐oriented	
  metal-­‐organic	
  framework	
  perfectby	
  preferentially-oriented
metal-organic
framework(MOF)ananofilms
by developing
a facile bottom-up(MOF)	
   nanofilms	
  developing	
   a	
   facile	
  bottom-­‐up	
  fabrication	
  t	
   liquid-­‐air	
  interfaces	
  fabrication at liquid-air interfaces 1-3. Employing liquid surfaces in order to tune 2D growth is highly promising as[1-­‐3].	
   Employing	
  liquid	   surfaces	
   in	   order	
   to	
   tune	
   2D	
   growth	
   is	
   highly	
   promising	
   as	
  spontaneous organizational features of the building components can be enhanced. In order to develop further
spontaneous	
  theorganizational	
  of	
   the	  building	  can	
  thebe	  enhanced.	
  strategy to growfeatures	  2D molecularassemblies
withcomponents	  fine control of both
domainsize and the moleculararrangement, understanding the formation mechanism associated with the coordinative linkages is necessary.
In	
  order	
  to	
  develop	
  further	
  the	
  strategy	
  to	
  grow	
  2D	
  molecular	
  assemblies	
  with	  fine	  control	
  of	
  both	  the	
  domain	
  size	  and	  the	
  molecular	
  arrangement,	
  understanding	
  the	
  Here I will present a discussion of the formation process of a 2D MOF array (NAFS-13) on a liquid surface byformation	
  mechanism	
  associated	
  with	
  the	  linkages	
  is	
  necessary.	
  	
   incidence synchrotron X-ray
varying the fabrication
conditions
withcoordinative	  the structural details
obtainedby the grazing
diffraction(GIXRD)techniqueattheair/waterinterface
(Fig.
1).
A
porphyrin
derivative(MTCPP) was selected
Here	
   I	
   will	   present	
   a	
   discussion	
   of	
   the	   formation	
   process	
   of	   a	   2D	
   MOF	   array	  as the molecular building unit. The results reveal that the highly-crystalline preferentially-oriented ultra-narrow(NAFS-­‐13)	
  on	
  NAFS-13a	
  liquid	
  sheetssurface	  by	
  varying	
  the	
  fabrication	
  conditions	
  with	  the	
  structural	
  form immediately after spreading the molecular building units on the copper ion aqueous
details	
   obtained	
  
by	
  
the	
  
grazing	
  incidence	
  diffraction	
  (GIXRD)	
  solution subphase (Fig. 1). Following
thesynchrotron	  insight obtainedX-­‐ray	  on the nanosheet
formation
process, a new approach of– post-injectionof the 1).	
  metal
into thederivative	  subphase – wasdevelopedthat effectively led to thetechnique	
   at	
  sheetthe	
  assembly
air/water	  interface	
   (Fig.	
  A	
  linkers
porphyrin	
  (MTCPP)	
  
was	
  
4-5
.
enlargementofthe
NAFS-13sheet
domainsize
selected	
  as	
  the	
  molecular	
  building	
  unit.	
  The	  results	
  reveal	
  that	  the	
  highly-­‐crystalline	
  preferentially-­‐oriented	
   ultra-­‐(a)	
   (110)30 mN/m (b)	  narrow	
   NAFS-­‐13	
   sheets	
   form	  20 mN/m
10 mN/m
immediately	
   after	
   spreading	  16.6 Å
5 mN/mthe	
   molecular	
   building	
   units	
  16.6 Å
1 mN/m0 mN/mon	
   the	   copper	
   ion	   aqueous	
  (200)
solution	
   subphase	
   (Fig.	
   1).	
  (220) (400)(330)(320)
Following	
  
the	
  
insight	
  bobtained	
   on	
   the	   nanosheet	
  aformation	
   process,	
   a	
   new	
  c3Å
approach	
   of	   sheet	
   assembly	
   ‒	
  
a
post-­‐injection	
   of	
   the	   metal	
  
C
N
O
Pd
Cu
linkers	
   into	   the	   subphase	   ‒	
  0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0
Q （1/Å）was	
  developed	
  
that	
  
Fig.	
  
1	
  
	
  
Structural	  evolution	
   of	
   the	   MTCPP-­‐Cu	  1 Structural
the MTCPP-Cu nanosheets on liquid surfaces. (a) GIXRD (λ=1.549 Å) profiles with change in
effectively	
   Fig.
led	  to	
   evolutionthe	
   of nanosheets	
  on	
  crystalline
liquid	   surfaces.	
  
GIXRD	   (l=1.549	
   Å)	  surface pressure. (b) Schematic
diagram of thestructure of(a)	
  NAFS-13.
enlargement	
   of	
   the	   NAFS-­‐13	
   profiles	
   with	
  change	
  in	
   surface	
  pressure.	
   (b)	
  Schematic	
  References
diagram	
  of	
  the	
  crystalline	
  structure	
  of	
  NAFS-­‐13.	
  sheet	
  domain	
  size	
  [4-­‐5]. 	
  
1. Makiura, R. et al. Nature Mater. 8, 476 (2009).
	  2. Motoyama, S., Makiura, R., Sakata, O. Kitagawa, H. J. Am. Chem. Soc. 133, 5640 (2011).
Reference	
   3. Yamada, T., Otsubo, K., Makiura, R., Kitagawa, H. Chem. Soc. Rev. 42, 6655 (2013).

[1]
[2]
[3]
[4]
[5]

Makiura,	
  4.R.	
  eMakiura,t	
  al.	  Nature	
  Mater.	
  O.8,	
  Sci.
476	
  (2009).	
  R., Konovalov,Rep.
3, 2506 (2013).
5.
Makiura,R.,
Konovalov,O.
DaltonTrans. 42, 15931
Motoyama,	
  S.,	
  Makiura,	
  R.,	
  Sakata,	
  O.	
  Kitagawa,	
  
H.	
  J.	
  A(2013).
m.	
  Chem.	
  Soc.	
  133,	
  5640	
  (2011).	
  Yamada,	
  T.,	
  Otsubo,	
  K.,	
  Makiura,	
  R.,	
  Kitagawa,	
  H.	
  Chem.	
  Soc.	
  Rev.	
  42,	
  6655	
  (2013).	
  Makiura,	  R.,	
  Konovalov,	
  O.	
  Sci.	
  Rep.	
  3,	
  2506	
  (2013).	
  Makiura,	  R.,	
  Konovalov,	
  O.	
  Dalton	  Trans.	
  42,	  15931	
  (2013).	
  11

Wolfgang Schmitt
School of Chemistry, Trinity College Dublin, Irelandschmittw@tcd.ie
Wolfgang Schmitt is currently an Associate Professor and working in the area of Inorganic and Materials
Chemistry at Trinity College Dublin. He studied Chemistry at the Technical University Darmstadt (TU), Germany
and graduated as Dipl. Ing. (Chemistry) in 1999. He was awarded the Dr. Anton Keller Prize from the Universityof Darmstadt and received his Ph.D. from the University of Karlsruhe in 2002. From 2002-2003 he worked as a
postdoctoral fellow at the Royal Institution of Great Britain. In March 2004 he was selected to join the International
Centre for Young Scientists at the National Institute for Materials Sciences in Tsukuba, Japan as an independent
research fellow. After joining Trinity College Dublin he was elected as ‘Fellow’ in 2009. He is an SFI Principal
Investigator and received further funding from SFI, EPA and IRCSET. Dr. Schmitt’s research interests focus on
the supramolecular chemistry of hybrid organic-inorganic materials aiming to exploit these advanced materials
for sustainable energy applications, catalysis and molecular magnetic devices. Current activities focus on
metal-organic frameworks (MOFs) for hydrogen storage applications, CO2 fixation and activation, bio-mimetic
syntheses, self-assembly processes, synthetic approaches to nanoscopic clusters (polyoxometalates and othercoordination clusters) and molecular coordination cages.

12Supramolecular approaches to nanoscopic coordination cages,
clusters and high-surface area coordination networks
Wolfgang Schmitt*, Lei Zhang, Nianyong Zhu and Camelia I. Onet
University of Dublin, Trinity College Dublin, School of Chemistry, Dublin, D2, Ireland
Coordination clusters and molecular capsules are supramolecular compounds that have received considerable
attention over the last years. The arrangement and connectivity of the metal centres in such nanoscopic
assemblies may result in unusual magnetic and electronic attributes whist the resulting inner cavities provide
unique, restricted chemical environments which allow the molecules to be applied for molecular recognition
purposes, as supramolecular containers or as catalysts.1 We studied the formation of VV/VIV cages which form
upon partial reduction of vanadates in the presence of organic ligands and identified new tetra- and pentanuclear
building units and utilized these pre-organized structural motifs to produce novel hybrid capsules, [H2V10O18(L)4]8with controllable dimensions (Fig.1, left).2 Our investigations further demonstrate that template aggregatescan be utilised to direct the assembly process of the tetranuclear building unitsallowing a successive built-up
of highly symmetrical nanosopic coordination cages that contain between 20 and 32 V and As centres.3 Our
research highlights the relation between Platonic Templates and Archimedean cage structures (Fig.1, right). We
demonstrated that the synthetic approach can be applied to prepare nanoscopic Mn coordination clusters thatgive rise to interesting molecular magnetic properties.4 Other aspects focus on self-assembly processes that yield
carboxylate-based MOFs that reveal high surface areas and can be used for gas storage applications.5

Fig 1. Left: Hybrid vanadate capsules; Right: Simplified core structures of vanadate coordination cages and theirencapsulated templates.

References
1. S. R. Seidel, P. J. Stang, Acc. Chem. Res., 2002, 35, 97; Y. Inokuma, T. Arai, M. Fujita, Nature Chem., 2010, 2, 780.
2. 	(a) M. B. Mahimaidoss, S. A. Krasnikov, L. Reck, C. I. Onet,J. M. Breen, N. Zhu, B. Marzec, I. V. Shvets, W. Schmitt, Chem.
Commun., 2014, 50, 2265;(b) J.M. Breen, W. Schmitt,Angew. Chem. Int. Ed., 2008, 47, 6904;
3. L. Zhang, W. Schmitt,J. Am. Chem. Soc, 2011, 133, 11240.
4.	(a) L. Zhang, R. Clérac, P. Heijboer, W. Schmitt, Angew. Chem. Int. Ed., 2012, 51, 3007;(b) L. Zhang, R. Clérac, C. I. Onet, M. Venkatesan, P. Heijboer, W. Schmitt, Chem.- Eur. J., 2012, 18, 13984;(c) L. Zhang , B. Marzec, R. Clérac, Y. Chen , H. Zhang, W. Schmitt, Chem. Commun., 2013, 49, 66;(d) L . Zhang, C.I. Onet, R. Clérac, M. Rouzières, B. Marzec, M. Boese, M. Venkatesan, W. Schmitt, Chem. Commun., 2013,
48, 7400.
5 	 (a) N. Zhu, G. Tobin, W. Schmitt, Chem. Commun. 2012, 48, 3638;(b) N.-Y. Zhu, M. J. Lennox, G. Tobin, L. Goodman, T. Düren, W. Schmitt, Chem. Eur. J., 2014,DOI: 10.1002/chem.201304856.

13

	
  

	
  

Yoshinori Takashima
Osaka University, Japan
takasima@chem.sci.osaka-u.ac.jp

Yoshinori Takashima was born in 1974 in Osaka, Japan.He received his Ph.D. degree in 2002 from Osaka
University, under the guidance of Prof. Akira Harada (Osaka Univ.), focusing on the polymerization catalyst
using group 4 transition metal catalyst.He was selected as a Research Fellow of the Japan Society for the
Promotion of Science (JSPS) in 1999–2002.During the winter of 2003, as a visiting fellow, he worked at Prof.
Jeffrey M. Stryker’s lab, Department of Chemistry, the Univ. of Alberta.In 2003, he obtained his PhD in Polymer
Science from Osaka Univ.Prior to joining the Graduate School of Science at Osaka Univ. in 2004 as an assistantprofessor for Professor Akira Harada, he served as a postdoctoral research fellow from JSPS in the Divisionof Applied Chemistry, Osaka Univ. for Professor Toshikazu Hirao. In 2011, he worked at Prof. Philip A. Gale’slab, Department of Chemistry, the Univ. of Southampton as a visiting researcher.His research interests include
supramolecular materials, catalysts, molecular motors and devices.

14

Stimuli responsive and self-healing supramolecular materials throughhost and guest interactions
Yoshinori Takashima
Department of Macromolecular Science, Graduate School of Science, Osaka University
1-1 Machikaneyama Chou, Toyonaka, Osaka 560-0043, Japan
Email: takasima@chem.sci.osaka-u.ac.jp
In biological system, there are some attractive functions such as enzymatic reactions, muscle motion, and self-healing
properties.Inspired by these functions, many supramolecular chemists engage the creation of supramolecular complexes
reminescent of biological functions. We have focused on the creation of supramolecular materials reminescence of the muscle
motion, self-organization of cell and self-healing properties through host-guest interactions (Fig. 1).We employ cyclodextrin(CD) as a host molecule because it is environmentally benign and has diverse applications.This presentation demonstrates asfollowing topics.
Supramolecular actuator
To prepare supramolecular actuators, azobenzene and ferrocene derivatives were chosen as photo and redox-responsive guest
molecules.The chemical crosslinked hydrogel with stimuli-responsive groups showed the bending behavior by external stimuli,
which controlled the ratio of inclusion complexes as a function of crosslinkers. 1-3
Stimuli-responsive self-healing materials
We have investigated two approaches to prepare self-healing materials. First method is a supramolecular materials using
poly(acrylic acid) modified with cyclodextrins (pAA-CDs) as a host polymer and pAA with ferrocene (pAA-Fc) as a guest polymer(Fig. 2).4 Second method is the radical copolymerization of βCD and adamantane (Ad) monomers to give supramolecular hydrogels
in water without crosslinkers (Fig. 3). The supramolecular hydrogels formed by host-guest interactions exhibits self-healing
properties to reach 99% of the initial gel’s strength.5
Macroscopic self-assembly through non-covalent bond
We achieved macroscopic self-assemblies through molecular recognition of CDs, which can be used to direct the assembly ofmacroscopic objects into larger aggregated structures.6 Here we report an A-B-C type redox–responsive gel assembly system
based on host–guest interactions between CD and Fc / cation–anion interactions between Fc+ and sodium p–styrenesulfonate(SSNa).7-8Such macroscopic assemblies remind us of the selective formation of cell organization.

	
  

	
  
Figure 1. Conceptual scheme of our studies.

Figure 2. Redox-responsive healing
experiment of the pAA-6βCD/pAA-Fc
hydrogel using oxidizing/reducing agents.

	
  Figure 3.Self-healing property of the βCD-Ad gel.

References
1.	S. Tamesue, Y. Takashima, H. Yamaguchi, S. Shinkai, A. Harada, A.Angew. Chem. Int. Ed. 49, 7461 (2010).
2.	Y. Takashima, S. Hatanaka, M. Otsubo, M. Nakahata, T. Kakuta, A. Hashidzume, Y. Yamaguchi, A. Harada, Nat. Commun. 3, 1270 (2012).
3.	M. Nakahata, Y. Takashima, A. Hashidzume, and A. Harada, Angew. Chem. Int. Ed., 52, 5731 (2013).
4.	M. Nakahata, Y. Takashima, H. Yamaguchi A. Harada, Nat. Commun. 2, 511 (2011).
5.	T. Kakuta, Y. Takashima, M. Nakahata, M. Otsubo, H. Yamaguchi, A. Harada, Adv. Mat., 25, 2849 (2013).
6.	A. Harada, R. Kobayashi, Y. Takashima, A. Hashidzume, H. Yamaguchi, Nat. Chem. 3, 34 (2011).
7.	M. Nakahata, Y. Takashima, A. Harada, Angew. Chem. Int. Ed., 2014, 53, 3617.
8.	M. Nakahata, S. Mori, Y. Takashima, A. Hashidzume, H. Yamaguchi, A. Harada, ACS Macro Lett., 3, 337 (2014).

15

Takashi UEMURA
Kyoto University, Japanuemura@sbchem.kyoto-u.ac.jp
Takashi Uemura received his PhD under the supervision of Prof. Yoshiki Chujo at Kyoto University in 2002. Duringthat time, he joined Prof. Christopher K. Ober group at Cornell University as a summer student (1999).He became
an assistant professor in Prof. Susumu Kitagawa group at Kyoto University (2002), and was promoted associate
professor (2010). He has also worked as a researcher in PRESTO program during 2006-2010 and was recently
selected as a research director in CREST program of Japan Science and Technology Agency (JST). He received
many awards including the Chemical Society of Japan Award for Young Chemists (2010) and the Commendationfor Science and Technology by the Minister of Education, Culture, Sports, and Technology, the Young Scientists’Prize (2013). His research interest focuses on the preparation and property of synergistic nanohybrids between
coordination compounds and polymer materials, in particular, polymer chemistry in confined coordination
frameworks.

16

Polymer chemistry in coordination nanochannels
Takashi Uemura1,2
1

Department of Synthetic Chemistry and Biological Chemistry, Graduate School of Engineering,
Kyoto University, Katsura, Nishikyo-ku, Kyoto 615-8510, Japan
2
CREST, Japan Science and Technology Agency (JST), 4-1-8 Honcho, Kawaguchi,
Saitama 332-0012, Japan
Email: uemura@sbchem.kyoto-u.ac.jp

Recently, Metal-Organic Frameworks (MOFs) composed of metal ions and organic ligands have been extensively
studied. The characteristic features of MOFs are highly regular channel structures, controllable channel sizes
approximating molecular dimensions, and designable surface functionality. Use of their regulated and tunablechannels for a field of polymerization can allow multi-level controls of the resulting polymer structures (Figure).1
In addition, construction of nanocomposites between MOFs and polymers will provide unprecedented material
platforms to accomplish many nanoscale functions (Figure).1

Controlled radical polymerization of vinyl monomers can be attained in MOF nanochannels.2 Considerable effects
of pore size, shape, and functionality on the resulting polymer structure and assembly were demonstrated. A varietyof polymerization reactions can be also catalyzed in MOFs, providing functional poly(substituted acetylene)s,
polypyrrole, and so on.3 We also studied the properties of polymer chains confined in the nanochannels of MOFs,
which led to produce many functional nanocomposite materials including sensor, adsorbent, and conductor.4
New application of a MOF-peptide composite for an autonomous motor was also performed.5
References
1.	(a) Chem. Asian J. 2006, 1, 36.
(b) Chem. Soc. Rev. 2009, 38, 1228.
(c) Chem. Eur. J. 2014, 20, 1482.
2.	(a) J. Am. Chem. Soc. 2010, 132, 4917.
(c) Macromolecules 2011, 44, 2693.
(c) Angew. Chem. Int. Ed. 2007, 46, 4987.
(d) Chem. Mater. 2013, 25, 3772.
(e) Nature Chem. 2013, 5, 335.
3.	(a) Angew. Chem. Int. Ed. 2006, 45, 4112.
(b) Angew. Chem. Int. Ed. 2008, 47, 9883.
(c) Chem. Mater. 2009, 21, 4096.
4.	(a) Nature Commun. 2010, 1, 83.
(b) Nature Mater. 2011, 10, 787.
(c) J. Am. Chem. Soc. 2012, 134, 8360.
5. Nature Mater. 2012, 11, 1081.

17

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