European Cooperation
in Science and Technology
- COST ——————————
Secretariat
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Brussels, 4 July 2012
COST 4121/12
MEMORANDUM OF UNDERSTANDING
Subject :
Memorandum of Understanding for the implementation of a European Concerted
Research Action designated as COST Action CM1203 : Polyoxometalate
Chemistry for Molecular Nanoscience (PoCheMoN)
Delegations will find attached the Memorandum of Understanding for COST Action as approved by
the COST Committee of Senior Officials (CSO) at its 185th meeting on 6 June 2012.
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MEMORANDUM OF UNDERSTANDING
For the implementation of a European Concerted Research Action designated as
COST Action CM1203
POLYOXOMETALATE CHEMISTRY FOR MOLECULAR NANOSCIENCE
(POCHEMON)
The Parties to this Memorandum of Understanding, declaring their common intention to participate
in the concerted Action referred to above and described in the technical Annex to the Memorandum,
have reached the following understanding:
1.
The Action will be carried out in accordance with the provisions of document COST 4154/11
“Rules and Procedures for Implementing COST Actions”, or in any new document amending
or replacing it, the contents of which the Parties are fully aware of.
2.
The main objective of the Action is to grow European polyoxometalate (POM) research and
create a platform for coordination and cooperation that will accelerate advances in
fundamental POM chemistry and world-leading POM-based Molecular Nanoscience.
3.
The economic dimension of the activities carried out under the Action has been estimated, on
the basis of information available during the planning of the Action, at EUR 56 million in
2012 prices.
4.
The Memorandum of Understanding will take effect on being accepted by at least five Parties.
5.
The Memorandum of Understanding will remain in force for a period of 4 years, calculated
from the date of the first meeting of the Management Committee, unless the duration of the
Action is modified according to the provisions of Chapter V of the document referred to in
Point 1 above.
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TECHNICAL ANNEX
A. ABSTRACT AND KEYWORDS
Polyoxometalates (POMs) are molecular metal oxides with dimensions in the nanometer range.
Their uniquely versatile properties provide the basis for advances in catalysis, alternative energy
sources, magnetic, electronic and photonic devices and medicine that are crucial to European
science and technology. However, the global pre-eminence of European POM research is currently
jeopardized by a rapid growth in activity in China, India and Pacific Rim states, where POM
chemistry is recognized as critically important.
The main objective of PoCheMoN is to accelerate POM-based Molecular Nanoscience by creating
a coherent network for world-leading education and research in POM chemistry. This first
overarching COST Action in this area will consolidate the European POM community and promote
strategic and efficient POM research through collaboration, thereby creating a readily accessible
knowledge base for the rapid uptake of POM chemistry into Molecular Nanoscience and generating
breakthrough technologies through links with aligned disciplines and companies. Coordinated
mobility will engender new research collaborations, training exchanges and rapid dissemination of
results, thereby protecting key skills, growing the skill-base of early-stage researchers and
enhancing research output to ensure that Europe benefits from sector leadership into the future in
the face of strong competition from the rapidly expanding far-east effort.
Keywords: Polyoxometalate synthesis, structure and properties; nanoscale functional materials;
directed assembly; computational studies; surface science.
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B. BACKGROUND
B.1 General background
Metal oxides are ubiquitous in modern technologies ranging from large-scale industrial catalysis to
microelectronics, but the emerging area of Molecular Nanoscience (MN), i.e. the study of advanced
functional materials and nanometric systems based on molecular components, has involved mainly
organic molecules and/or metal complexes. A key goal in the development of MN is therefore the
incorporation of metal oxide components. In this regard, polyoxometalates (POMs) are archetypal
molecular metal oxides and their uniquely diverse structural, electronic, magnetic and chemical
properties provide a versatile platform for inorganic Molecular Nanoscience (MN) that has hardly
been exploited.
Encompassing some of the most exciting challenges facing modern chemists and materials
scientists, POM-based MN is a truly interdisciplinary field in which areas such as supramolecular
chemistry, molecular electronics and molecular magnetism converge. Technologies arising from
this research will have major societal impact and shape future economies in areas relevant to
international Grand Challenges such as alternative energy conversion and storage, water
purification, CO2 conversion and molecular electronics. POM-based MN will allow the design,
synthesis and full characterization of metal oxide components with specific properties prior to their
incorporation into functional nanosystems, providing a wider diversity of materials and higher
chemical precision than nanoscience that relies purely upon the manipulation of particle size,
morphology and dimensionality of elements or simple compounds. For example, (i) the inorganic
nature of POMs (lack of carbon-based components) makes them ideal candidates for catalysts under
harsh conditions such as water oxidation, (ii) their unique electronic structures can be exploited for
molecular electronics and spintronics with functionalities that potentially reach beyond
the paradigms of von-Neumann architectures and binary logics, and (iii) self-assembly into
molecule-based analogues of solid-state oxides produces complex architectures that can host
numerous additional functional components and provide ‘soft’ routes to active oxide systems.
Translating these key advantages into real-world applications requires joint large-scale efforts from
the diverse specialist groups that will be organized in this Action.
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European groups are at the forefront of POM chemistry and this strength provides a world-leading
European capability for POM-based MN that could impact on science, industry and society.
However, POM research is increasingly complex and requires an increasingly interdisciplinary
approach with access to facilities and skills that exceed the capabilities of individual groups.
Consequently, without the consolidation of European POM knowledge and expertise, European
influence will decline along with any scientific advantage over the USA, Japan and China at a time
when ever-more applications for POMs are emerging. To date, there has been no coordinated effort
to integrate the European POM community and no other COST Action with a similar scientific
scope.
COST is the only scheme to provide funding for a network of this type that will coordinate
nationally-funded POM research projects and provide the mobility necessary to share expertise and
facilities and stimulate new, ground-breaking collaborative research based on established strengths.
Given the successful COST format for large network operation, this Action will create an efficient
structure for managing a programme of meetings, workshops, schools and exchanges that would be
difficult, if not impossible, to coordinate under any of the other research Frameworks. Another
important aspect of COST is the open nature of Actions, which greatly enhances the chances of
identifying new research synergies.
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B.2 Current state of knowledge
An exponential growth in POM chemistry since the 1970’s was triggered by advances in analytical
techniques such as X-ray crystallography and NMR spectroscopy, and a fertile, global POM
community emerged from landmark meetings in France, Germany and Spain. SciFinder hits for
'polyoxometalate' increase from 30 in 1960 to >1300 per year from 2009, and the Web of
Science analysis of worldwide journal article output for 2000-2011 shown below illustrates the
European strength in the area.
Worldwide
China
COST
USA
Japan
Russia
Australia
%
44
28
9
6
2
1
COST
%
France 26
Germany 18
UK
13
Spain
8
Israel
7
Italy
5
Portugal 5
Underpinned by meticulous, aqueous speciation studies in France and Sweden, new frontiers
emerged from this renaissance, including the ability to incorporate a wider range of elements or
organic functionalities, expansion into non-aqueous solvents, the preparation and characterization of
giant POMs and the assembly of POMs into micelles and vesicles. Parallel developments in
catalysis, magnetism, photochemistry and medicinal applications served to attract even more
interest. As powerful computing facilities became more readily available, theoretical groups began
to tackle these large, complex inorganic molecules with increasing success and analysis and
predictions of electronic and hence spectroscopic properties are becoming more reliable.
The detailed understanding of fundamental POM chemistry (e.g. self-organisation and assembly
from complex mixtures of precursors) remains a major challenge which will be addressed in this
Action through advances in the state of the art. The following examples serve to illustrate current
state of the art and how it will add new dimensions to MN.
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
Chemists can systematically manipulate POM size, shape and functionality and incorporate
selected elements or organic groups into specific positions. This tuneability of molecular
features is unmatched in inorganic chemistry.

POMs are thermally robust and can undergo multiple redox processes without structural
change or degradation, hence their potential as sustainable oxidation catalysts or storage units
in molecular memory devices, molecular transistors and single-molecule spintronics.

The redox and superacidic properties of POMs can facilitate proton-coupled multiple electron
transfer, e.g. for photochemical water oxidation, and O2 reduction in fuel cells.

POMs serve as a platform for molecular quantum magnetism, allowing research on spin
arrays giving rise to diverse characteristics such as molecular spin frustration and associated
features, or magnetic metastability common to single-molecule magnets.

Methods are emerging for the surface immobilisation of POMs and for their assembly into
complex, cooperative systems.

Living cells have been observed to interact with POMs, suggesting new biomedical
applications.
The holistic application of POM expertise to MN is a major innovation in itself, and it should be
noted that all of the above expertise is available within Europe to a greater extent than in the USA,
Japan and China. This gives Europe a distinct advantage for the creation of a unique coordinated
network that encompasses all aspects of POM-related science.
B.3 Reasons for the Action
This Action is crucial to the development of European POM science, which is currently carried out
by largely independent, separate groups. It will provide a platform for collaboration and exchange
that will integrate European POM research, create a strong, coherent, high-profile POM community,
and facilitate the assimilation of POM chemistry into cutting-edge nanoscience. Without this
coordination, the timely translation of this expertise into world-leading MN-based technology could
be jeopardized by the expanding Chinese POM effort. For example the ‘Institute of
Polyoxometalate Chemistry’ at Northeast Normal University in China has assembled the largest
group of POM chemists in the world.
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Immediate benefits include:

Broader-based training for ESRs.

Accelerated advances in POM chemistry through mutual awareness of research programmes,
sharing of facilities and access to pre-publication data within a trusted environment.

Maximization of research impact and elimination of wasteful duplication.

Greater opportunities for interdisciplinary innovation through cross-fertilisation of ideas.

Easy access to a unique pool of talent, technical expertise and IP.

Critical mass that will assist in funding applications.
Over the longer term, further benefits are envisaged, including:

A higher profile that will attract the best young researchers to world-leading interdisciplinary
MN projects.

Greater openness within the European POM community.

A stable, long-term future for globally-competitive POM chemistry in Europe.
PoCheMoN is aimed mainly at scientific and technological advances; the Training Schools,
Workshops and Short-Term Scientific Missions, aimed principally at Early Stage Researchers
(ESR), will improve the education and provide enhanced career pathways of younger scientists in
the area.
This Action will address globally recognised major challenges in POM chemistry and will also
stimulate interactions with researchers from non-COST countries, e.g. the USA, China, Russia and
Australia (where similar networks are non-existent).
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B.4 Complementarity with other research programmes
This Action is a direct result of an European Science Foundation Exploratory Workshop on
"Polyoxometalate-Based Nanoscale Devices". The core POM research of PoCheMoN is separate
from other network programmes, and any overlap with existing networks only concerns peripheral
aspects but serves to highlight complementarities. For example, research in PoCheMoN associated
with POM-based MN faces similar challenges in terms of characterisation to those identified in the
MPNS (Materials, Physics and Nanosciences) COST Action MP0901 (Designing novel materials
for nanodevices: from Theory to Practice). Indeed, for PoCheMoN to succeed it must stimulate new
interactions between POM chemists and MPNS groups with complementary skills. The most
relevant theme within FP7 is NMP (Nanosciences, nanotechnologies, materials & new production
technologies) and, although there is no direct overlap with current projects, PoCheMoN will
provide expertise that will benefit nanosciences in general.
C. OBJECTIVES AND BENEFITS
C.1 Aim
The aim of the Action is to provide a platform for coordination and cooperation in European
polyoxometalate research that will accelerate advances in (i) fundamental polyoxometalate
chemistry and (ii) world-leading polyoxometalate-based molecular nanoscience.
C.2 Objectives
PoCheMoN will make a significant contribution to the ERA (European Research Area) in terms of
shared capability, training and coordinated research with regard to the following objectives.
High-level objectives

Invigorate and grow European POM research

Provide coordinated broad-based training for ESRs

Accelerate advances in fundamental POM chemistry
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Develop world-leading POM-based MN

Create new technology with POM-based MN
Specific scientific objectives

Develop a wider range of rational POM synthesis methods.

Advance state of the art analytical techniques for POM chemistry and POM-based MN.

Develop improved computational methods for POMs.

Achieve precise manipulation of POMs on surfaces – from monolayers to single molecules
Deliverables against these objectives

A higher profile for European POM research within Europe and worldwide

Larger numbers of ESRs in POM chemistry and POM-based MN (aim initially at 10%
increase)

New ambitious joint research projects (at least 2 per year)

Increased number of joint publications from PoCheMoN participants (at least 10 per year)

High profile international meetings on POM science held in Europe (two or three)

Fabrication of one or more devices using POM-based MN.
Regular interactions between participants will prevent isolation of smaller research groups and
provide a large, well equipped consortium within which they can make valuable contributions to
ambitious projects.
C.3 How networking within the Action will yield the objectives?
An indication of how the Action PoCheMoN will achieve the various objectives is given below.
Profile – By establishing PoCheMoN, the European POM community will immediately raise its
profile, which will be further enhanced through dissemination of the Action's activities and outputs
as described in Section H.
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Assimilation of POM chemistry into MN – A proper appreciation of the capabilities and limitations
of state of the art nanoscience techniques is paramount before devising experiments to incorporate
POMs into MN systems. By forming strong links with MPNS scientists, particularly physicists and
device engineers, realistic targets will be established for POM-based MN. Several physicists have
already stated that they will join the network, some of whom have previous links with POM
chemists.
Accelerated advances – Through the various COST networking instruments, PoCheMoN will
identify key complementary capabilities where close collaboration could rapidly accelerate progress
or stimulate research in new directions. ESRs will be encouraged to bring their ideas to the fore and
provision of access to a wide range of techniques and facilities will enable original and innovative
ideas to be explored more readily. Collaboration will be facilitated by creation of an on-line
knowledge database which will hold all of the output from PoCheMoN as well as research project
details, pre-published data, archives from on-line discussions, and contact details. Methods for
sharing literature databases will be explored (e.g. Papers Livfe for the Mac). At least 10 Short-Term
Scientific Missions (STSMs) per year, at least 70% for ESRs, will be used for strategic visits or
exchanges to share knowledge or transfer skills.
Enhanced research output – In collaborations between experts in different sub-areas (POM
chemistry, computational modelling, surface science, scanning probe microscopy, molecular
magnetism and molecular electronics), access to the full breadth of analytical techniques and
computational capability will ensure that all aspects of a project are fully explored and that the
resulting joint papers are of the highest quality.
Training – Coordinated cross-disciplinary training through Training Schools and Workshops will
provide ESRs with a broad appreciation of the background science relevant to POM-based MN.
This, and the enhanced profile of the area, will help attract larger numbers of high-quality ESRs to
the area. The successful European School in Molecular Nanoscience (ESMolNa) will be used as a
basis for regular Training Schools and there will be a 'brain-storming' Workshop specifically for
ESRs, which they will organise. An application for a Marie Curie ITN is planned, and the
possibility of recording training sessions as video clips will be explored to add an extra dimension
to the available on-line material.
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New research projects – Where ideas generated lie outside current projects, PoCheMoN will
generate applications for new research projects funded by other Frameworks e.g. EU Framework
Programme and Marie Curie Fellowships, or by national funding agencies.
Industrial involvement – PoCheMoN will provide a single point of access to expertise in POM
chemistry and POM-based MN, initially through the website, but also via awareness sessions that
will be organised for interested companies. Existing industrial collaborators will be encouraged to
join the network and one has already indicated their enthusiasm to be involved.
Exploitation of research – In consultation with the IP departments of member institutions, a
Consortium Agreement (CA) will be established to provide a legal framework for
protection/exploitation of IPR (Intellectual Property Rights) in collaborations between different
institutions and/or industrial partners.
C.4 Potential impact of the Action
The benefits of this integrated approach to POM science can be summarised as below.
Benefits to the ERA – PoCheMoN will strengthen the European POM skills base, improve training
and establish a lead in a new branch of nanoscience. Advances in POM chemistry will benefit the
European chemistry, catalysis, materials and device communities and their associated industries and
the training will provide future leaders in the area.
Benefits to Early Stage Researchers (ESRs) – The broad-based appreciation of the wider science
involved in POM-based MN provided by Training Schools, Workshops and STSMs will enhance
career prospects of these researchers. Opportunities will also be provided to take on leadership roles
within projects and engage in project design.
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Benefits to network partners – In addition to the benefits of interdisciplinary collaboration itemised
in Section B.3, PoCheMoN will enable researchers to apply their research to high-level integrated
projects, which will enhance research quality and scientific reputations and establish long-lasting
collaborations. Training sessions also represent continuing professional development (CPD) for
mid-career scientists, which will assist career progression.
Technological benefits – A deeper understanding of POM chemistry with an ability to immobilise
and characterize POMs on surfaces will establish new methods for fabricating nanoscale devices
that ultimately will provide European industry with a competitive edge in disruptive new
technology; surface-appended POMs provide a direct route to adjust and enhance current CMOS
(complementary metal–oxide–semiconductor) technology. Once established, PoCheMoN will
enable any technologist to easily gain access to experts in POM science.
Longer-term societal benefits (economy, jobs, welfare) – These will arise through incorporation of
cutting-edge POM chemistry into potentially disruptive MN applications that will fuel new regional
and global economies. The catalytic, photocatalytic, electronic and magnetic properties of POMs
are already being investigated for e.g. environmental clean-up and water purification (oxidation),
solar energy conversion (water splitting), fuel cells (oxygen reduction) , molecular electronics or
molecular spintronics (switchable electronic/magnetic states), and other applications are envisaged.
The training and joint research experience afforded to ESRs will prepare them for leading roles in a
technology-based economy.
C.5 Target groups/end users
PoCheMoN is primarily centered on basic research and, as such, it targets the European academic
research groups active in POM chemistry and Molecular Nanoscience. Early Stage Researchers are
at the focus of the training components of this Action, in particular the workshops, Training
Schools, and STSMs. In addition, companies active in the development of new device technology
or in the application of POM-based catalysis will gain advantage by interacting with the network,
and a dialogue will be maintained with companies that can directly exploit near-to-market
applications e.g. POM-modified CMOS for gas sensors.
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D. SCIENTIFIC PROGRAMME
D.1 Scientific focus
PoCheMoN will nucleate interactions leading to innovations in POM synthesis, surface assembly
and immobilization, physical measurements and analysis in the drive to achieve (i) the advancement
of fundamental POM chemistry and (ii) the development of POM-based MN. Four complementary
Working Groups (WGs) and associated research tasks are outlined below. These tasks are not
mutually exclusive and projects will necessarily be interconnected in order to achieve the goals.
WG1. POM chemistry and characterisation
Targeted synthesis and reactivity of functional POMs and multifunctional POM-based hybrid
materials.
The number of structurally characterised POMs has grown enormously over recent years, while the
detailed understanding of POM formation has advanced much more slowly and remains a major
challenge. This task will advance the rational, designed synthesis of POMs with specific properties,
and provide a deeper understanding of fundamental POM chemistry through systematic reactivity
studies. Specific targets for synthesis will emerge in discussions between chemists, physicists and
materials scientists. One particular focus will be detailed investigations of solution speciation using
a range of new and established techniques.
Exploration of supramolecular interactions
Supramolecular, non-covalent interactions are involved in the formation of POMs as well as in the
higher-level aggregation of POM building blocks into larger structures, and also leads to the
emergence of self-organising 'system-level' functions. It is clear that, in addition to interactions
between cations and the oxide surfaces of POMs, a range of O---H–E interactions (E =, N, O etc)
must also be considered, while incorporation of Lewis acidic or basic heteroatoms in the POM
framework provides extra sites for association with organic or inorganic species. This task will
identify ways to use these interactions for controlled assembly of POMs into functional structures
(WG2).
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Development of state-of-the art analytical techniques* (see below)
WG2. POM-based materials and modified surfaces
Self-assembling POM-based materials and supermolecules
Electrostatic interactions with cations can cause POMs to self-organise and assemble in solution,
and aggregation through oxo bridges or organic linking groups is also possible. These interactions
will be used for the controlled assembly of large, functional, molecular systems or new extended
solid materais. Self-organising systems showing non-equilibrium emergent behaviours will also be
targeted.
POM-based nanostructures e.g. monolayers, thin films and hierarchical superlattices.
POMs exhibit high affinities towards a diverse range of surfaces, including those of carbon
nanotubes, metallic nanoparticles, or ionic nanocrystals. Electrostatic, coordinative and covalent
interactions will be tuned to control POM surface monolayer deposition and subsequent aggregation
to give multi-layers or superlattices. The attachment of functionalised POMs to defect sites of metal
oxide surfaces will be investigated as a means of integrating POMs into CMOS devices.
Position, immobilize and organise POMs on surfaces.
The study of isolated, individual, immobilised POMs represents one of the ultimate challenges in
POM-based MN. In working towards this goal, initial experiments will be aimed at controlled, lowdensity dispersed monolayers in order to learn how to (i) achieve site-specific binding to the surface
and (ii) prevent aggregation into ion clusters. Strategies for the connection of electrodes to a single
POM sited on a charge-injection gate will be explored and, with input from computational groups to
match the charge transport properties of the clusters to the electrodes in real devices, will result in
new POM-based CMOS technologies.
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Development of state-of-the art analytical techniques* (see below)
WG3. Physical characterization and theoretical modelling
Properties of extended POM systems and isolated POMs in nanoscale systems.
The collective expertise of the European POM community in elucidating structural, chemical,
electronic, and magnetic characteristics of POMs represents the current state-of-the-art, and a key
development will be single-molecule microscopy studies of POMs deposited on substrates where, in
the case of scanning tunnelling spectroscopy, the widespread redox stability of POMs will be
advantageous.
Theoretical modelling of chemical, electronic and magnetic properties of POM nanostructures and
single molecules.
Modern computational methods are being applied with some success to the study of spectroscopy,
magnetism, structure and reactivity of POMs, providing insight into and rationalisation of chemical
and physical properties. However, the quantum mechanical model, where the number of atoms is
minimised to reduce computing time, is in tension with the physical model, i.e. POM structures,
solvent, counter ions and any substrate present. Inclusion of all components leads to large
simulation systems (there is typically a cubic scaling with system size). Collaborations with
physicists developing the AIMPRO software system will be aimed at significantly reducing
computation times without introducing approximations. Charge transport through POMs as
tunnelling devices will be explored using non-equilibrium Green's functions with a view to
matching the work function of electrodes to the molecular properties of the POM.
WG4. Applications of POM-based molecular nanoscience
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POM spin qubits for quantum computing.
POMs are candidates for spin qubits with long quantum decoherence times, where the sources of
decoherence (nuclear spins, magnetic dipolar interactions) can be minimized by tuning the POM
chemistry. In addition, these qubits can be coupled in a single POM molecule to produce quantum
gates. Collaboration between POM chemists and physicists has established the theoretical
possibility of controlling the coupling between two spins situated on groups at opposite sides of a
POM by manipulating, via an electric field/current, the electron spin density on the reduced POM.
Also, proposal for new Flash-RAM and D-RAM using POMs has emerged from collaborations
between chemists and electrical engineers. Target POMs are being synthesised to build a device in
which switching and data storage is realised, and the next challenging steps require close
collaboration between the various groups, which will be coordinated by PoCheMoN.
Spintronic devices based on POM single molecule magnets.
A new approach towards molecular spintronics aims to utilise molecular magnets to realize
nanospintronic devices analogous to the classical spintronic devices (spin valves) but exhibiting
quantum effects. The charge states of molecular magnets based on redox-stable POMs, embedded
in the environment of a single-molecule transistor, can be addressed by a gate field and is expected
to result in a multitude of charge-transport mechanisms. Experiments will be carried out to
understand the effects of contact with the interfaces of extended solid on the POM electronic and
magnetic properties, e.g. hybridization with surface states or charge transfer effects that affect spinorbit coupling within the clusters. Introducing self-assembled monolayers of POM molecules at the
organic/inorganic interface of a hybrid spintronic device, with the aim of tuning the spin injection
from the ferromagnetic electrode to the organic spin collector, may provide a way of improving the
efficiency of molecular-based spin valves.
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Develop far-reaching ideas for data storage and manipulation.
In molecular electronics, the redox and structural stability of POMs provides advantages over
classical coordination complexes, the handling of which on redox-active interfaces is frequently
limited by their lability. Chemically interlinking POM building blocks to one-, two-, and threedimensions in a controlled manner will provide be a multitude of routes towards fieldprogrammable architectures and/or neuromorphic concepts with a density of functions and
switchable states, which is larger than for any other approach.
POM-based catalysts for small-molecule activation e.g. H2O, O2, CO2.
POMs offer unprecedented opportunities to design and engineer active catalytic sites in metal oxide
environments, as highlighted by recent advances in POM-catalysed water oxidation. PoCheMoN
will bring together groups working on POM synthesis, surface immobilisation and catalysis to
explore the assembly of robust, nanoscale, POM-based synthetic enzymes (synzymes) and, in a
highly ambitious MN approach, study fundamental chemical and electron/energy transfer processes
in immobilized multifunctional systems. New water-splitting devices that use the redox properties
of POMs will be developed with electrical and chemical engineers.
Biomedical applications of POM-functionalised nanosurfaces.
POM-protein and POM-carbohydrate interactions will be investigated in order to understand the
effects of this type of binding on enzyme activity and cell behaviour. Through these studies, POMbased MN might be used to control biological systems by coupling these interactions with
proton/electron transfer, photoactivation etc.
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Photo-chemistry/physics of POMs for photocatalysis and charge separation and storage.
This WG will investigate the photochemistry and photophysics of POM-based assemblies.
Conjugate systems with e.g. organic dyes or semiconducting nanoparticles anchored to POMs will
be explored as innovative solutions for light-harvesting devices in the context of photochemical
water splitting or solar cells.
* Development of state-of-the art analytical techniques
Rather than have a separate WG it will be more beneficial to have experts in the relevant techniques
in the appropriate WG. For example, WG1 will require mainly 'molecular' analytical techniques,
whereas surface analysis is more relevant for WG2. Some techniques have well-established
methodologies that may not be available to all researchers, so sharing of expertise, best practice and
emerging developments is important.
Human resources for these tasks will comprise (i) undergraduate research project students, who
may engage in ERASMUS exchanges, (ii) PhD students, (iii) PDRAs (post-doctoral Research
Assistants), (iv) experienced Principal Investigators, while technical resources comprise (v) high
quality laboratory provision, (vi) specialist equipment for synthesis and molecular characterisation,
(vii) software for computation and (viii) state-of-the-art surface analysis. These are nationally
funded resources, but the Action PoCheMoN will deliver added value through collaboration and
resource sharing.
D.2 Scientific work plan – methods and means
Efficient communication between WGs is essential to gain maximum benefit from the Action
PoCheMoN. WG1, WG2 and WG3 are highly inter-dependent, and all three provide the basis for
advances in WG4. Feedback of results via e-mail or the website will optimise experiment design
and identify any bottle-necks in the work. Some specific details and examples within the context of
the WGs are given below.
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WG1. POM chemistry and characterisation
Targeted synthesis and reactivity of functional POMs and multifunctional POM-based hybrid
materials.
Separate groups have developed different methodologies. Aqueous approaches generally
involve pH-triggered polycondensation, hydrothermal assembly or the use of nucleophilic lacunary
species to assemble larger structures. In non-aqueous solvents, hydrolytic condensation of metal
alkoxides in the presence of nucleophilic oxometalates provides rational and systematic access to a
range of derivatised POMs and this method also provides an efficient way of introducing 17O
enrichment for NMR studies. The introduction of organic functionalities is sometimes possible in
water, but is more often achieved in organic solvents. Expertise will be combined to focus on
specific targets, decided in discussions with theoreticians, analytical chemists, physicists and device
engineers. Capabilities that will improve through cooperation include (i) inclusion of heteroatoms
from s-, p-, d- and f- blocks, (ii) the use of pre-formed functional building blocks to link POM subunits, (iii) the grafting of electrophilic moieties onto reduced, electron-rich
POMs. Polycondensation and other assembly processes are little understood and techniques such
as ion-trapping in combination with e.g. electrospray and cryospray mass spectrometry, 2D
multinuclear NMR, X-ray absorption and enhanced-Raman spectroscopies will be used to shed light
on these fundamental processes. The first time-resolved, variable-temperature EXAFS studies of
hydrolytic aggregation were recently carried out and PoCheMoN will seek to extend interactions
with synchrotron scientists.
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WG2. POM-based materials and modified surfaces
Self-assembling POM-based materials and super-molecules
The identification of nanoscale metal-oxide rings with 140 to 154 molybdenum atoms, formed in
reduced aqueous solutions of MoO42–, opened the door to a world of 'self-assembled' inorganic 'big
rings' and 'Keplerate' nanocapsules. Reliable routes to these amazing POMs have provided building
blocks for new types of active metal oxide-based architectures with dynamic behaviour and tunable
porosity. The stabilisation of metal nanoparticles (MNPs) by POMs provides interesting
possibilities for POM-based MN. The nature and properties of the metal-POM interface in these
systems has yet to be properly explored and only the simpler POMs have been used to date. One
can imagine that the properties of the MNP might be manipulated via the chemistry of the POMs at
the surface, and that isolated MNPs might be used as individual components in MN. Such scenarios
will be explored by collaborations between groups with the relevant expertise.
POM-based nanostructures e.g. monolayers, thin films and hierarchical superlattices.
The construction of superlattices on surfaces by (i) the functionalisation of POMs to give polytopic
building blocks and (ii) connection through complementary organic linkers/spacers will be
explored. This approach has been used for the preparation of POM-organic framework materials
(POMOFs), providing a way of introducing new functionality into extended solids but, in this case,
assembly will originate from a surface monolayer by designing the chemistry to prevent
aggregation away from the surface.
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WG3. Physical characterization and theoretical modelling
Properties of extended POM systems and isolated POMs in nanoscale systems.
Charge transport and spin-injection experiments utilizing multi-tip scanning tunneling microscopy
and conducting atom force microscopy are planned on individual well-characterized magnetic
POMs, in particular redox-active POMs with diameters up to 3 nm. Special attention will be given
to the development of strategies for handling and depositing POMs under the UHV
conditions necessary for handling reactive metallic surfaces. An understanding of the electronic
interactions between redox-active POMs and conductive interfaces will be obtained through
spatially resolved spectroscopy variants such as angular-resolved photoemission or Xray magnetocircular dichroism. New experimental tools are critical for the development and
optimization of novel devices.
Theoretical modelling of chemical, electronic and magnetic properties of POM nanostructures and
single molecules.
Computational groups in Europe have extensive experience in the use of e.g. DFT and ab
initio methods, molecular dynamics, Carr-Parrinello molecular dynamics, surface state methods and
other techniques to study POMs. PoCheMoN will establish wider cooperation between synthetic
and computaional groups, including the developers of AIMPRO, to address specific projects that
require new computational strategies, e.g. in the calculation of: NMR chemical shifts; electronic
properties of POMs on surfaces; interactions between cations and POMs in solution; very large
POMs; photochemistry and photophysics of POM-based assemblies; magnetic properties of POMs;
reactivity of POMs relevant to catalysis. AIMPRO has significantly improved calculation speed
without introducing any approximation, and systems of 1000s of atoms are routinely within reach at
a first-principles level of theory. Tests using the software for properties of individual POMs, as well
as POMs localised on a Si surface in solution with the explicit inclusion of counter-ions and solvent
species have shown AIMPRO to be suitable for use as a complementary technique. There is an
existing community of AIMPRO users throughout Europe, exploring diverse systems, including
metal oxides, for electronics and opto-electronic applications.
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WG4. Applications of POM-based molecular nanoscience
POM spin qubits for quantum computing and spintronic devices
Several approaches are envisaged: (1) In one particular type of capped, reduced POM, the spin
coupling between {VO}2+ caps is determined by the spin density on the electron-rich core, and can
be switched through electrical oxidation/reduction of the core in an STM setup. Different redox
states of this POM will be synthesised and immobilised on suitable surfaces with a view to
developing spintronic type devices, which will be useful as spin quantum gates, and targets for
related systems will be identified for synthesis; (2) a POM will be placed between two electrodes in
a single-molecule transistor structure to enable measurement of the effect of applying a magnetic or
electric field on the transport through these molecules. Both magnetic and non-magnetic POMs with
suitable functionalities will be used, with the extra option of using magnetic electrodes; (3) layered
heterostructures will be fabricated in which POM monolayers will be deposited onto a
ferromagnetic surface, then covered by a thin layer of an organic semiconductor onto which a
ferromagnetic metal will be evaporated. This type of spin-valve configuration will be investigated
to establish the role of the interfacial POM in improving the spin injection and hence the efficiency
of the device. A variety of POM molecules with different electron acceptor capabilities (i.e. redox
properties) and magnetic character will be tested. In order to promote SAM formation on the
ferromagnetic surface, the POMs will be functionalisated with an organic 'tail'.
Biomedical applications of POM-functionalised nanosurfaces.
The biological activity of POMs is well documented but details of molecular interactions remain
largely unknown. The incorporation of POM chemistry into biological nanoscience could provide
advances in drug discovery, imaging and sensors as well as providing an insight into degenerative
disease development (e.g.Alzheimer's). Discussion groups within PoCheMoN will establish the
state of the art and provide a vision for POM-based biomolecular nanoscience. Experts within
PoCheMoN have already isolated enantiopure POM-peptide conjugates and developed the use of
DOSY NMR to study the effect of POMs on enzyme kinetics.
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Photo-chemistry/physics of POMs for photocatalysis and charge separation and storage.
Illumination at the O to M charge-transfer band of POMs renders them powerful oxidizing agents,
and oxidation of organic compounds accumulates electrons on the POM that can be
delivered, via thermal reactions, to a variety of oxidants. Hence, photocatalytic processes can be
devised in which POMs serve as electron relays. The POM environment can leverage multi-electron
catalysis in a narrow potential window by establishing a staircase of low energy intermediates,
coupled proton translocation and template bond formation/dissociation events. Key discoveries in
the field of artificial photosynthesis involve new POM-based water oxidation catalysts which mimic
the oxygen evolving center of the photosynthetic II system (OEC-PSII). These unprecedented
molecular catalysts enable solution-phase photo-induced electron transfer in the nano- to microsecond time scale, far surpassing the activity of state of the art catalysts. Breakthroughs have been
also obtained in CO2 reduction and O2 activation. All of this expertise is within PoCheMon, and its
translation to the assembly of multifunctional synzymes for chemical devices or nano-reactors will
be facilitated by close links with surface scientists in the network.
E. ORGANISATION
E.1 Coordination and organisation
The management and organisation of this Action conforms to the COST Document 4154/11 "Rules
Procedures for implementing COST Action". Specifically, the Action will run for 4 years and will
be managed by a Management Committee (MC), whose members will be nominated in the
respective participating COST Countries.
In the initial stage the Action will be widely publicised via learned society websites, e-mail
distribution, at conferences and social networking (LinkedIn etc) to promote participation.
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The MC will also be responsible for the Action budget, and will ensure a significant allocation of
funds to the Short-Term Scientific Missions (STSMs), Training Schools and workshops. During the
first MC meeting, the MC will appoint:

The Action Chair (AC), Vice-Chair (VC)

The Working Group (WG) Coordinators

The STSM Manager

The Training Schools and Workshops Coordinator(s)

The Website and Dissemination Manager
Working Groups will have their kick-off meetings within three to four months from the first
MC/kick-off meeting.
A Steering Committee (SC), formed by the AC and VC, Website and Dissemination Managers and
the WG Coordinators will be responsible for interaction with and recruiting new research groups
interested in joining the COST Action. The SC will work in close contact with the Dissemination
Manager who may also act as Web Manager.
Membership of WGs will be competitive and based on research quality and complementarity to WG
members. It is therefore important for the efficient operation of this Action that the WGs capture the
full portfolio of current and recent research projects being undertaken by the participants in order to
establish the scope for inter-disciplinary interactions. This information will be collated by the MC,
made available via the website and will give an indication of the dimension of the Action. This will
be monitored for the duration of the Action, providing a means of establishing the effectiveness
PoCheMoN.
Milestones include: (i) successful installation of AC, VC and WGCs, (ii) assignment of participants
to WGs (iii) establishment of new research collaborations (iv) receipt of annual reports, (v)
successful completion of events.
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E.2 Working Groups
The research of this COST Action will be organized in four Working Groups, each of which will be
led by a Working Group Coordinator with an Assistant Coordinator. Wherever possible, one of
these positions in each WG will be held by an ESR in order to promote leadership capability within
the Action.
The WG Coordinator and/or Assistant Coordinator will be responsible for:

Setting and monitoring WG milestones

Coordinating WG contributions to the website

Interacting with the Website and Dissemination Manager

Coordinating the WG meetings (about one per year)

Leading the scientific discussions

Interacting with the STSM Manager for managing the STSMs within the WG

Participating in the Steering Committee

Requesting and collecting Annual Reports from individual participants

Writing reports of the WG activities
In many ways, these are the most important operational tasks of the Action and diligence is
essential for the success of the Action.
The progress of the different activities, especially the STSMs involving ESRs, will be recorded in
the annual Monitoring Progress Report.
Projects within different WGs will necessarily be interconnected in order to achieve their goals. To
coordinate these links, a matrix of interacting researchers will be distributed amongst the WGs to
ensure cross-fertilisation, sharing of best practice and avoidance of duplication of effort. This will
allow new expertise to be imported into projects, and some areas to be modernised by introduction
of new challenges. The establishment of a PoCheMoN industry focus group (IFG) will provide an
awareness of developing technology road-maps that can immediately build on new fundamental
developments from WGs.
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E.3 Liaison and interaction with other research programmes
The Action will highlight any events that are pertinent to PoCheMoN. Similarly, where Action
members who are also involved with other COST Actions, e.g. D40 ‘Innovative Catalysis: New
Processes and Selectivities’ and MP0901 'Designing Novel Materials for Nanodevices: from Theory
to Practice', become aware of anything relevant to PoCheMoN, they will be encouraged to
disseminate the information promptly by electronic means (e-mail, website), where it will be
captured and reported at MC meetings. Where there is a perceived need, joint seminars or
workshops may be organised for the mutual benefit of the respective Actions.
E.4 Gender balance and involvement of early-stage researchers
This COST Action will respect an appropriate gender balance in all its activities and the
Management Committee will place this as a standard item on all its MC agendas. The Action will
also be committed to considerably involve early-stage researchers. This item will also be placed as a
standard item on all MC agendas.
With regard to gender balance, women's participation in research will be encouraged both as active
participants and as part of the evaluation, consultation and implementation processes. All efforts
will be made to maintain a good gender balance throughout the management structure of the Action.
To grow the proportion of female participants in the Action, participating research groups will be
instructed to ensure that any young female researchers, including postgraduates, are made fully
aware of PoCheMoN and given every opportunity to participate. Female ESRs will be offered
support as necessary to address any gender-related issues that may affect their research career
or participation in the Action and, to this end, the Action will provide mentoring from among the
senior female contingent and, if there is the demand, an online women's discussion area on the
website. Any issues identified will be raised at Management Committee meetings.
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With regard to ESR involvement, it is the intention of the Action to maximise the Action resources
available for training through STSMs, Training Schools or Workshops and to actively encourage
ESRs to become involved. In addition, ESRs will be appointed to positions of responsibility within
PoCheMoN wherever possible. In particular, the Website and Dissemination Manager(s) will be
ESRs, given their greater familiarity with modern social networking and the Action wishes to
exploit the dynamic imaginations of its younger members.
STSMs will be identified that provide maximum benefit not only to the respective research groups
but specifically to the ESRs. Potential STSMs will be discussed at WG meetings in order to
highlight scientific and cultural issues associated with the visits and provide an opportunity for the
ESRs to familiarise themselves with the host institution and access any relevant information well in
advance of the event.
For all training events, PoCheMoN Certificates will be awarded to recognise ESR involvement and
achievement. Attendance and performance will be monitored and recorded by the host/organiser.
WGs will also the highlight the availability of Conference Grants offered by the CMST (Chemistry
and Molecular Sciences and Technologies) Domain Committee and encourage suitable ESRs to
apply for these.
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F. TIMETABLE
The general Timetable for this four-year Action is indicated below, which is flexible. Numbers of
STSMs and workshops will be determined by the WGs and MC and the timing of Training Schools
will depend upon when the Action starts. It is intended to use the established European School for
Molecular Nanoscience as a kernel for the organisationTraining Schools, and this is usually held in
October. As far as possible, meetings will be timetabled to coincide with events to minimise
expenses and maximise funds available for STSMs and training events.
Year 1
MC established; 1st MC/Kick-off meeting and designation of Action Chair
(AC), Vice-Chair (VC), Working Group Coordinators, the STSM Manager,
the Schools Coordinator, the Steering Committee and the Website and
Dissemination Manager.
WG meetings; Steering Committee (SC) and MC meeting; STSMs; proposal
for WG Training Schools and workshops.
Year 2
MC Meeting for mid-term evaluation preparation. WG Training Schools.
WG meetings and Steering Committee Meeting. STSMs. Conference
Year 3
MC meeting and proposal for WG Training Schools. WG meetings and
Steering Committee Meeting. STSMs. Workshops.
Year 4
WG meetings. SC and MC meetings for Action closing conference and for
final evaluation preparation. WG Training Schools. Closing conference and
MC meeting for final report.
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G. ECONOMIC DIMENSION
The following COST countries have actively participated in the preparation of the Action or
otherwise indicated their interest: BE, CH, DE, EL, ES, FR, IE, IL, IT, NL, PL, PT, SI, UK. On the
basis of national estimates, the economic dimension of the activities to be carried out under the
Action has been estimated at 56 Million € for the total duration of the Action. This estimate is valid
under the assumption that all the countries mentioned above but no other countries will participate
in the Action. Any departure from this will change the total cost accordingly.
H. DISSEMINATION PLAN
H.1 Who?
Several communities can be identified as targets for outreach and dissemination.
1)
The PoCheMoN community
2)
The Scientific Community (the international POM community; the international nanoscience
community; the more general scientific community including learned societies and students in
Higher Education)
3)
Policy-making bodies (including national and European funding organisations)
4)
Industry
5)
The general public (including school-teachers and schoolchildren)
H.2 What?
Dissemination methods will be tailored to match the targeted audience and can be summarised as:
Internal activities

Website information in restricted or open area.

e-Mail distribution.
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Publications in high profile peer-reviewed international journals.

The COST Action consortium will endeavour to convene and manage international
congresses in the area of molecular metal oxides and related fields.

Short-Term Scientific Missions between the COST participants will allow for dissemination
of knowledge among adhering countries.
External activities

Open pages of the website.

The Action will be presented at major international and national congresses and workshops.

The Action will be described in Wikipedia.

YouTube/iTunes U presentations will be created.

COST Action profiles on popular community portals (Facebook, Twitter) will be created.
In addition, PoCheMoN will aim to identify and offer suitable speakers for Public lectures, Schools
events and public discussion sessions. In addition, individuals will be identified who have the
necessary skills to interact with the media (e.g. popular science magazines, TV, radio) for interview
regarding research advances
The Dissemination Manager, who will be an ESR, will be tasked with devising imaginative
methods to convey high impact messages.
H.3 How?
The communication model is designed to:
1)
Define the intended goal for the information to be communicated (e.g. research data,
significant advances etc.).
2)
From the intended goal the groups required to achieve the goal can be identified.
3)
Once the targets are determined, the most suitable way for the message to be sent can be
identified (e.g. an economic argument can be presented to a company).
4)
The most suitable medium can be selected to convey the message such as a trade magazine or
a scientific conference.
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The scientific community will be reached mostly through meetings, workshops conferences,
publications and the Action’s website. The website will be used to disseminate information and
outputs to all end-user groups and stakeholders, as summarized in H.1. Furthermore, direct contacts
will be needed to interact with policy makers, governmental and international organizations and to
recommend future European research programs and actions. The strong network of internationally
recognized experts that is already in place makes such connections possible. It is emphasized that
the dissemination strategy and implementation will be both proactive and responsive, remain
flexible and throughout the project to include innovative ideas, actions and campaigns that will
further increase awareness on the field. Action participants will be encouraged to facilitate the
dissemination of findings through their own national and local networks.
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