Curriculum Vitae

RUHLMANN Laurent, Jean-claude, Jacques

Nationality: French

Phone: 00-33-(0)3 68 85 14 15

Position: Full Professor, permanent staff (PR CE)

Institute of Chemistry – UMR 7177

Director of the Laboratory of Electrochemistry and

of Physical Chemistry of Solid State

CS 90032

F-67081 Strasbourg Cedex, France.

Email: lruhlmann@unistra.fr

SKILLS

(a) Expert with porphyrin and polyoxometalate chemistry as well as formation of hybrid

organic – inorganic chromophore(s) – polyoxometalate complexes. (b) Expert with

photocatalysis, electrocatalysis and photoelectrocatalysis. (c) Expert with the electrochemical

techniques: coulometry - and exhaustive electrochemical synthesis (preparative

electrochemistry) - polarography, spectroeletrochemistry (UV-vis-NIR-IR, cyclic and

stationary voltammetry, etc… (e) Expert with purification, characterization and studies of

organic and inorganic compounds (UV-vis, IR, Fluorescence, photochemistry and

paramagnetic and diamagnetic NMR techniques). (f) Familiar with ESR, photochemical and

magnetic studies. (g) Teaching undergraduate courses in electrochemistry, thermodynamic,

kinetic and general chemistry.

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Figure 2. Mechanisms for the photoreduction of silver ions by the use

of the porphyrin-POM complexes.

Research:

A) Hybrid Polyoxometalate - Porphyrin

The main goal is to obtain organic hybrids of polyoxometalates (POMs) and

porphyrins — molecules as well as polymeric materials — able to photocatalytically

reduce metallic ions, NOx (NO, nitrate, nitrite or CO2.

In these hybrid systems, the porphyrin sub-units will be used as photosensitizers

capable of delivering electrons to the strongly oxidant POMs under light irradiation.

The reduced POMs can then catalyze reductions, e. g. the reduction of the NOx or of

the metalic ions such as Ag(I), Au(III), Pt(IV), Pd(II), etc. The porphyrins can be

regenerated in the presence of a sacrificial electron donor.

• Our first objective is to prepare and characterize POM-porphyrin model

compounds helping understand and predict the characteristics required for good

photocatalytic properties. Several types of POM/porphyrin have been introduced

(Figure 1).

N

HNN

NHN

HNN

NH

Figure 1. Porphyrin(s) – polyoxometalate complexes obtained via coordination.

• The second objective is the

formation of electrostatic

porphyrins/POM complexes in

solution from tetracationic porphyrin

and polyanion (Scheme 1).

Then, visible light-induced reduction

of metal cations such as Hg (II), Cd (II),

Cr (VI), As (III/V)), as well as noble

metals with limited resources (Au(III),

Pd(II), Pt(II)...), and NOx under aerobic

and anaerobic conditions is pursued.

The main rationale for using these

porphyrin(s)-polyoxometalate

complexes is the possibility to carry out

photocatalysis with visible radiation,

contrary to polyoxometalates only.

Indeed, porphyrins are photosensitizers capable of giving electrons to polyoxometalates after

excitation, both through space and through bonds. The complexes are especially attractive,

because photocatalysis could proceed with solar radiation.

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Systems in solution

Previous experiments conducted using electrostatic porphyrins/POM complexes in

solution, have already given a positive outcome. Indeed, the electrostatic complexes obtained

using tetracationic porphyrins and polyoxometalate have shown a high efficiency toward the

model reaction of photocatalytic reduction of Ag(I) even under aerobic conditions. The catalyst

was stable under turnover conditions, which is an important criterion for this type of catalysis

and bodes well for future applications. Ag (I) was chosen as a model system because it

involves the exchange of a single electron. Thus, the photo-excitement of porphyrin units of

the complex in the presence of propan-2-ol (sacrificial donor) allowed the catalysis of Ag(I)

reduction in Agn.

The mechanism proposed for silver nanoparticle formation (Figure 2) corresponds to a direct

intramolecular electron transfer from the excited porphyrins to polyoxometalate. Then, the

reduced POM – porphyrins complex can transfer electrons to silver ions. The mechanism is

similar to that reported for the POM alone excited in the UV domain.

Figure 3. TEM micrograph of the formed silver nanoparticles and change in the UV–visible absorption spectrum after

illumination of aqueous solution containing A) [Co4(H2O)2(P2W15O56)2]16- (0.8.10-5 M) et [ZnTMePy]4+ (3.2.10-5

M) in the presence of sacrificial donnor propan-2-ol (0.13 M) and Ag+ (3,2.10-4 M). Aerated aqueous solution. B)

[Co4(H2O)2(P2W15O56)2]16- (0,8.10-5 M) in the presence of propan-2-ol (0.13 M) and Ag+ (1.28.10-4 M). Deaerated

aqueous solution.

Indeed, the preliminary results shows the efficient photocatalytic reduction of Ag+ in the

presence of the complex [ZnTMPyP4+]4[Na2FeIII2(H2O)(P2W15O56)2] using propan-2-ol as

sacrificial donor both in aerated and deaerated aqueous solutions (Figure 3). The formed silver

nanoparticles are stable in air without illumination.

Band of the

reduced POM

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• The third objective is the formation of supported tetracationic porphyrins – POM.

First, tetracationic porphyrins – POM multilayers were formed. The formation of

photocatalysts supported with tetracationic porphyrins and polyoxometalates has

been developed using [ZnTMePyP]4+ or (py)ZnOEP(py)44+ in the presence of

polyoxometalates in varied structures (Keggin or Dawson). More complex structures

of the type sandwiches [M4(H2O)2(P2W15O56)2]16-/12- (where M = Zn2+, Cd2+, Cu2+, Ni2+,

Co2+, Mn2+, Fe3+) have also been used.

The feasibility of this approach has been assessed by dipping a glass plate or a

transparent electrode of ITO (Indium Tin Oxide) in an alternated way, in a solution

0.5 mM of [ZnTMePyP]4+ and in a solution 0.5 mM of [Co4(H2O)2(P2W15O56)2]16-. Stable

multilayers were formed (Figure 4).

Figure 4. Left: UV-visible absorption spectra of [ZnTMePyP4+ / Co4(H2O)2(P2W15O56)216-]n films (onto quartz) with

different numbers of deposition cycles (after porphyrin and POM depositions). (The measured absorption

corresponds to the deposition of material on both sides of the quartz). Inset: Plots of the absorbance at 452 nm as a

function of the number n of deposition cycles of [ZnTMePyP4+ / Co4(H2O)2(P2W15O56)216-] in pure aqueous solution.

Middle: quartz slide with 25 with different numbers of deposition cycles. Right: TEM images of the silver

nanowires with the [ZnTMePyP4+ / Co4(H2O)2(P2W15O56)216-]n film in desaerated solutions.

The photocatalytic reduction of AgI2SO4 under visible irradiation in the presence of

propan-2-ol worked out well. It led to the formation of metallic Ag0 nanowires (Figure 4).

Second, our previous results showed that a supported catalyst, the cationic copolymer of

porphyrins can be prepared by electropolymerization of the bisubstituted monomer 5,10-

ZnOEP-meso-(bpy)22+ (1-Zn, Figure 5) via successive scannings between 0.9 V and 1.9 V /

SCE leading to the formation of directed nanostructures. Then, the "cationic" electrodes have

been soaked in a POM solution to generate a new material.

Figure 5. AFM a) of the copolymer 1-poly-Zn, and b)

of the modified electrode dipped 12 hours into a solution of K4[SiW12O40] (c = 1.10-3 mol.L-1).

• Our fourth objective is the formation of functional polymers including

polyoxometalate.

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The key-method for this approach was the electro-copolymerization of hybrid

porphyrins developed recently. It is based on the polarization of a working electrode

at the porphyrin’s second ring-oxidation potential in the presence of the

functionalized POM bearing two pyridyl groups [MnMo6O18{(OCH2)3CNHCO(4-

C5H4N)}2]3– (Py-POM-Py), which generates {POM-porphyrin}n copolymers after one

pot electropolymerization (Figure 6).

The photocatalytic reduction of AgI2SO4 or HAuIIICl4 under visible irradiation in

air in the presence of propa-2-nol at the 2-D interface between water and the

copolymeric films worked out well. It led to the formation of metallic Ag0 nanowires

and triangular nanosheets or Au0 nanosheets (Figure 6).

Figure 6. Electropolymerization of the 5,15-ZnOEP(py)22+ with the Anderson type polyoxometalate Py-POM-Py

leading to the copolymer porphyrin – POM. Cyclic voltammograms recorded during the electropolymerization,

AFM micrograph, TEM images of nanoparticles obtained after illumination in aerated solution of the copolymer

deposited on a plate of quartz in the presence of the sacrificial donor propan-2-ol (0.13 M) and of Ag(I) or Au(III)

(1.6 x 10-4 M).

The formation of hybrid POM-porphyrin copolymeric films (Fig. 7, film I) can be

obtained by the electro-oxidation of porphyrin in the presence of the POM bearing

two pyridyl groups (Py-POM-Py). This process is feasible for various type of POMs

such as Dawson, Lindqvist or Keggin type POMs (Fig. 8). A second methodology is

also proposed to form hybrid POM-porphyrin films (Fig. 7, film II): first the

formation of cationic poly-porphyrin electropolymer. Then, by metathesis reaction,

the (partial) exchange onto the surface of the initial counter ions by the POMn-. The

photovoltaic performances of these hybrid materials have been investigated by

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photocurrent transient measurements under visible-light illumination given by now

good efficiency.

Figure 7. Various type of porphyrin-POM films.

Figure 8. Left: Electropolymerization py-Dawson-py with ZnOEP. Right: EQCM and optical properties of the

films.

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• Our last objective is the formation of films based on covalent and electrostatic

interactions between porphyrin and Dawson type polyoxometalate. Their photovoltaic

performances are investigated by photocurrent transient measurements which showed

significant photocurrent response (Figure 7).

In the case of the example, the enhanced photocurrent, around 25 times higher for

the [-FeIIIP2W17O617-/ H2TPhN(Me)3P4+]n can be explained by the presence of

-FeIIIP2W17O617- which is a strong acceptor of electron and can take one electron from

the excited porphyrin. Then in turn, the reduced form can give one electron to

reduced I3-. Consequently, POM assists to relay the electron via a downhill

electrochemical cascade where the separated charges (oxidized and reduced) are

more taken away which decrease the charge recombination and simultaneously

enhance the photocurrent response (Figure 9).

Figure 9. Left: Schematic representation of the internal layer structure of [-FeIIIP2W17O617- / H2TN(Me)3PhP4+]m

film on a ITO substrate in the photo-electrochemical cell and schematic diagram showing electron transfer

processes. Right: Photoelectrochemical response for [H2TPhN(Me)3P4+] film (blue curve) [-FeIIIP2W17O617- /

H2TPhN(Me)3P4+]25 films (red curve) with on-off light illumination from 300 W Xe arc lamp (with 385 nm long

pass filter) in acetonitrile containing I3- 0.1 mol L-1 and I- 0.5 mol L-1. Applied potential:

-0.1 V vs. SCE.

B) Electrosynthesis of Di- and Poly-porphyrins

The electrochemical properties of porphyrins are now well established. Indeed, it is well

known that the oxidation of the -ring of a porphyrin proceeds via two one-electron steps

generating the -radical cation and the dication. The reactivity of porphyrin -radical

cations and dications with nucleophilic compounds has also been intensively studied. For

instance, a direct electrochemical oxidation of the -octaethylporphyrin (OEP) in the presence

of pyridine as Lewis base leads to substitutions of protons by pyridiniums in meso-positions

onto the macrocycle. Mechanism of such meso-substitutions is based on nucleophilic attacks

of the Lewis bases onto the electrooxidized macrocycle and is described as an ECEC process

(Figure 10). Similarly, such an electrochemical oxidation of the meso-tetraphenylporphyrin

(TPP) leads to -substitutions by pyridiniums. A similar reactivity of the oxidized porphyrins

has also been observed in using phosphanes as nucleophilic groups instead of pyridyl groups.

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Furthermore, this method has allowed the electrosynthesis of dimers, and more generally

oligomers, of porphyrins, either in using 4,4’-bipyridine which possesses two nucleophilic

sites, or in using porphyrins substituted by pendant pyridyl group(s). The control of the degree

of substitution of the oligomers obtained is permitted by a judicious choice of the applied

potential or in varying the number of pyridyl groups onto the porphyrin used as Lewis base,

respectively. Then, dimers and oligomers obtained possess pyridinium or viologen spacers

having interesting electrochemical properties (Figures 12-14).

Moreover, this reactivity-type of porphyrins has also allowed the development of an original

and easy methodology for the electropolymerization of porphyrins, in using porphyrins and

species having two nucleophilic sites. Such electropolymerization is performed with iterative

scans by cyclic voltammetry. With this method of electropolymerization, it is possible to

modulate easily the nature of the bridging spacers between the porphyrin macrocycles,

allowing the formation of polymers with specific chemical and structural properties.

Moreover, this novel way of electropolymerization opens up also interesting synthesis routes

for the elaboration of new functional materials. Indeed, for instance, copolymers containing

two different types of porphyrins can be obtained in using porphyrins substituted by pendant

pyridyl groups. Original organic-inorganic copolymers can also be obtained in using

inorganic compounds functionalized by two pendant pyridyl groups. For example, inorganic

compounds such as polyoxometalates, having interesting catalytic properties, can be

employed, the presence of the porphyrin within the copolymer allowing then a

photosensibilization for applications in photocatalysis.

Figure 10. E1CNmesoE2CB mechanism explaining the reactivity of a pyridine in meso-position of the ZnOEP.

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Figure 11. E1CNmesoE2CNCB mechanism explaining the reactivity of a pyridine in -position of the ZnTPP.

Figure 12. Electrosynthesis of di-porphyrins by electrooxidation of ZnOEP in the presence of 5,10,15-tritolyl-

20-(2-, 3-, or 4-pyridyl)porphyin.

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Figure 13. Electrosynthesis of di-, tri-, tetra- and pentaporphyrins via electrooxidation of ZnOEP in the presence

of free base porphyrin with pyridyl pendant group(s).

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Figure 14. Electrosynthesis scheme of the substituted ZnOEP(bpy)nn+ macrocycles (n = 1 to 4) and of the

ZnOEP(bpy2+-ZnOEP)n dimer (n = 1), trimers (n= 2), tetramer (n = 3) and pentamer (n = 4).

C) Polyoxometalates Functionalized by Tetrathiafulvalene and Spiropyran Groups

Polyoxometalates (POMs) functionalized by tetrathiafulvalene (TTF) molecules have been

synthesized at the Institut Lavoisier de Versailles, Université de Versailles Saint-Quentin

(Prof. P. Mialane, DR. A. Dolbecq et al) by a coupling reaction between the Anderson-type

POMs [MnMo6O18{(OCH2)3CNH2}2]3- or [AlMo6O18(OH)3{(OCH2)3CNH2}]3- and the TTF

carboxylic acid derivative (MeS)3TTF(S-CH2-CO2H). The mono-functionalized TTF-AlMo6

POM contains one TTF group covalently grafted on an Al Anderson platform. The

symmetrical TTF-MnMo6-TTF POM possesses two TTF groups grafted on each side of a

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C)

D)

Mn Anderson derivative while the asymmetrical TTF-MnMo6-SP POM contains a TTF and a

spiropyran groups (Figure 15). Their electrochemical and spectroelectrochemical properties

have been thoroughly investigated (Figure 16).

Figure 15. Schematic representation, abbreviation and synthetic procedures for the three POMs functionalized

by TTF groups. Blue octahedra = MoO6, orange octahedra = MnO6, gray octahedra = AlO6.

Figure 16. Cyclic voltammogramms (GC electrode) and UV-Vis-NIR spectroelectrochemical study (Pt-grid

electrode) of (MeS)3TTF(S-CH2-CO2H) and TTF-MnMo6-SP.

0.6 eq. SPCO2H

EEDQ

3 eq. (MeS)3TTF(SCH2-CO2H)

EEDQ

4 eq. (MeS)3TTF(SCH2-CO2H)

EEDQ

H2N-MnMo6-SP

H2N-MnMo6-NH2

TTF-MnMo6-SP

TTF-MnMo6-TTF

H2N-AlMo6

2 eq. (MeS)3TTF(SCH2-CO2H)

EEDQ

TTF-AlMo6

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D) Immobilization of polyoxometalates in the metal organic framework

(POM@MOF)

The feature of MOFs, such as their pore sizes, shapes, dimensionalities and chemical

environment can be finely controlled for proposes of the specific applications. Despite the fact

that POMs possess high metal content, they have not been widely used in catalysis domain.

This is due to the low stability of POMs and the lack of accessible active sites in their

structure.5 Hence, the use of MOFs as a support of POM is considered as an interesting

strategy to develop their applications in catalysis.

Several advantages can be obtained by inserting POM into the cavities of MOF: i) improve of

the specific surface area of POM; ii) uniform dispersion of POM units in a MOF skeleton; iii)

introduce magnetic POM into MOF can lead to the application as molecular quantum

spintronic devices; iv) allow the selective catalysis as a function of size and easy recycling

after catalytic reactions; v) easily recycling after catalytic reactions.

Several systems of POM@MOF have been investigated. The POM@MOF have been

synthesized at the Institut Lavoisier de Versailles, Université de Versailles Saint-Quentin

(Prof. P. Mialane, DR. A. Dolbecq et al). Firstly, three different POMs [PW12O40]3-,

[PW11O39]7- and [P2W18O62]

6- have been inserted to UiO-67 MOF (UiO for University of

Oslo; Figure 17). The electrochemical properties of POM@MOF have been studied and

compared to the corresponding POM (Figure 18). In the second part, POM

[Fe4(FeW9O39)2(H2O)2]10- (Fe6W18) has been inserted into three different support: gelatin,

MOFs MIL-101(Cr) (Material of Institute Lavoisier) and MOF UiO-67, the influence of these

three supports on electrochemical properties of POM has been studied.

Figure 17. Polyhedral representations of the octahedral cages of (A) UiO-67, (B) [PW12O40]3- (PW12), (C)

[PW11O39]7- (PW11) and (D) [P2W18O62]6- (P2W18)

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Figure 18. Cyclic voltammograms of (A) P2W18, (B) P2W18@UiO-67 and (C) P2W18+UiO-67 (mechanical

mixing) immobilized on a PG electrode at different scan rate from 0.025 to 1.000 V·s-1. (Inset) plots of Ipc vs. v

for reduction peaks. D) Reduction potentials of each composite immobilized on PG electrode. Buffer Solution:

pH 2.5 0.5 mol·L-1 Na2SO4 + H2SO4.

This hybrid systems have been extended to

[Zr6IVO4(OH)4(C14H8O4)5.5][Fe4

III(FeW9O39)2(H2O)2]0.1(DMF)1.8·17H2O (Fe6W18@UiO-67)

and [CrIII3(H2O)3O(O2CC6H4CO2)3][(FeW9O39)2Fe4(H2O)2]0.083(NO3)0.17·30H2O

(Fe6W18@MIL101-(Cr)) as well as Fe6W18@Gelatin prepared at the Institut Lavoisier de

Versailles, Université de Versailles Saint-Quentin (Prof. P. Mialane, DR. A. Dolbecq et al).

Again, the electrochemical properties of POM@MOF have been studied and compared to the

corresponding POM.

A preliminary study of electrocatalysis of nitrite by immobilizing POM@MOF on PG

electrode has been studied for the reduction of NOx. An enhancement of catalytic current is

observed showing that POM encapsulated into MOF is still active for NOx reduction.

E) Photoredox-Switchable Resorcin[4]arene Cavitands: Radical Control of

Molecular Gripping Machinery via Hydrogen Bonding

Molecular grippers feature a binary conformational switch in response to external stimuli

that results in reversible encapsulation of smaller molecules. This behavior makes them

potentially applicable as delivery systems, sensors, receptors, or elements in nanorobotics.

However, the control of molecular machinery by physical stimuli, such as electrical charge or

light, is a prerequisite to their application. We therefore developed in collaboration with Prof.

F. Diedrich and Dr. Jovana Milić (ETH Zurich) photoredox-switchable molecular grippers

based on resorcin[4]arene cavitand platforms equipped with alternating quinone (Q) and

quinoxaline walls carrying hydrogen bond donating groups, which were inspired by the role

of semiquinones (SQ) in natural photosynthesis (Figure 19). The SQ state was generated

electrochemically via cyclic voltammetry and photochemically by using [Ru(bpy)3]2+ as a

photocatalyst.

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Figure 19. Schematic representation of the (a) photosynthetic reaction center of Rb. sphaeroides (PDB 1DV3)

that inspired the design of (b) the switching concept of the photoredox-switchable molecular grippers.

Figure 20. Schematic representation of the (a) photosynthetic reaction center of Rb. sphaeroides (PDB 1DV3)

that inspired the design of (b) the switching concept of the photoredox-switchable molecular grippers.

The properties were studied by UV-Vis-NIR spectroelectrochemistry, EPR, ENDOR, and

transient absorption spectroscopy, in conjunction with DFT calculations. It was shown that

these systems adopt an open conformation in the oxidized Q state until redox interconversion

to the paramagnetic SQ radical anion provides the stabilization of the closed form through

hydrogen bonding. The SQ state was generated electrochemically and photochemically,

whereas properties were studied by UV-Vis-NIR spectroelectrochemistry (Figure 20),

transient absorption, and EPR spectroscopy. This study demonstrates a photoredox-controlled

conformational switch towards a new generation of molecular grippers.

The tunable magnetic properties and enhanced binding affinities of the grippers, along with

high reversibility and responsiveness to electrical and electromagnetic stimuli, set the stage

for a new generation of artificial molecular machines and devices based on this switching

concept in the future.

F) Flexible Viologen Cyclophanes

The ability of bis-viologen cyclophanes to act as redox triggered contractile switches is

investigated by EPR and electrochemistry in collaboration with DR. Jean Weiss (group

CLAC, Institute of Chemistry, UMR 7177). Comparative electro- and spectro-

electrochemical studies of flexible cyclophane with different linkers show that the

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development of intramolecular interactions in aqueous solution depends on the length of the

bridges (Figure 21). Comparative spectro-electrochemical studies of this macrocycle with two

other pentyl- or heptyl-linked cyclic bis-viologens show that the development of

intramolecular interactions in aqueous solution depends on the length of the bridges. This

dependence is confirmed by EPR and DFT studies of the magnetic coupling in the diradical

dication species.

Figure 21. Cyclic voltammogram, UV/Vis/NIR monitoring of -dimer formation for cyclophanes 2Cl4 and X-

band EPR spectrum of 2Cl4+ in H2O containing 0.1 mM KCl.

G) Communication in Multi-porphyrins

The periphery of porphyrins can be modified and various functions containing heteroatoms

(N, O, S, etc.) can be introduced (Figure 22). The new exocyclic chelates can be used for

stepwise formation of dimer, trimers, … and the corresponding species are investigated by

electrochemistry, spectroelectrochemistry and EPR to evaluated the degree of communication

between the metal centers (collaboration with the CLAC and POMAM groups, Insitute of

Chemistry).

The synthesis has been conducted by Dr. Romain Ruppert (CLAC group, Insitute of

Chemistry).

Figure 22. Left: Structures of the nickel(II)porphyrin monomer 3b and Pd- or Pt-linked dimers 1b and 4b. Right:

Cyclic voltammograms of nickel(II)porphyrin monomer 3b and of porphyrin homodimers 1b (Pd-linked) and 4b

(Pt-linked).

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EDUCATIONAL BACKGROUND

2011-present: Full professor (PR CE1), University of Strasbourg, Laboratory of

Electrochemistry and of Physical Chemistry of the Solid State, Institute of

Chemistry (UMR 7177). Head of the Laboratory.

“Electrosynthesis of porphyrins”, “Synthesis of polyoxometalates and study

of their electrocatalytical properties” and “Synthesis and study of the

catalytic behaviour of new hybrid system polyoxometalate – porphyrin(s)”

First class professor since 2014.

1998-2011: Associate Professor, Université Paris-Sud 11, Chemical Physics

Laboratory. “Electrosynthesis of porphyrin”, “Synthesis of polyoxometalate

and study of their electrocatalytical properties” and “Synthesis and study of

the catalytic behaviour of new hybrid system polyoxometalate –

porphyrin(s)”

1997-1998: European Post-doc, TMR Research Network "Artificial Photosynthesis for

Energy Production (Mn-Ru chemistry, Contract CT 96-0031" under the

supervision of Professor Jurgen-Hinrich Fuhrhop, Laboratory of Bioorganic

Chemistry, Freie Universität Berlin, Germany (Prof. Dr. J.-H. Fuhrhop).

Synthesis of various models, in solution or incorporated in

the membrane system, for the biomimetism of the PS II.

Study of this model with: electrochemistry,

spectroelectrochemitry, EPR, and photochemistry.

1994-1997: PhD in chemistry, in the field of the organic and the physical chemistry. "

Anodic coupling of porphyrins: new route to obtain multiporphyrins ".

Supervisors: Professors Alain Giraudeau and Maurice Gross in the

« Laboratory of Electrochemistry », University Louis Pasteur, Strasbourg,

France. 06 June 1997.

1993-1994: National Service in the " Radiological Protection Laboratory of the French

Army " (Clamart, Paris).

1992-1993: Master of Inorganic Chemistry, Strasbourg, University Louis Pasteur (first

in one's year).

HDR (Capacitating to steer researches)

[1] ”From the study of porphyrin and polyoxometalate complexes to the

formation of new hybrid porphyrin – polyoxometalate complexes.”, 13

December 2006, University Paris-Sud 11, Orsay.

PUBLICATIONS

[1] A. Giraudeau, L. Ruhlmann, L. El Kahef, M. Gross, ” Electrosynthesis and

characterization of symmetrical and unsymmetrical linear porphyrin dimers

and their precursor monomers ”, J. Am. Chem. Soc., 1996, 118, 2669-2679.

[2] L. Ruhlmann, A. Giraudeau, ” One-pot electrochemical generation of a

porphyrin dimer with bis(diphenylphosphonium)acetylene bridge ”, J. Chem.

Soc., Chem. Comm., 1996, 2007-2008.

[3] M. El Baraka, J. M. Jannot, L. Ruhlmann, A. Giraudeau, M. Deunié, P. Seta,

” Photoinduced energy transfert and electron transfert in a porphyrin triad

H2TPP-V2+-ZnOEP,2ClO4- ”, Photochem. Photobio. A: Chem., 1998, 113, 163-

18

169.

[4] L. Ruhlmann, A. Nakamura, H. Vos, J.-H. Fuhrhop, ” Manganese porphyrin

heterodimers and -trimers in aqueous solution ”, Inorg. Chem., 1998, 37, 6052-

6059.

[5] J.–H. Fuhrhop, S. Svenson, C. Böttcher, C. Träger, P. Demoulin, J. Schneider,

C. Messerschmidt, L. Ruhlmann, J. Zimmermann, ” Non-covalent Chiral

Fibers in Aqueous Gels and Their Functionalization ”, Bull. Mater. Sci., 1999,

22, 101-106.

[6] L. Ruhlmann, S. Lobstein, M. Gross, A. Giraudeau, ” An electrosynthetic path

towards pentaporphyrins ”, J. Org. Chem., 1999, 64, 1352-1355.

[7] J.–H. Fuhrhop, L. Ruhlmann, C. Messerschmidt, J. Zimmermann, W.

Fudickar, ” Rigidity in Synkinetic Molecular Monolayers of Functional

Lipids ”, Pure. Appl. Chem., 1999, 70, 12, 2385-2391.

[8] L. Ruhlmann, A. Schulz, A. Giraudeau, C. Messerschmidt, J.–H. Fuhrhop,

” Polycationic Zinc-5,15-Dichlorooctaethylporphyrinate - Viologen Wire ”, J.

Am. Chem. Soc., 1999, 121, 6664-6667.

[9] J. Zimmermann, W. Fudickar, L. Ruhlmann, J. Schneider, B. Roeder, U.

Siggel, J.–H. Fuhrhop ” Fluorescence Quenching and Size Selective

Heterodimerization of a Porphyrin Adsorbed to Gold and Embedded in Rigid

Membrane Gaps” , J. Am. Chem. Soc., 1999, 121, 9539-9545.

[10] Ch. Draeger, Ch. Böttcher, Ch. Messerschmidt, L. Ruhlmann, U. Siggel,

J.–L. Hammarström, H. Berglund-Baudin, J.-H. Fuhrhop, ” Isolable and

Fluorescent Mesoscopic Micelle Made of an Amphiphilic Derivative of Tris-

bipyridyl Ruthenium Hexafluorophosphate ”, Langmuir, 2000, 16, 2068-2077.

[11] L. Ruhlmann, J. Zimmermann, W. Fudickar, U. Siggel, J.–H. Fuhrhop,

” Heterodimers and –Trimers of Meso-tetra(isophtalicacid)porphyrin with

meso- and -tetramethyl pyridinium-porphyrins in Water ”, J. Electroanal.

Chem. 2001, 503, 1-14.

[12] L. Ruhlmann, A. Giraudeau, ” A first series of diphosphonium

electrochemically bridged porphyrins ”, Eur. J. Inorg. Chem. 2001.659-668.

[13] A. Giraudeau, S. Lobstein, L. Ruhlmann, D. Melamed, K. M. Barkigia, J.

Fajer, ” Electrosynthesis, Electrochemistry, and Crystal Structure of the

Tetrationic Zn-meso-Tetrapyridinium--Octaethylporphyrin ”, J. of Porphyrin

and phtalocyanine. 2001, 793-797.

[14] L. Ruhlmann*, L. Nadjo, J. Canny, R. Thouvenot, ” Di- and Tetranuclear

Dawson-Derived Sandwich Complexes: Synthesis, Spectroscopic

Characterization and Electrochemical Behavior”, Eur. J. Inorg. Chem. 2002,

975-986.

[15] L. Ruhlmann*, J. Canny, R. Thouvenot : ” Two Novel Dawson-Derived

Sandwich of Composition: Na18[(NaOH2)2Co2(P2W15O56)2] and

Na17[(NaOH2)Co3(H2O)(P2W15O56)2]. Synthesis, Spectroscopic

Characterization and Electrochemical Behaviour ”, Inorg. Chem. 2002, 41,

3811-3819 (cover of the journal).

[16] L. Ruhlmann, M. Gross, A. Giraudeau, ” Bisporphyrins with bischlorin

features obtained by direct anodic coupling of porphyrins ”, Chem. Eur. J.

2003, 9, 5085-5096.

[17] L. Ruhlmann*, J. Canny, J. Vaissermann, R. Thouvenot : ” Mixed-Metal

Sandwich Complexes [MII2(H2O)2FeIII

2(P2W15O56)2]14- (MII = Co, Mn):

Synthesis and Stability. The molecular structure of

[MnII2(H2O)2FeIII

2(P2W15O56)2]14- ” J. Chem. Soc. Dalton Trans. 2004,5, 794-

800 .

19

[18] L. Ruhlmann*, G. Genet, ” Wells-Dawson-Derived Tetrameric Complexes

{K28H8[P2W15Ti3O60.5]4}. Electrochemical Behaviour and Electrocatalytic

Reduction of Nitrite and of Nitric Oxide ” J. Electroanal. Chem. 2004, 568,

315-321.

[19] B. Godin, Y.-G. Chen, J. Vaissermann, L. Ruhlmann, M. Verdaguer, P.

Gouzerh, “ Coordination Chemistry of the Hexavacant Tungstophosphate

[H2P2W12O48]12- with FeIII Ions: Towards Original Structures of Increasing Size

and Complexity ” Angew. Chem. Int. Ed. 2005, 44, 3072-3075.

[20] B. Godin, J. Vaisserman, P. Herson, L. Ruhlmann, M. Verdaguer, P.

Gouzerh, “ Coordination chemistry of the hexavacant tungstophosphate

[H2P2W12O48]12-: synthesis ans characterization of complexes derived from the

unprecedented {P2W14O54} fragment. ” Chem. Comm. 2005, 5624-5626.

[21] L. Ruhlmann*, C. Costa-Coquelard, J. Canny, R. Thouvenot, “Mixed-Metal

Dawson Sandwich Complexes: Synthesis, Spectroscopic Characterization and

Electrochemical Behaviour of Na16[MIICo3(H2O)2(P2W15O56)2] (M = Mn, Co,

Ni, Zn and Cd).”, Eur. J. Inorg. Chem. 2007, 1493-1500 (cover of the journal).

[22] L. Ruhlmann*, C. Costa-Coquelard, J. Canny, R. Thouvenot “

Electrochemical and Electrocatalytical Investigations on the Tri-manganese

Sandwich Complex [NaMn3(H2O)2(P2W15O56)2]17-. ” J. Electroanal. Chem.

2007, 603, 260-268.

[23] J. Hao, L. Ruhlmann, Y. Zhu, Q. L,i Y. Wei “ Naphthylimido-Substituted

Hexamolybdate: Preparation, Crystal Structures, Solvent Effects and Optical

Properties of Three Polymorphs ” Inorg. Chem. 2007 46(11), 4960-4967.

[24] A. Flambard, L. Ruhlmann, J. Canny, R. Thouvenot, “ Solution and solid-

state 31P NMR study of paramagnetic Polyoxometalates ” C. R. Chimie, 2008,

11, 415-422.

[25] L. Ruhlmann*, C. Costa-Coquelard, S. Sorgues, I. Lampre. “ Photocatalytic

Reduction of Ag2SO4 by Dawson-Derived Sandwich Complex ”

Macromolecular Symposia, 2008, 270, 117-122.

[26] J. Hao, A. Giraudeau, Z. Ping, L. Ruhlmann*, “ Supramolecular assemblies

obtained by large counter anion incorporation in a well oriented polycationic

copolymer ”, Langmuir, 2008, 24, 1600-1603.

[27] J. Hao, Y. Xia, L. Wang, L. Ruhlmann*, Y. Zhu, Q. Li, Y. Wei

“Unprecedented Replacement of Bridging Oxygen Atom in Polyoxometalate

by Organic Imido Ligand.“ Angew. Chem. 2008, 120, 2666-2670.

[28] C. Allain, S. Favette, L.-M. Chamoreau, J. Vaissermann, L. Ruhlmann*, B.

Hasenknopf* “ Hybrid organic-inorganic porphyrine-polyoxometalates

complexes ” Eur. J. Inorg. Chem. 2008, 22, 3433-34441 (cover of the journal).

[29] L. Ruhlmann*, J. Hao, Z. Ping, A. Giraudeau, “ Self-oriented Polycationic

copolymers obtained from bipyrinium meso-substituted-octaethylporphyrins ”

J. Electroanal. Chem. 2008, 621, 22-30.

[30] C. Costa-Coquelard, D. Schaming, I. Lampre, S. Sorgues, L. Ruhlmann* “

Photocatalytic Reduction of Ag2SO4 by [P2W18O62]6- and tetracobalt complex “

Applied Catalysis B: Environmental, 2008, 84, 835.

[31] C. Costa-Coquelard, H. Jian, I. Lampre, S. Jiang, C. He L. Sun, L.

Ruhlmann*, “ Association of ruthenium complexes [Ru(bpy)3]2+ or

[Ru(bpy)2(Mebpy-py)]2+ with Dawson polyanions -[P2W18O62]6- or 2-

[FeIII(H2O)P2W17O61]7-.” Can. J. Chem. 2008, 86, 1034-1043.

[32] D. Schaming, A. Giraudeau, S. Lobstein, R. Farha, M. Goldmann, J.-P.

Gisselbrecht, L. Ruhlmann*, “ Electrochemical behavior of the tetracationic

porphyrins (py)ZnOEP(py)44+4PF6

- and ZnOEP(py)44+4Cl-. ” J. Electroanal.

Chem. 2009, 635, 20-28.

20

[33] D. Schaming, J. Canny, K. Boubekeur, R. Thouvenot, L. Ruhlmann*, “ An

Unprecedented Trinuclear Dawson Sandwich Complex with Internal Lacuna.

Synthesis and 31P NMR Spectroscopic analysis of the symmetrical

[NaNi3(H2O)2(P2W15O56)2]17- and [CoNi3(H2O)2(P2W15O56)2]

16- anions. ”, Eur.

J. Inorg. Chem. 2009, 5004–5009.

[34] A. Giraudeau, D. Schaming, J. Hao, R. Farha, M. Goldmann, L. Ruhlmann*, “

A simple way for the electropolymerization of porphyrins ”. J. Electroanal.

Chem. 2010, 638, 70-75.

[35] D. Schaming, C.Costa-Coquelard, S. Sorgues, L. Ruhlmann*, I. Lampre, “

reduction of Ag2SO4 by electrostatic complexes formed by tetracationic zinc

porphyrins and tetracobalt Dawson-derived sandwich polyanion. ”, Applied

Catalysis A: General, 2010, 373, 160-167.

[36] D. Schaming, C. Allain, R. Farha, M. Goldmann, S. Lobstein, A. Giraudeau, B.

Hasenknopf, L. Ruhlmann*, “ Synthesis and Photocatalytic properties of

Mixed Polyoxometalate-Porphyrin copolymers obtained from Anderson-type

polyoxomolybdates “ Langmuir, 2010, 26, 5101-5109.

[37] D. Schaming, C. Costa-Coquelard, I. Lampre, S. Sorgues, M. Erard, J. Canny,

R. Thouvenot, L. Ruhlmann* “ Formation of a new hybrid complex via

coordination interaction between 5,10,15-tritolyl-20-(4- and 3-pyridyl)

porphyrin or 5,10,15-triphenyl-20-(4-pyridyl) porphyrin and the

[MSiW11O39]6- Keggin-type polyoxometalate (M = Co2+ and Ni2+). ”,

Inorganica Chimica Acta, 2010, 363, 1185-1192.

[38] N. Karakostas, D. Schaming, S. Sorgues, I. Lampre S. Lobstein, J-P.

Gisselbrecht, A. Giraudeau, L. Ruhlmann* “ Synthesis, Electrochemistry,

Spectroelectrochemistry and Photochemistry of a fully deformed Zn-

substituted Porphyrin ZnOEP(py)44+4Cl- in aqueous solution. “ J. Photobiol.

Photochem. A., 2010, 213, 52-60.

[39] C. Costa-Coquelard, S. Sorgues, L. Ruhlmann* “ Photocatalysis with

polyoxometalates associated to porphyrins under visible light: an application of

charges transfer in electrostatic complexes. ” J. Phys. Chem. A.,2010, 114,

6394-6400.

[40] Y. Leroux, D. Schaming, L. Ruhlmann, P. Hapiot “ SECM investigations of

immobilized porphyrins films. ” Langmuir, 2010, 26, 14983-14989.

[41] D. Schaming, R. Farha, H. Xu, M. Goldmann, L. Ruhlmann* “ Formation and

photocatalytic properties of nanocomposite films containing both a tetracobalt

Dawson-derived sandwich polyanion and tetracationic porphyrin. “ Langmuir,

2011, 27, 132-143.

[42] D. Schaming, J. Hao, V. Alain, R. Farha, M. Goldmann, H. Xu, A. Giraudeau,

P. Audebert, L. Ruhlmann*, “ Easy methods for the electropolymerization of

porphyrins based on the oxidation of the macrocycles ”, Electrochimica Acta.,

2011, 56, 10454-10463.

[43] D. Schaming, S. Marggi-Poullain, I. Ahmed, R. Farha, M. Goldmann, L.

Ruhlmann,* “ Electrosynthesis and electrochemical properties of porphyrin

dimers with pyridinium as bridging spacer. ”, New J. Chem., 2011, 35, 2534–

2543.

[44] Y. Xia, D. Schaming, R. Farha, M. Goldmann, L. Ruhlmann*, “ Bis-

porphyrin copolymers covalently linked by pyridinium spacers obtained by

electropolymerization from -octaethylporphyrins and pyridyl-substituted

porphyrins ”, New J. Chem, 2012, 36, 588-596.

[46] L. Ruhlmann*, D. Schaming, I. Ahmed, A. Courville, J. Canny, R.

Thouvenot, “ Spectroscopic and Electrochemical Study of the Interconversion

of Cobalt Dawson Sandwich Complexes. “ Inorg. Chem. 2012, 51, 8202-8211.

[47] I. Ahmed, X. Wang, N. Boualili, H. Xu, R. Farha, M. Goldmann, L.

21

Ruhlmann*, “ Photocatalytic synthesis of silver dendrites using electrostatic

hybrid films of Porphyrin-Polyoxometalate ”, Applied Catalysis A: General,

2012, 447-448, 89-99.

[48] D. Schaming, Y. Xia, R. Thouvenot, L. Ruhlmann* “ An original

electrochemical pathway for the synthesis of porphyrin oligomers ”, Chem.

Eur. J. 2013, 19,1712-1719.

[49] I. Ahmed, R. Farha, M. Goldmann, L. Ruhlmann* “ Molecular photovoltaic

system based on Dawson type polyoxometalate and porphyrin formed by

layer-by-layer self assembly ” Chem. Comm., 2013, 49, 496-498.

[50] C. Allain, D. Schaming, S. Sorgues, J.-P Gisselbrecht, I. Lampre, L.

Ruhlmann*, B. Hasenknopf, “ Synthesis, electrochemical and photophysical

properties of covalently linked porphyrin-polyoxometalates. ”, Dalton Trans.,

2013, 42, 2745-2754.

[51] I. Alzcarate, I. Ahmed, R. Farha, M. Goldmann, X. Wang, H. Xu, B.

Hasenknopf, E. Lacôte, L. Ruhlmann*, “ Synthesis and Characterization of

conjugated Dawson-Type polyoxometalate-porphyrin copolymers. “, Dalton

Trans., 2013, 42, 12688-12698.

[52] X. Wang, H. Long, W. Shen, L. Ruhlmann, F. Qin, S. Sorgues, C. Colbeau-

Justin, “ Synthesis of Ternary Hybrid TiO2-SiO2-POMs and its Application in

Degrading Rhodamine B under Visible Illumination. “ Acta Phys.-Chim. Sin.

2013, 29, 1837-1841.

[53] I. Ahmed, R. Farha, Z. Huo, C. Allain, X. Wang, H.Xu, M. Goldmann, B.

Hasenknopf, L. Ruhlmann* “Porphyrin–polyoxometalate hybrids connected

via a Tris-alkoxo linker for the generation of photocurrent” Electrochimica

Acta, 2013, 110, 726-734.

[54] J. Lesage de la Haye, P. Beaumier, L. Ruhlmann, B. Hassenknopf, E. Lacôte,

J. Rieger, “Synthesis of Well-defined Dawson-Type Poly(N,N-

diethylacrylamide) Organopolyoxometalates.” ChemPlusChem, 2014, 79, 250-

256.

[55] Z. Huo, J.-P. Gisselbrecht, R. Farha, M. Goldmann, E. Saint-Aman, C. Bucher,

L. Ruhlmann*, “ Alternating electro-copolymerization of zinc--

octaethylporphyrin with a flexible bipyridinium ” Electrochimica Acta, 2014,

122, 108-117.

[56] J. Lesage de la Haye, A. Pontes da Costa, G. Pembouong, L. Ruhlmann, B.

Hasenknopf, E Lacôte, J Rieger « Study of the temperature-induced

aggregation of polyoxometalate-poly(N,N-diethylacrylamide) hybrids in water

”, Polymer, 2015, 57, 173-182.

[57] J. Lesage de La Haye, J.-M. Guigner, E. Marceau, L. Ruhlmann, B.

Hasenknopf, E. Lacôte, J. Rieger, “ Amphiphilic Polyoxometalates for the

Controlled Synthesis of Hybrid Polystyrene Particles with Surface Reactivity ”,

Chem. Eur. J., 2015, 21, 2948-2952.

[58] W. Salomon, C. Roch-Marchal, P. Mialane, P. Rouschmeyer, C. Serre, M.

Haouas, F. Taulelle, S. Yang, L. Ruhlmann, A. Dolbecq, ” Immobilization of

Polyoxometalates in the Zr-based Metal Organic Framework UiO-67 ” Chem.

Comm. 2015, 51, 2972-2975.

[59] I. Azcarate, Z. Huo, R. Farha, M. Goldmann, H. Xu, B. Hasenknopf, E. Lacôte,

L. Ruhlmann*, “ Generation of Photocurrent from Visible Light Irradiation of

Conjugated Dawson Polyoxophosphovanadotungstate-Porphyrin Copolymers”

Chem. Eur. J. 2015, 21, 8271-8280.

[60] Z. Huo, D. Zang, S. Yang, R. Farha, M. Goldmann, B. Hasenknopf, H. Xu, L.

Ruhlmann*, “Synthesis and characterization of Lindqvist-type

polyoxometalate–porphyrin copolymers”, Electrochimica Acta, 2015, 179,

326-335.

22

[61] Z. Huo, I. Azcarate, R. Farha, M. Goldmann, H. Xu, B. Hasenknopf , E.

Lacôte, L. Ruhlmann*, “Copolymeric films obtained by electropolymerization

of porphyrins and dipyridyl-spacers including Dawson-type polyoxometalates”

J. solid State Electrochemistry, 2015, 19, 2611-2621.

[62] J. Cao, G. London, O. Dumele, M. v. W. Rekowski, N. Trapp, L. Ruhlmann,

C. Boudon, A. Stanger, F. Diederich, "The Impact of Antiaromatic Subunits in

[4n+2]-Systems: Bispentalenes with [4n+2]-Electron Perimeter but

Antiaromatic Character. " J. Am. Chem. Soc. 2015, 137, 7178–7188.

[63] E. Donckele, A. Finke, L. Ruhlmann, C. Boudon, N. Trapp, F. Diederich,

"The [2+2] Cycloaddition–Retroelectrocyclization and [4+2] Hetero-Diels-

Alder Reactions of 2-(Dicyanomethylene)indan-1,3-dione (DCID) with

Electron-Rich Alkynes: Influence of Lewis Acids on Reactivity" Organic

letters.2015, 17, 3506-3509.

[64] F. He, L. Ruhlmann, J.-P. Gisselbrecht, S. Choua, M. Orio, M. Wesolek,

Andreas A. Danopoulos, P. Braunstein, “Dinuclear Iridium and Rhodium

Complexes with Bridging Arylimidazolide-N3,C2 Ligands: Synthetic,

Structural, Reactivity, Electrochemical and Spectroscopic Studies”, Dalton

Trans. 2015, 44, 17030-17044. Hot paper and Back Cover of the journal.

[65] T. A. Reekie, E. J. Donckele, L. Ruhlmann, C. Boudon, N. Trapp, F.

Diederich, “Ester-Substituted Electron-Poor Alkenes for the Cycloaddition–

Retroelectrocyclization and Related Reactions, Eur. J. Org. Chem. 2015, 33,

7264-7275.

[66] O. Oms, S. Yang, W. Salomon, J. Marrot, A. Dolbecq, E. Rivière, A.

Bonnefont, L. Ruhlmann*, P. Mialane, Heteroanionic Materials Based on

Copper clusters, Bisphosphonates and Polyoxometalates: Magnetic Properties

and Comparative Electrocatalytic Studies”, Inorg. Chem., 2016, 55,

1551−1561.

[67] W. Salomon, Y. Lan E. Rivière, S. Yang, C. Roch-Marchal, A. Dolbecq, C.

Simonnet-Jégat, N. Steunou, N. Leclerc-Laronze, L. Ruhlmann, T. Mallah,

W. Wernsdorfer, P. Mialane “ Single Molecule Magnet Behaviour of

Individual Polyoxometalate Molecules Immobilized in a Biopolymer or Metal

Organic Framework Matrices”, Chem. Eur. J., 2016, 22, 6564- 6574. Front

cover of the journal. [68] H. Dekkiche, A. Buisson, A. Langlois, P.-L. Karsenti, L. Ruhlmann, R.

Ruppert, P. Harvey “Metal Linkage Effects on Ultrafast Energy Transfer”,

Chem. Eur. J., 2016, 22, 10484-10493.

[69] C. Dengiz, C. Prange, G. Przemyslaw, N. Trapp, L. Ruhlmann, C. Boudon, F.

Diederich, “Push-pull chromophore by reaction of 2,3,5,6-tetrahalo-1,4-

benzoquinones with 4-(N,N-dialkylanilino)acetylenes”, Tetrahedron, 2016, 72,

1213-1224.

[70] G. Jayamurugan, V. Gowri, D. Hernández, S. Martin, P. Cea, C. Dengiz, J.-P.

Gisselbrecht, C. Boudon, W. Bernd Schweizer, B. Breiten, A. D. Finke, G.

Jeschke, B. Bernet, L. Ruhlmann, F. Diederich, “Design, Synthesis of

Aviram–Ratner-Type Dyads, and Rectification Studies in Langmuir Blodget

(LB) film”, Chem. Eur. J., 2016, 22, 10539-10547 (Hot paper).

[71] J. Milic, M. Zalibera, I. Pochorovski, N. Trapp, J. Nomrowski, D. Neshchadin,

L. Ruhlmann, C. Boudon, O.S. Wenger, A Savitski, W. Lubitz, G. Gescheidt,

F. Diederich, “Paramagnetic Molecular Grippers: The Elements of Six-State

Redox Switches”, J. Phys. Chem. Letters, 2016, 7, 2470-2477.

[72] P. Gawel, E.A. Halabi, D. Schweinfurh, N. Trapp, L. Ruhlmann, C. Boudon,

F. Diederich, “Synthesis of Dicyano-Substituted Benzo[c]fluorenes from

Tetraaryl[3]cumulenes”, Eur. J. Org. Chem., 2016, 17, 2919-2924.

23

[73] K. Merahi, A.M.V.M. Pereira, C. Jandon, L. Ruhlmann, J.A.S. Cavaleiro,

M.G.P.M.S. Neves, M. Orio, P. Turek, S. Choua, R. Romain, “Electronic and

magnetic interactions in diporphyrinylamines“ J. Phtalocyanine and

Porphyrin, 2016, 20, 1223-1243.

[74] H. Dekkiche, A. Buisson, A. Langlois, P.­L. Karsenti, L. Ruhlmann, P. D.

Harvey, R. Ruppert, Ultrafastest Singlet Energy Transfer in Porphyrin Dyads,

Inorg. Chem. 2016, 55, 10329-10336.

[75] M. Berville, C. Boudon, L. Ruhlmann, C. Bailly, J. Wytko, J. Weiss, S. Cobo,

E. Saint-Aman “Flexible viologen cyclophanes: odd/even effects on π-

dimerization”, ChemPhysChem, 2017, 18, 1-10.

[76] L. Xia, H. Zhang, Z. Wei, Y. Jiang, L. Zhang, J. Zhao, J. Zhang, L. Dong, E.

Li, L. Ruhlmann, Q. Zhang “ Catalytic Emulsion Based on Janus Nanosheets

for Ultra-Deep Desulfurization”, Chem. Eur. J., 2017, 23, 1920–1929.

[77] D. Specklin, C. Fliedel, C. Gourlaouen, J.-C. Bruyere, T. Avil, C. Boudon, L.

Ruhlmann, S. Dagorne, N-Heterocyclic Carbene Based Tri-organyl-Zn–Alkyl

Cations: Synthesis, Structures, and Use in CO2 Functionalization, Chem. Eur.

J., 2017, 23, 1-12.

[78] T. A. Reekie, M. Sekita, L. M. Urner, S. Bauroth, L. Ruhlmann, J.-P.

Gisselbrecht, C. Boudon, N. Trapp, T. Clark, F. Diederich, D. M. Guldi,

“Porphyrin Donor and Tunable Push-Pull Acceptor Conjugates - Experimental

Investigation of Marcus Theory”, Chem. Eur. J., 2017, 23, 6357-6369.

[79] N. Kerisit, P. Gawel, B. Levandowki, Y-F. Yang, V. Garcia Lopez, N. Trapp,

L. Ruhlmann, C. Boudon, K.N. Houk, F. Diederich, “A Four-Step Synthesis

of Substituted 5,11-Dicyano-6,12-diaryltetracenes with Enhanced Stability and

High Fluorescence Emission”, Chem. Eur. J., 2018, 24, 159-168.

[80] J. Milic, M. Zalibera, D. Talaat, J. Nomrowski, N. Trapp, L. Ruhlmann, C.

Boudon, O.S. Wenger, A. Savisky, W. Lubitz, F. Diederic, “Photoredox-

Switchable Resorcin[4]arene Cavitands: Radical Control of Molecular

Gripping Machinery via Hydrogen Bonding”, Chem. Eur. J., 2018, 24, 1431-

1440.

[81] S. Haberland, A. D. Finke, N. Kerisit, C. Katan, Y. Trolez, P. Gawel I. Leito,

M. Lõkov, R. Järviste, K. Kaupmees, N. Trapp, L. Ruhlmann, C. Boudon, D.

Himmel, F. Diederich, “Enhancement of Push–Pull Properties of Pentafulvene

and Pentafulvalene Derivatives by Protonation at Carbon”, Eur. J. Org. Chem.,

2018, 6, 739-749.

[82] A. Boulmier, A. Vacher, D. Zang, S. Yang, A. Saad, J. Marrot, O. Oms, P.

Mialane, I. Ledoux, L. Ruhlmann, D. Lorcy, A. Dolbecq,,“Anderson-type

Polyoxometalates Functionalized by Tetrathiafulvalene Groups: Synthesis,

Electrochemical Studies and NLO Properties”, Inorg. Chem. 2018, accepted.

CHAPTER OF BOOK

[1] L. Ruhlmann, J. Zimmermann, C. Messerschmidt, J. –H. Fuhrhop*, ” Rigid

Angströn Clefts in Lipids Membrane on Solid Surfaces ”, NATO ASI series, in

Supramolecular Chemistry, Kluwer Academic Publishers, Dordrecht,

Netherland, 1999, 527, 225-232.

[2] D. Schaming, A Giraudeau, L. Ruhlmann*, C. Allain, J. Hao, Y. Xia, R.

Farha, M. Goldmann, Y. Leroux, P. Hapiot, “Oxidation of Porphyrins in the

Presence of Nucleophiles: From the Synthesis of Multisubstituted Porphyrins

to the Electropolymerization of the Macrocycles” Publisher InTech, Editor Ewa

Schab-Balcerzak, Electropolymerization, ISBN: 978-953-307-693-5, december

2011, pp 53-76.

24

[3] D. Schaming, A. Giraudeau, L. Ruhlmann*, “Reactivity of Porphyrin Radical

Cations and Dications towards Nucleophiles: An Easy and Original

Electrochemical Method for the Synthesis of Substituted, Oligomeric and

Polymeric Porphyrin Systems” Handbook of Porphyrins: Chemistry, Properties

and Applications, Series: Chemical Engineering Methods and Technology

Publisher Nova, Editors: Ayumu Kaibara and Genji Matsumara, Pub. Date:

2012 4rd Quarter. ISBN: 978-1-61668-757-1.

[4] D. Schaming, A. Giraudeau, L. Ruhlmann*, “Reactivity of Porphyrin Radical

Cations and Dications towards Nucleophiles: An Easy and Original

Electrochemical Method for the Synthesis of Substituted, Oligomeric and

Polymeric Porphyrin Systems” Chapter 12, pp 23-24. Chemistry Research

Summeries 12. Publisher Nova, Editor: Lucille Monaco Cacioppo, Pub.

Date: 2014 4rd Quarter. ISBN: 978-1-61668-757-1.

[5] D. Schaming, L. Ruhlmann*, Handbook of Porphyrin Science, Karl Kadish,

Roger Guilard, Kevin Smith, Eds., Published by World Scientific, 5 Toh Tuck

Link, Singapore 596224. USA office: 27 Warren Street, Suite 401-402,

Hackensack, NJ 07601. Chapter 5. “Electrosynthesis Processes Based on

Oxidative Couplings of Porphyrins for the Formation of Eletrosynthesis

Supramolecular Assemblies”, volume 32, chapter 167, pp 127-172, 2014.

[6] D. Schaming*, L. Ruhlmann*, “Polyoxometalates Associated with Porphyrins used as Efficient Visible Photosensitizers” ; ”Trends in

polyoxometalate research”, Publisher Nova, Editors: L. Ruhlmann and D.

Schaming, pp 237-264, Pub. Date: 2015. [7] D. Schaming, L. Ruhlmann* “Electrosynthesis of oligo- and polyporphyrins

based on oxidative coupling of Macrocycles“, chapter in the book

“Electrochemistry of MN4 Macrocyclic Complexes”, Springer, Zagal, J.H.,

Bedioui, Fethi, Dodelet, J.P. (Eds.). Vol 2, Biomimesis, electroanalysis, and

electrosynthesis of MN4 metal complexes, 2016, pp 395-432.

[8] D. Schaming, L. Ruhlmann

Electrosynthesis of oligo- and polyporphyrins based on oxidative coupling of

Macrocycles chapter in the book “Electrochemistry of MN4 Macrocyclic

Complexes”, Vol 2, Biomimesis, electroanalysis, and electrosynthesis of MN4

metal complexes, Springer, J.H. Zagal, F. Bedioui, J.P. Dodelet, (Eds.), 2016,

pp 395-432.

BOOK

[1] “Trends in polyoxometalate research”, Editors, L. Ruhlmann* and D.

Schaming. Publisher: Nova Science Publishers Inc, Imprint: Nova Science

Publishers Inc, ISBN-13: 9781634826563, Publication date: 1st june 2015,

Pages: 1-427.

25

PROCEEDING

[1] S. Favette, C. Allain, B. Hasenknopf, L. Ruhlmann, « Polyoxometalates as

molecular building blocks. » ACS Meeting, Division of Polymer Chemistry,

Boston (USA), August 19-23, 2007. Polymer Preprints (American Chemical

Society, Division of Polymer Chemistry) 48(2), 663-664, 2007.

A VULGARISATION PAPERS

[1] D. Schaming, L. Ruhlmann*, « Assemblages polyoxométallates-porphyrines

pour la photocatalyse solaire», Actualité Chimique, 2012, 362, 34-39. Prix de

thèse SFC division chimie physique.

[2] D. Schaming, L. Ruhlmann*, “ Substitutions nucléophiles sur porphyrines

oxydées : une voie simple et originale d’obtention de systèmes

multiporphyriniques par électrochimie “ Actualité Chimique, April 2014, pp 8-

13.

[3] L. Ruhlmann*, “ Oligoporphyrines et électrosynthèse “ Actualité Chimique,

2015, 400-401, pp 31-32.

26

Covers of journal

Back cover of journal

27

ORGANISATION OF CONFERENCES

8ème Journées Francophones des Jeunes Physico-Chimistes, Marly-le-Roi, 28-30

september 2005.

First workshop in Chemistry between Fudan University and University Paris-Sud

11, Shanghai (Chine), April 2011.

2nd Workshop on Molecular Science co-organized by Fudan and Paris-Sud 11

Universities, Orsay (France), 11-13 January 2012.

First workshop in Chemistry between Fudan University and Strasbourg University,

Shanghai (Chine), 19 May 2015.

First workshop in Chemistry between Tsinghua University and Strasbourg

University, Shanghai (Chine), 22 May 2015.

Gecom-Concoord 2016 at Obernai, France, 16-20 may 2016.

Second workshop in Chemistry between Fudan University and Strasbourg

University, Strasbourg (France), 16-17 April 2016.

Joint Workshop, Osaka University – Strasbourg University, Strasbourg 11-12 May

2017

VISITING PROFESSORS

Senior visiting professor of the University of Technology of Dalian (China): 2003-

2004.

Senior visiting professor of Fudan University, Shanghai (China) since 2005.

Senior visiting professor of Liaoning Normal University, LNU, Shenyang (China)

since 2016.

Senior visiting professor at Osaka University (Osaka, Japan) in November 2015.

OTHERS

« Cordée de la réussite », Students from « Sciences de l'ingénieur en PSI, lycée

Schweitzer, Mulhouse », « Electrochemsitry and Energy Conversion », 20th october

2017, Strasbourg.