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Supramolecular Water Oxidation with Ru-bda Based Catalysts
Craig J. Richmond,[a] Roc Matheu,[a] Albert Poater,[b] Laura Falivene,[c] Jordi Benet-Buchholz,[a] Xavier Sala,*,[d]
Luigi Cavallo,*,[c] and Antoni Llobet,*,[a],[d]
Abstract: Extremely slow and extremely fast new
water oxidation catalysts based on the Ru-bda
systems are reported with turnonver frequencies in
the range of 1 and 900 cycles/s respectively. Detailed
analyses of the main factors involved in the water
oxidation reaction have been carried out and are
based on a combination of reactivity tests,
electrochemical experiments and DFT calculations.
These analyses, give a convergent interpretation that
generates a solid understanding of the main factors
involved in the water oxidation reaction, which in turn
allows the design of catalysts with very low energy
barriers in all the steps involved in the water oxidation
catalytic cycle. We show that for this type of system stacking interactions are the key factors that influence
reactivity and by adequately controlling them we can
generate exceptionally fast water oxidation catalysts.
Today a transition from fossil to solar fuels is needed
in order to provide us with a clean and sustainable
energy model. A viable option to achieve this
challenge is to split water with sun light, however,

[a]

[b]

[c]

[d]

Craig J. Richmond, Roc Matheu, Dr. Jordi Benet-Buchholz , Prof.
Antoni Llobet
Institute of Chemical Research of Catalonia (ICIQ)
Av. Països Catalans 16 – 43007, Tarragona, Spain
E-mail: allobet@iciq.es
Dr. Albert Poater
Institut de Química Computacional i Catàlisi and Departament de
Química, Universitat de Girona, Campus de Motilivi, E-17071
Girona, Spain
Dr. Laura Falivene, Prof. Luigi Cavallo
KAUST Catalysis Center, Chemical and Life Sciences and
Engineering, King Abdullah University of Science and Technology,
Thuwal 23955-6900, Saudi Arabia.
Dr. Xavier Sala, Prof. Antoni Llobet
Departament de Química, Universitat Autonoma de Barcelona,
Cerdanyola del Vallès, 08193 Barcelona, Spain.
Supporting information for this article is given via a link at the end of
the document and it contains additional experimental, spectroscopic,
electrochemical, crystallographic (cif files; CCDC 1014178) and DFT
data.

before this can be realized, one of the key issues that
needs to be understood and mastered is water
oxidation catalysis. In this respect significant progress
has been accomplished over the last five years, mainly
based on molecular transition metal complexes.[1]
Among the best water oxidation catalysts (WOCs)
reported today are dinuclear Ru complexes that make
O-O bonds via a water nucleophilic attack mechanism
(WNA)[2] and a family of mononuclear Ru complexes
based on the tetradentate ligand [2,2'-bipyridine]6,6'-dicarboxylic acid (H2bda; see Scheme 1 for the
ligand structures described in this paper) that make OO bonds via a bimolecular Ru-oxo coupling
mechanism (I2M).[3] Spectacular performances both in
terms of maximum turnover frequencies (TOFmax) and
turnover numbers (TONs) have been reported, with
[Ru(bda)(isoq)2], 1, (isoq = isoquinoline), which has a
TOFmax ≈ 300 s-1, comparable to that of the oxygen
evolving systems of photosystem II (OEC-PSII).
Complex 1 has been modified by introducing
additional functionalities at the axial monodentate
pyridyl ligands, allowing it to be anchored on carbon
nano-tubes or oxide surfaces, both of which have
proved to be useful methods to create efficient
photoanodes for electrochemical cells.[4] For the
success of the latter it is crucial that the water
oxidation catalysis is sufficiently fast so that it can
compete favorably with the potential non-productive
and deactivating reactions. Thus a detailed
mechanistic analysis at a molecular level is essential in
order to gain knowledge about the origin of the
activation barriers that are responsible for the rate
determining step (rds). For the particular case of
[Ru(bda)(Isoq)2], 1, it was found that the rds, under
catalytic conditions at pH = 1.0, involves the
dimerization of the complex at the formal oxidation

state V generating a peroxo dinuclear complex, thus
following a mechanism that involves the interaction of
two M-O units (I2M). Further one electron oxidation
of the peroxide generates the species responsible for
the dioxygen release.[3b]

Scheme 1. Ligand structures and abbreviations.

MeOH and heating to reflux. The as prepared
compounds were characterized by standard
electrochemical and spectroscopic techniques (for full
experimental details and spectra see ESI). An X-ray
structure of 4 is presented in Figure 1, the bonding
parameters are typical for a Ru(II) d6 low spin
complex,[5] however, the most interesting feature of
the X-ray analysis is its 3D packing, where strong stacking interactions can be clearly observed between
the isoquinoline ligands (See Figure 1). Spiraling
columns of three separate molecules form, with
distances between -systems in the range of 3.4-3.7
Å, thus providing precedence for the stacking
interactions also proposed to be present during the
catalytic cycle.

Attempts to improve the performance of Ru-bda
complexes include the exertion of electronic
perturbations at the metal site via sigma and interactions through substituents at the 4-position of
the axial groups.[3] For example, the complex
containing ethyl isonicotinate, [Ru(bda)(4-COOEtpy)2], 2, is significantly faster than the 4-methyl
pyridine complex [Ru(bda)(4-Me-py)2], 3, with an
impressive TOFmax of 119 s-1. Another important factor
that improves reaction rates is the stacking
interaction of the axial ligands, as can be deduced by
comparing the TOFmax of 1 (c.a. 300 s-1) with that of 3
(c.a. 32 s-1), which under similar conditions is about
one order of magnitude slower.
In this work two new Ru-bda complexes;
[Ru(bda)(L)2]n+, (L = MeO-isoq, n = 0, 4; L = Me-bpy+, n
= 2, 5(PF6)2) are reported in order to further explore
the benefit of the -stacking interaction for this type
of catalyst. Whilst the complex containing the MeOisoq was expected to lead to favorable -stacking
effects in water, the opposite was expected for that
containing the Me-bpy+ ligand due to its cationic
nature and the non-parallel orientation of the pyridyl
rings.
Ru(bda) WOCs 4 and 5 were synthesized following the
previously reported one-pot method,[3a,4b] mixing
[RuCl2(DMSO)4] with the aryl axial ligands and bda2- in

Figure 1. Left, Ortep view for the molecular X-ray
structure of 4. Ellipsoids are plotted at 50 %
probability. Color codes: Ru, cyan; N, blue; O, red; C,
black; H, light blue. Right, representation of the πstacking observed in groups of three molecules. The
distance between the aromatic rings is in the range
3.4-3.5 Å.
The electrochemical properties of 1, 4 and 5 were
investigated by means of cyclic voltammetry (CV) and
differential pulse voltammetry (DPV) using the
Hg/Hg2SO4 as a reference electrode with the results
shown in Figure 2 and Table 1 and the supporting

information. From these experiments it is found that
the III/II redox potential is the one that suffers the
strongest shift due to the electronic effects exerted by
the axial ligands. On the other hand the IV/III and V/IV
redox potentials are slightly modified. Ironically the
most affected redox potential is irrelevant for the
catalysis kinetics since the oxidation state II is not
involved in the catalytic cycle, it acts only as a catalyst
precursor to the oxidation state III that is the lowest
oxidation stated involved in the catalytic cycle.[3a] For
complex 4, the V/IV wave is associated with a large
electrocatalytic current, as can be observed in the CV
of Figure 2, whereas for complex 5 the current is
practically identical to the blank, indicating that for
the latter the catalysis, if it exists, is very slow. Since
the potentials for the redox couples correlated to the
catalytic cycles of both 4 and 5 are very similar to each
other, it seems probable that the large difference in
their reactivity is relevant to the intermolecular
stacking associations.

Figure 2. Cyclic voltammograms and DPV (inset) of 4
(dashed line, 0.32 mM), 5 (solid line, 0.32 mM) and
bare glassy carbon electrode (red line) in a 0.1 M triflic
acid solution containing 25% TFE. The scan rate was
100 mV/s and a glassy carbon electrode (0.07 cm2)
was used as working, Pt mesh was used as counter
and Hg/Hg2SO4 (MSE) as reference electrodes.

The assessment of the complexes’ activity towards
water oxidation was further investigated chemically
using Ce(IV) as a sacrificial oxidant at pH = 1.0, the
results are reported in Figure 3 and Table 1.
Manometric gas measurements were used to assess
the activity for both the individual catalysts (1, 4 and
5) and 1:1 mixtures of 4 and 5. Online mass
spectrometry and headspace analysis with a Clark
electrode were used to confirm O2 as the only
component of the gas produced (see ESI Figures S2728)
Figure 3. Oxygen evolution profile for Ru-bda catalysts
4 and 5 in varying catalyst ratios and concentrations,
[CAN] = 0.1 M, in 2.0 mL 0.1 M triflic acid at 25 °C; [4]
= 5.0 µM green, [4] = [5] = 2.5 µM blue, [4] = 2.5 µM
purple, [4] = [5] = 1.25 µM yellow, [4] = 1.25 µM
orange, [5] = 5.0 µM red.

Table 1 shows the impressive performance of the Rubda family of catalysts under different conditions at
pH = 1.0. For instance in entry 3, complex 4 5.0
µM/Ce(IV) 100 mM (1/20000) generates oxygen at a
maximum velocity (vmax) of 3.81 µmols/s (TOFmax = 381
s-1) with basically 100% oxidative efficiency that
illustrates the ruggedness of this family of catalysts.

9

10

1

5.0

100

2.56
±0.01

256
±1

Table 1. Reactivity and electrochemical parameters for
Ru-bda catalysts.

11

4+5

1.25+1.25 100

0.52
±0.07

103
±3

4+5

2.5+2.5

2.01
±0.07

201
±7

Entry[a] WOC [WOC] /
µM

[CeIV] vmax /
/ mM µmol s-1
[c]

4

1.25

100

0.320
±0.005

130
±2

2

4

2.5

100

1.26
±0.01

252
±2

3

4

5.0

100

3.81
±0.16

381
±16

4[b]

4

50

350

23.07
±0.08

923
±3

5

5

2.5

100

0.0055

1.10

±0.0002 ±0,02

6

5

5.0

100

0.0200 2.00
±0.0002 ±0.02

7

5

20

100

0.350
±0.008

8.8
±0.2

8

1

1.25

100

0.104
±0.001

41.8
±0.4

2.5

100

0.637
±0.006

127
±1

0.70
1.17
1.38

12
TOFmax E1/2
vs.
/
NHE
s-1 [c]
[d]

1

1

100

[a] Headspace = 8.5 mL, Temperature = 25 °C, solvent = 3%
0.67
TFE in 0.1 M triflic acid (2.0 mL), [CAN] = 0.1 M. [b]
Headspace = 27.0 mL, Temperature = 25 °C, solvent = 3% TFE
1.14
in 0.1 M triflic acid (0.5 mL), [CAN] = 0.35 M. [c] Calculations
1.35 on averaged data obtained from duplicate reactions.
based
[d] III/II, IV/III and V/IV redox potentials respectively in V vs.
NHE. Potentials converted from MSE. [e] data from reference
3b.
A kinetic analysis (see ESI Figure S24 and S25) of the
reactivity of complexes 4 and 5 based on initial rates,
maintaining the Ce(IV) concentration constant and
varying the concentration of 4 and 5, gives a second
order behavior, which is again consistent with the fact
0.78 the stacking interactions are involved in the rate
that
determining step.
1.15
It is also very interesting to point out that under
1.37
identical conditions (entries 1-3 vs. 8-10), complex 4
containing the MeO substituted isoquinoline is about
two to three times faster than the non-substituted
isoquinoline complex, 1. This can be attributed to a
better stacking match in rds transition state (TS), due
to the offset of the two Ru-bda moieties. In sharp
contrast, under identical conditions, complex 5
containing the Me-bpy+ ligand has maximum
velocities that are 190 and 128 times slower than 4
and 1 respectively (see entries 3, 6 and 10). Clearly
here the positive charge around the Me-bpy+ ligand

outweighs the stacking effect and as a consequence
lacks the low energy pathway for oxygen formation
provided by the bimolecular mechanism is less
favorable.
In order to extract further evidence regarding the
nature of the -stacking interaction 1:1 mixtures of
complexes 4 and 5 were evaluated (see Figure 3. and
Table 1 entries 11-12). Entry 11 shows that a 1.25
µM:1.25 µM combination of 4:5 and 100 mM Ce(IV)
gives a maximum velocity of 0.52 µmols/s. Combining
this data with the rest of the table, the following
considerations and conclusions can be extracted: i)
Following a bimolecular pathway, three types of
interactions can contribute to reach this rate; the 4:4,
the 4:5 or the 5:5. The latter, as we have shown
previously, is more than 2 orders of magnitude slower
than the 4:4 and thus cannot significantly contribute
to the final velocity observed; ii) If there was only the
4:4 type of interaction then the rate obtained should
be 0.32 µmols s-1, similar to entry 1 of the Table. The
fact that the rate observed is 0.52 µmols/s clearly
manifests the existence of a 4:5 interaction; iii)
Assuming no contribution from the 4:4 interaction,
then the maximum velocity for the 4:5 (1.25 µM:1.25
µM) interaction would be 0.52 µmols/s, and hence a
TOFmax of 103 s-1; iv) For the 4:4 (1.25 µM:1.25 µM)
interaction under these conditions (entry 2) a rate of
1.26 µmols s-1 is observed, resulting in a TOFmax of 252
s-1.
If the activation energy in the rds is inversely
proportional to the strength of the stacking
interaction, then the rate of oxygen production should
also follow this trend, which is what was observed for
1.25 µM:1.25 µM pairs of 4 and 5, 4:4 > 4:5 >> 5:5
(1.26 > 0.52 >> --). A similar analysis with identical
conclusions can be carried out by comparing the 2.5
µM combination (entry 12, 3 and 6) giving the same
trend, 4:4 > 4:5 >> 5:5 (3.81 > 2.01 >> 0.02).

Figure 4. Calculated TS structure for the 4:4 dimer
(distances in Å).
DFT calculations were performed to support the
scenarios emerging from the experiments. Focusing
on the O-O bond formation step, the free energy
barrier, calculated as the free energy difference
between the dimeric [Ru-O - - O-Ru]2+ TS and two
separated [Ru(V)=O]+ species, increases from 18.0
kcal/mol for 4:4 (see Figure 4), to 20.7 kcal/mol for
1:1, to 24.5 kcal/mol for 4:5, in very good qualitative
agreement with the experimental trend. Transition
state structural analysis of 1:1 and 4:4 also evidences
shorter distances between the tips of the axial ligands
in the 4:4 TS (3.24 Å) compared to the 1:1 TS (3.54 Å),
suggesting that stronger stacking, stabilizes the 4:4 TS
relative to the 1:1 TS (see Figure S30.). To have
additional support for this hypothesis, the stacked
axial ligands were rigidly extracted from 4:4 TS and
1:1 TS, and their interaction energy was calculated.
This results in a stacking interaction energy of 6.5
kcal/mol for the MeO-Isoq dimer, while for the
unsubstituted Isoq dimer the stacking energy
amounts to 3.5 kcal/mol only. Natural population
analysis indicates that the increased stacking energy
of the MeO-Isoq dimer is due to stabilizing
electrostatic interaction between the positively
charged C atom bearing the OMe substituent on one

MeO-Isoq ligand, and negatively charged C atoms of
the other MeO-Isoq ligand, see Figure S31. This
arrangement therefore has a favorable off-centerparallel stacking geometry between aromatic units.[6]
In addition, analysis of the steric maps of the
monomeric species [Ru(V)=O]+, see Figure S32, clearly
indicates that the Me-bpy+ ligands in 5, are also
destabilized by the higher steric hindrance between
the Me-bpy+ ligands. Steric hindrance is instead
negligible in the [Ru(V)=O]+ species 1 and 4, see again
Figure S32.
Finally under extreme conditions (entry 4, Table 1) the
system 4 50 µM/Ce(IV) 350 mM, yields an impressive
maximum velocity of oxygen generation of 23.07
µmols s-1 which implies a TOFmax of 923 cycles/s, which
is among the highest reported for a molecular WOC.7
In conclusion convergent chemical, electrochemical
and DFT experiments involving Ru-bda type catalysts
generates a solid knowledge on these systems
regarding the key factors that influence their
reactivity. This knowledge in turn allows the judicial
design of systems for extremely fast water oxidation
reactivity, as is the case of 4, which is vital for the
building up of efficient photoanodes.
Experimental Section
Materials: RuCl3·3H2O and 6-methoxyisoquinoline
were supplied by Precious Metals Online PMO Pty Ltd
and Apollo Scientific. All other reagents were
purchased from Sigma-Aldrich. 6,6'-Dicarbonixilic
acid-2,2'-dipyridyl (H2bda),[4] [RuCl2(DMSO)4][8] and [1Methyl-4,4’-bipyridinium]PF6 (Me-bpy(PF6))[9] were
prepared according to the reported procedures.
Methanol (MeOH) was distilled over Mg/I2. All
synthetic manipulations under N2/Ar were performed
using standard Schlenk tubes and vacuum-line
techniques.
Synthesis of 4: The procedure was modified from a
previously reported procedure.[4] [RuCl2(DMSO)4] (100
mg, 0.21 mmol), 6,6'-dicarbonixilic acid-2,2'-dipyridyl

(H2bda) (59.50 mg, 0.2 mmol) and Et3N (0.1 mL) were
dissolved in anhydrous MeOH (10 mL) and heated to
reflux for 3 hours under Ar. 6-methoxyisoquinoline
(65 mg, 0.41 mmol) was subsequently added to the
solution and the reaction was then heated to reflux
overnight. The product precipitated as a brown
powder, which was filtered, washed with acetone (3 x
15 mL) and diethyl ether (3 x 15 mL) and dried under
vacuum (20 mg, 18% yield based on Ru). 1H NMR (400
Hz, [d4]-methanol): = 3.91 (6H, s), 7.19 (2H, d, J=2.3
Hz), 7.23 (2H, dd, J=2.3, 9.0 Hz), 7.50 (4H, q, J=7.58
Hz), 7.75 (2H, d, J=9.0 Hz), 7.92 (2H, t, J=7.9 Hz), 8.05
(2H, dd, J=0.9, 7.9 Hz), 8.42 (2H, s), 8.66 (2H, dd, J=0.9,
7.9 Hz). 13C NMR (500Hz, [d4]-methanol) = 28.0,
102.5, 119.5, 120.4, 123.2, 123.6, 124.4, 127.5, 130.1,
136.1, 141.4, 153.2, 154.8, 159.1, 161.4, 172.7. UV-vis
[λmax, nm (ε, M-1 cm-1)]: 237 (122000), 300 (37000) and
400 (16000). E1/2 (MeOH/Acetone 1:1, 0.1M TBAPF6):
0.10 V vs Hg/Hg2SO4. MALDI+-HRMS m/z: Calc for
{(MeOIsoq)2Ru(bda)}+: 662.0734, found: 662.0811 (12
ppm). Anal. Calc. for 4·3.5H2O (C32H31N4O9.5Ru): C,
53.04%; H, 4.31%; N, 7.73%. Found: C, 52.96%; H,
3.97%; N, 7.61%.
Synthesis of 5: The procedure was modified from a
previously reported procedure.[4] [RuCl2(DMSO)4] (75
mg, 0.17 mmol), 6,6'-dicarbonixilic acid-2,2'-dipyridyl
(H2bda) (50.6 mg, 0.17 mmol) and Et3N (0.1 mL) were
dissolved in anhydrous MeOH (6 mL) and heated to
reflux for 3 hours under Ar. [1-Methyl-4,4’bipyridinium]PF6 ([Me-bpy]PF6) (100 mg, 0.31 mmol)
was subsequently added to the solution and then
heated to reflux overnight. A brown solid (95mg)
precipitated as a brown powder, which was filtered,
washed with MeOH (3 x 5 mL) and diethyl ether (3 x
15mL) and allowed to dry in air. The dry precipitated
was dissolved in 80 mL of 1:1 MeOH/acetone and
evaporated to a final volume of 10 mL. Then 40 mL of
MeOH were added and the solvent evaporated until
precipitation occurred. The suspension was filtered
and the solid washed with MeOH (10 mL) and diethyl
ether (3 x 15 mL) and finally dried under vacuum (45
mg, 27% yield based on Ru). 1H NMR (400Hz, [d4]-

methanol): =7.92 (4H, dd, J=1.5, 5.4 Hz), 8.15 (4H,
m), 8.32 (4H, dd, J=1.36, 5.4 Hz), 8.55 (4H, d, J=6.8 Hz),
8.86 (2H, dd, J=1.5, 7.5 Hz), 9.17 (4H, d, J=6.8 Hz). 13C
NMR (500Hz, [d4]-methanol) = 46.1, 121.5, 124.1,
124.3, 124.6, 131.6, 140.3, 144.95, 150.6, 152.5,
154.7, 158.5, 171.9. UV-vis [λmax, nm (ε, M-1 cm-1)]:
250 (50000), 300 (29000), 510 (16800). E1/2
(MeOH/acetone 1:1, 0.1 M TBAPF6): 0.17 V vs
Hg/Hg2SO4. MALDI+-HRMS m/z: Calc. for
{[Ru(bda)(MeBpy)2]PF6-dctb}+: 1081.2322, found:
1081.2314 (1ppm). Anal. Calc. for 5·2H2O
(C34H32F12N6O6P2Ru): C, 40.37%; H, 3.19%; N, 8.31%.
Found: C, 40.14%; H, 2.76 %; N, 8.11 %.
Acknowledgements.
CR thanks the European Commission and Marie Curie
Actions for an Intra-European Fellowship. AL thanks
MINECO CTQ-2013-49075-R and “La Caixa”
foundation for financial support. M.R. thanks “La
Caixa” foundation for a PhD grant. XS thanks MINECO
CTQ2011-26440 for financial support. LC thanks King
Abdullah University of Science and Technology for
financial support. AP thanks the Spanish MINECO for a
Ramón y Cajal contract (RYC-2009-05226) and
European Commission for a Career Integration Grant
(CIG09-GA-2011-293900).
Keywords: Ru complexes, water splitting,
supramolecular interactions, redox catalysis, water
oxidation catalysis, supramolecular catalysis, DFT
calculations
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Entry for the Table of Contents (Please choose one layout)

COMMUNICATION
Supramolecular interactions
boost water oxidation
turnover frequencies in Rubda type of complexes

Craig J. Richmond,[a] Roc
Matheu,[a] Albert Poater,[b]
Laura Falivene,[c] Jordi BenetBuchholz,[a] Xavier Sala,*,[d] Luigi
Cavallo,*,[c] and Antoni
Llobet,*,[a],[d]
Page No. – Page No.
Supramolecular Water
Oxidation with Ru-bda Based
Catalysts