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Electron transfer reactions of ruthenium(II)-bipyridine complexes carrying

tyrosine moiety with quinones

Article in Luminescence · November 2014

DOI: 10.1002/bio.2617 · Source: PubMed

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Research article
Received: 31 July 2013, Revised: 7 October 2013, Accepted: 27 October 2013 Published online in Wiley Online Library

(wileyonlinelibrary.com) DOI 10.1002/bio.2617

Electron transfer reactions of ruthenium(II)–

bipyridine complexes carrying tyrosine moiety
with quinones
Paulpandian Muthu Mareeswaran,a Eswaran Rajkumar,a,b
Veerasamy Sathisha and Seenivasan Rajagopala*
ABSTRACT: Three ruthenium(II)–bipyridine complexes carrying a tyrosine moiety were synthesized and photophysical and
electron transfer studies with quinones were carried out using absorption and emission spectral techniques. The binding
efficiency of quinones with ruthenium(II)–bipyridine complexes was also studied using these techniques. The binding
efficiency was moderate and similar for all complexes with all quinones. The quenching modes were also similar and efficient
for all complexes with all quinones. The quenching processes were diffusion controlled. The rate of electron transfer was
calculated using semiclassical theory. Copyright © 2013 John Wiley & Sons, Ltd.

Additional supporting information may be found in the online version of this article at the publisher’s web-site.

Keywords: electron transfer; photophysics; ruthenium(II)–bipyridine–tyrosine; quinones; semiclassical theory

Introduction
Electrons shuttle between water and CO2 during photosynthesis
(1). Water is split and transfers its electron on the water oxida-
tion catalyst (WOC, manganese cluster) (1,2). The reaction center
of photosystem II (PSII) receives the electron from WOC via a
tyrosine moiety attached to the active center of PSII, which is
also undergoing a hydrogen bonding interaction with the
WOC (3–5). In the excited state, PSII transfers its electron to
nearby electron acceptors, pheophytin and quinones (QA and
QB) (6–8). These quinones deliver the electron to photosystem
I (PSI) in the excited state, which is further used in reduction of
CO2 to form carbohydrates (1,9). Thus, the excited states of PSI
and PSII attached to tyrosine and nearby quinones are the media-
tors of electron transfer (ET) between the WOC and PSI (6–11).
Therefore, it is essential that the tyrosine–reaction center–quinone
system is mimicked exactly in order to understand more precisely
the redox processes occuring in photosynthesis (9–14).
Ruthenium(II) polypyridyl complexes ([Ru(NN)3]2+) are widely
used to mimic the ET behavior of the PSII reaction center
(15–17). The advantage with [Ru(NN)3]2+ complexes is that the
properties of the excited state can be varied systematically by
introducing electron-donating and electron-withdrawing subs-
titutents in the 4,4′-position of the 2,2′-bipyridine (bpy) ligand
(17–21). Various amino acid moieties have been introduced into
ligand bpy of [Ru(bpy)3]2+ complexes via peptide linkage, and
the photophysical properties have been studied widely (22–25).
However in PSII, tyrosineZ is the amino acid that mediates ET from
the manganese cluster (3,11). Therefore, [Ru(NN)3]2+ complexes
carrying the tyrosine moiety may be an excellent mimic of the PSII
reaction center carrying tyrosine (26). Excitation of a [Ru(NN)3]2+
complex by a photon leads to the formation of a triplet metal-
to-ligand charge transfer (3MLCT) excited state and transfer of
its electron to the electron acceptor (quinones). Ru3+ is then
reduced in two ways: (i) back ET from the electron acceptor
(quinones) and (ii) intramolecular electron transfer from the
tyrosine moiety (27–30).
Quinones are ubiquitous in nature. They are ET mediators
between PSI and PSII, and act as anticancer drugs in medicine
(31–38). Quinones appear to be predestined as electron
acceptors in nature for a variety of reasons (39–41). In order to un-
derstand the electron-accepting properties of quinones in natural
photosynthesis, several model photosensitizers (metal–porphyrin,
[Ru(NN)3]2+ complexes) have been designed and inter- and intra-
molecular ET reactions with quinones have been studied (42–44).
The ET reactions of several quinones with excited state [Ru(NN)3]2+
complexes have been reported previously (42–45). ET from
phenolate to [Ru(NN)3]2+ has been reported extensively from this
laboratory (46–49). Herein, we report a detailed study on the excited
state ET reactions of [Ru(NN)3]2+ complexes carrying a tyrosine
moiety with quinones using steady-state and time-resolved
measurements. The semiclassical theory of ET has also been applied
successfully for the excited state ET reactions of [Ru(NN)3]2+
complexes carrying a tyrosine moiety with quinones.
Experimental
The compounds bpy (98.9%), RuCl3·3H2O (99.98%) were from
Merck and used without further purification. Benzoquinone
* Correspondence to: Seenivasan Rajagopal, School of Chemistry,
Madurai Kamaraj University, Madurai, Tamil Nadu, India. E-mail:
rajagopalseenivasan@yahoo.com
a
School of Chemistry, Madurai Kamaraj University, Madurai, Tamil Nadu, India
b
Vel Tech University, Avadi, Chennai, Tamil Nadu, India

Luminescence 2013 Copyright © 2013 John Wiley & Sons, Ltd.


(BQ; > 98.0%); naphthoquinone (NQ; 97.0%); 2,5-dichlo-
robenzoquinone (DCBQ; 99.0%); tetrachloro-1,4-benzoquinone
(TCBQ; 99.0%); and 7,7,8,8-tetracyanoquinodimethane (TCNQ;
98.0%) were from Sigma-Aldrich and their structures are shown
in Scheme 1. The compounds 4,4′-dimethyl-2,2′-bipyridine
(dmbpy; 99%); 2,2′-bipyridine-4,4′-dicarboxylic acid (dcbpy; 98%)
and tyrosine ethyl ester (99.0%) were also from Sigma-Aldrich.
Synthesis of ruthenium(II)–bipyridine
complexes carrying a tyrosine moiety
The ligands 4-methyl-4′-carboxy-2,2′-bipyridine (cmbpy), 4,4′-
dicarboxyethyl ester-2,2′-bipyridine (dcet) and the complexes [Ru
(bpy)2]Cl2, [Ru(dmbpy)2]Cl2, [Ru(dcet)2]Cl2, [Ru(bpy)2(cmbpy)]·2PF6,
[Ru(dmbpy)2(cmbpy)]·2PF6 and [Ru(dcet)2(cmbpy)]·2PF6 were
synthesized using reported procedures (50–53). [Ru(NN)3]2+
complexes carrying a tyrosine moiety, Ru(bpy)3–T, Ru(dmbpy)3–
T, Ru(dcet)3–T, were synthesized using the following procedure
and characterized using ESI-MS spectral techniques. The spectral
results were similar to existing reports (22,53,54).
Preparation of [Ru(bpy)3–T)]·2PF6
[Ru(bpy)2(cmbpy)]·2PF6 (400 mg, 0.43 mmol) was dissolved in 30
mL of thionyl chloride and the solution was heated to reflux
under nitrogen for 2 h. Evaporation of the excess thionyl
chloride in vacuum gave a dark red oil, which was immediately
used for the next step of the reaction. Tyrosine ethyl ester (160
mg, 0.65 mmol) was suspended in acetonitrile (15 mL, 99.9%)
and the solid in the suspension was dissolved after addtion of
triethylamine (0.4 mL, 2.5 mmol). The clear solution was added
dropwise to the above complex in acetonitrile (5 mL). White
Scheme 1. Structure of ruthenium (II) complexes and quinones used in this study.
wileyonlinelibrary.com/journal/luminescence Copyright © 2013 John Wiley & Sons, Ltd.
P. M. Mareeswaran et al.
smoke formed above the solution in the reaction flask, and the
solution was heated to reflux under nitrogen for 2.5 h and then
cooled to room temperature. White crystals of triethylamine
hydrochloride formed and were filtered off. The filtrate was
concentrated to ~ 5 mL. The crude product was purified by
repetitive column chromatography on neutral aluminum oxide
with gradient eluents, CH2Cl2 and CH2Cl2/CH3OH (90:10 v/v). The
desired fractions were combined and the solvents evaporated
to dryness to give a red solid. The red solid was dissolved in water
and to this aqueous solution was added concentrated aqueous
solution of NH4PF6 to produce a red precipitate. Filtration and
washing with water and petroleum ether gave a red solid with
70% yield. ESI-MS (M-PF6+ Na) 1074.44 m/z.
Preparation of [Ru(dmbpy)3–T)]·2PF6
The same synthetic procedure was adopted for the synthesis of
[Ru(dmbpy)2(c-t)]·2PF6 complex. The product yield is 66%.
ESI-MS (M-2PF6) 875.03 m/z.
Preparation of [Ru(dcet)3–T)]·2PF6
[Ru(dcet)2(cmbpy)]·2PF6 (470 mg, 0.39 mmol) was refluxed in 15
mL of thionyl chloride for 3 h. Excess of thionyl chloride was
removed under reduced pressure, and the residue dried under
vacuum at 50°C for 1 h. The resulting solid (acid chloride) was
redissolved in 5 mL of dry CH2Cl2. The solution was added
dropwise to a solution of tyrosine ethyl ester (265 mg, 0.42
mmol) and triethylamine (0.5 mL) in dry CH2Cl2 (10 mL). The
resulting solution was stirred under nitrogen at room temperature
overnight. The solvent was removed, and water (50 mL) added
and extracted with CH2Cl2 (4 × 50 mL). The crude product was
purified on a silica gel column using a mixture of MeCN/H2O/
KNO3 (saturated) (40/3/1) as the eluent. After purification, the
solvent was evaporated, the solid dissolved in a minimum amount
of water, and a saturated aqueous solution of NH4PF6 was added.
The mixture was extracted with CH2Cl2, and the combined organic
phase was washed with a diluted aqueous Na2CO3 solution and
then dried over Na2SO4. Solvent was removed under reduced
pressure to afford 63% yield of the desired product. ESI-MS
(M-PF6 + Na) 1335.63 m/z.
Absorption and emission spectral
measurements
Sample solutions of the [Ru(NN)3–T]2+ complexes and the quinones
were freshly prepared for each measurement. The [Ru(NN)3–T]2+
concentration was fixed at 2 × 10-5 M and the quinone concentra-
tion was varied between 2 × 10-5 and 2 × 10-4 M. The same sample
solutions were used for both absorption and emission studies. The
absorption spectrum was recorded using an Analtik-Jena Specord
S100 spectrometer and the emission spectrum using a JASCO
spectrofluorometer. All the sample solutions used for emission
measurements were deaerated for ~ 30 min using dry N2 gas
purging by keeping solutions in cold water to ensure that there
was no change in the volume of the solution. All measurements
were carried out at room temperature.
Electrochemical measurements
Electrochemical measurements were carried out using cyclic
voltammetric technique with a EG&G Princeton Applied
Luminescence 2013
A photophysic approach
Research Potentiostat/Galvanostate Model 273A. Measurements
were taken in acetonitrile using a platinum electrode as the
working electrode with 0.1 M tert-butyl ammonium perchlorate
as the supporting electrolyte and platinum wire as the auxiliary
electrode. The separation between the cathodic and anodic
peaks and the relative intensities of the cathodic and anodic
currents were taken as criteria for reversibility.
Determination of binding constants using
absorption and emission techniques
a ) for the binding of [Ru(NN)3–T]
The binding constant (Kabs 2+
com-
plexes with quinones was evaluated using Benesi–Hildebrand
method (equation (1)) (55).
h
2þ i
1=ΔA ¼ 1=K a abs Δε RuðNNÞ3 –T þ 1=Δε½Q (1)
Here, ΔA is the change in the absorbance of the [Ru(NN)3–T]
complex on the addition of quinone. Δε is the difference in the
molar extinction coefficient between the free and quinone-bound
[Ru(NN)3–T]2+ complex. [[Ru(NN)3–T]2+] is the total concentration
of [Ru(NN)3–T]2+and [Q] is the total concentration of quinone.
We have calculated the binding constant for the system from
the luminescence intensity data using the following modified
Stern–Volmer equation (equation (2)) (18,56).
log ½ðI0 –IÞ=I ¼ nlog ½Q þ log K a em
where, I0, I, [Q], Kemand n are the emission intensity in the ab-
a
sence of quencher, emission intensity in the presence of
quencher, concentration of quinone, binding constant and
stoichiometric ratio, respectively.
Determination of luminescence quenching
constant kq
The observed quenching rate constant kq for the oxidative
quenching of [Ru(bpy)3–T]2+ with quinones used in the study was
obtained from the Stern–Volmer plots using equation (3)(56).
Io =I ¼ 1 þ K sv ½Q
Ksv ¼ kq τ
where, Ksv, kq and τ are the Stern–Volmer constant, quenching con-
stant and excited sate lifetime, respectively. The plot of Iο/I vs [Q] is a
Figure 1. (a) Absorption spectra and (b) normalized emission spectra of [Ru(bpy)3]
Luminescence 2013 Copyright © 2013 John Wiley & Sons, Ltd.
straight line with an intercept of unity in all quenching studies. The
Stern–Volmer plots for the quenching of [Ru(NN)3–T]2+ with
quinones are shown in Figs S8-S10. The slope of this plot, the
Stern–Volmer constant, Ksv is related to kq through equation (4).
Results and discussion
[Ru(NN)3]2+ complexes carrying tyrosine moiety ([Ru(bpy)3–T]2+,
[Ru(dmbpy)3–T]2+ and [Ru(dcet)3–T]2+) were synthesized, as
given in the Experimental section and characterized using mass
spectra (22). The structures of complexes are shown in Scheme 1
and the mass spectra are shown in Figs S1–S3.
Steady-state absorption and emission prop-
erties of [Ru(NN)3–T]2+ complexes
The 1MLCT state of the parent complex [Ru(bpy)3]2+ has absorp-
2+ tion in the visible region at 450 nm. Introduction of a tyrosine
moiety via amide linkage produces a red-shift in the absorption
maximum to a λmax of 458 nm. The electron-releasing methyl
group is a good σ donor, but a poor π acceptor and the reverse
is the case with the electron-withdrawing carboxyethyl ester
group. Thus, the operation of σ-donor and π-acceptor properties
of the substituents in the ligand bipyridine increases the
electron density on the metal–ligand bond, thereby stabilizing
the 1MLCT state, leading to a red-shift in the absorption
(2) maximum. Therefore, the absorption, maximum corresponding
to the MLCT transition of [Ru(dmbpy)3–T]2+ and [Ru(dcet)3–T]2+
is shifted towards the red region with respect to the [Ru(bpy)
3–T]
2+
complex. The overlayed spectra of [Ru(bpy)3]2+, [Ru(bpy)
3–T] 2+
, [Ru(dmbpy)3–T]2+ and [Ru(dcet)3–T]2+ are shown in Fig. 1
(a). The respective absorption λmax values are shown in Table S1.
The emission maximum of [Ru(bpy)3]2+ in CH3CN is 612 nm.
Introduction of a tyrosine moiety via amide linkage produces a
red-shift in the emission maximum to a λmax of 644 nm. Because
of the σ electron donation capacity of methyl group, the energy
gap between the ground and 3MLCT states decreases. Therefore,
a red-shift is observed when a –CH3 group is introduced into
bpy. However, when the carboxyethyl ester group is introduced,
(3) the ligand becomes highly π accepting. Therefore, the energy
gap between 3MLCT and the ground state increased. Thus, for
(4) the complex [Ru(dcet)3–T]2+, a blue-shift to the tune of 22 nm
is observed compared with [Ru(dmbpy)3–T]2+. The normalized
emission spectra of four Ru(II) complexes are shown in Fig. 1
(b). The respective emission λmax values are given in Table S1.
2+ 2+ 2+ 2+
(----), [Ru(bpy)2C–T)] (—), [Ru(dmbpy)2(C–T)] (- - - ) and [Ru(dcEt)2(C–T)] (-.-.-).
wileyonlinelibrary.com/journal/luminescence

Excited state lifetime and redox properties
The excited state lifetime of parent [Ru(bpy)3]2+ in CH3CN is 850
ns. Introduction of a tyrosine moiety via an amide group
increases the excited state lifetime of the complex (1250 ns).
However, introduction of an electron-releasing group in the ligand
destabilizes the 3MLCT state by higher σ-donating ability and poor
π-accepting ability. Thus lifetime is reduced. Even though it has
higher lifetime than the parent complex [Ru(bpy)3]2+, it has
lifetime of 985 ns which is 265 ns less than that of the similar
complex [Ru(bpy)3–T]2+. However, introduction of the carboxyethyl
ester group into the 2,2′-bipyridine ligand increases the π-accepting
capacity. It stabilizes the system up to 1350 ns, which is 100 ns
higher than the [Ru(bpy)3–T]2+ and of 500 ns higher than the
parent complex. The respective excited state lifetime values are
given in Table S1.
The parent complex, [Ru(bpy)3]2+, has an oxidation potential of
+1.26 V and introduction of the tyrosine moiety via amide bonding
increases the oxidation potential to +1.39 V. However, the introduc-
tion of substituents into the 2,2′-bipyridne ligand produces little shift
in the oxidation potential of the Ru(II) complex. The complex
[Ru(dmbpy)3–T]2+ has an oxidation potential of +1.37 V and
[Ru(dcEt)3–T] 2+ has an oxidation potential of +1.29 V. The cyclic
voltammogram of [Ru(dmbpy)3–T]2+ is shown in Fig. 2.
2+
Figure 2. Cyclic voltagram of [Ru(dmbpy)2(C–T)] .
-5
Figure 3. Absorption spectrum of Ru(dcet)3–T (2 × 10 M) with incremental addition of quinones (a) BQ (2 × 10 to 2 × 10 M), (b) NQ (2 × 10 to 2 × 10 M).
wileyonlinelibrary.com/journal/luminescence Copyright © 2013 John Wiley & Sons, Ltd.
P. M. Mareeswaran et al.
Study of the binding of *[Ru(NN)3–T]2+ with
quinones using absorption spectral technique
The changes in the absorption spectra of [Ru(NN)3–T]2+ com-
plexes in the presence of increasing concentrations of quinones
are shown in Figs 3, S4–S6. There is a slight change in the
absorption intensity of MLCT of [Ru(NN)3–T]2+, which is
sufficient for the determination of binding constant for the
binding of quinone with [Ru(NN)3–T]2+ complexes. Li et al.
(57–59) have already established the importance of the π–π
stacking between phenols and [Ru(bpy)3]2+. We have used
Benesi–Hildebrand method to calculate the binding constant.
The binding constants (Kabs a ) are given in Table 1. The
Benesi–Hildebrand plots are shown in Figs S7–S9. From the
binding constant values it can be inferred that the efficiency
of binding is moderate and similar to all quinones in the
range of 9–33 M-1.
Binding and oxidative quenching of
*[Ru(NN)3–T]2+ with quinones using
emission spectral technique
The increase in the concentration of quinones quenched
the emission intensity of [Ru(NN)3–T]2+ complexes. The
quenching of [Ru(NN)3–T]2+ complexes with quinones is
shown in Figs 4, S10–S12. The binding constant (Kem a ) for
the binding of quencher with the sensitizer is calculated using
the modified Stern–Volmer equation (18). The modified Stern–
Volmer plots are shown in Figs S13–S15. The binding constant
values are given in Table 1. In this case, the binding efficiency
for all five quinones is similar with all three [Ru(NN)3–T]2+
complexes. The bimolecular quenching rate constants, kq, of the
*[Ru(NN)3–T]2+ complex by quinones in CH3CN were calculated
using the Stern–Volmer equation (51). Stern–Volmer plots are
shown in Figs S16–S18. From the slope of the Stern–Volmer
plots, the bimolecular quenching rate constants, kq, are
calculated and these values are given in Table 2.
Although the quenching constant kq is similar for both
[Ru(bpy)3–T]2+ and [Ru(dmbpy)3–T]2, the value is one order
higher for [Ru(dcet)3–T]2+. This is because of the favorable
ΔG0 value for [Ru(dcet)3–T]2+. Although there is a possibility
of quenching due to energy transfer, it has already been
established that quenching of the emission of [Ru(NN)3–T]2+
-5 -4 -5 -4
Luminescence 2013
A photophysic approach

Table 1. Binding constants of [Ru(NN)3–T] complexes with quinones using absorption (Kabs -1 em -1
a , M ) and emission (Ka , M )
techniques

Quinones [Ru(bpy)3–T]2+ [Ru(dmbpy)3–T]2+ [Ru(dcet)3–T]2+

Kabs
a n Kem
a Kabs
a n Kem
a Kabs
a n Kem
a

BQ 9.9 ± 0.34 0.71 18.1 ± 0.43 8.3 ± 0.22 0.82 17.6 ± 0.41 10.6 ± 0.57 0.66 25.7 ± 0.91
NQ 10.2 ± 0.12 0.94 20.1 ± 0.61 9.7 ± 0.78 0.78 22.6 ± 0.77 11.1 ± 0.33 0.73 32.8 ± 1.10
TCNQ 10.7 ± 0.55 0.67 22.6 ± 0.21 10.8 ± 0.67 0.69 19.1 ± 0.24 9.8 ± 0.63 0.85 31.4 ± 0.22
DCBQ 9.6 ± 0.10 0.58 20.5 ± 0.32 10.4 ± 0.34 0.72 27.5 ± 0.54 10.1 ± 0.42 0.59 29.1 ± 0.13
TCBQ 10.5 ± 0.78 0.95 25.8 ± 0.89 11.1 ± 0.54 0.55 30.3 ± 0.32 11.7 ± 0.12 0.91 33.7 ± 0.58

-5 -5 -4 -5 -4
Figure 4. Emission spectrum of Ru(dmbpy)3–T (2 × 10 M) with incremental addition of quinones (a) BQ (2 × 10 to 2 × 10 M), (b) NQ (2 × 10 to 2 × 10 M).

Table 2. Rate constants for oxidative quenching, rate of electron transfer, equilibrium constant and free energy

Quencher Equilibrium Rate of oxidative Rate of electron log k23 ΔGο, eV

constant, Keq quenching, kq transfer, k23
[Ru(bpy)3–T]
BQ 6.6 1.2 × 109 2.9 × 109 9.46 0.13
NQ 8.4 6.5 × 109 9.6 × 108 8.98 0.29
TCNQ 7.1 2 × 1010 7.2 × 109 9.86 -0.28
DCBQ 7.6 1.9 × 109 5.9 × 109 9.77 -0.39
TCBQ 10.3 2.6 × 1010 1.2 × 1010 10.08 -0.55
[Ru(dmbpy)3–T]
BQ 5.2 8.0 × 109 8.7 × 108 8.94 0.11
NQ 6.7 4.4 × 109 3.4 × 108 8.53 0.27
TCNQ 6.9 1.0 × 109 2.6 × 109 9.43 -0.57
DCBQ 7.2 9.1 × 109 2.3 × 109 9.38 -0.30
TCBQ 9.7 8.7 × 109 3.8 × 109 9.59 -0.41
[Ru(dcet)3–T]
BQ 7.1 5.2 × 1010 2.0 × 109 9.31 0.23
NQ 8.7 3.4 × 1010 1.3 × 109 9.14 0.32
TCNQ 7.7 2.5 × 1010 6.3 × 109 9.88 -0.65
DCBQ 8.1 2.1 × 1010 7.4 × 109 9.87 -0.42
TCBQ 11.1 1.8 × 1010 4.5 × 109 9.66 -0.67

with quinones is due to ET (22). The probability of reduction of
oxidized [Ru(NN)3–T]2+ by intramolecular ET from a tyrosine
moiety in acetonitrile medium is also negligible (22).
Therefore, we have assigned the quenching as ET and used
the quenching constant values for calculating rate of
electron transfer.
Dynamics of ET reactions of [Ru(NN)3–T]2+
with quinones
The rate of ET from a donor molecule to an acceptor in a solvent
is controlled by the change in free energy of the reaction (ΔG0),
the reorganization energy (λ) and the ET distance (d) between

Luminescence 2013 Copyright © 2013 John Wiley & Sons, Ltd. wileyonlinelibrary.com/journal/luminescence

the donor and the acceptor. The ET rate constant (ket) in both
the classical and semiclassical theories can be represented by
equation (5)(17)(38).


ket ¼ кel υn exp ΔG # =ðRTÞ (5)
where, кel is the electronic transmission coefficient, υn the nu-
clear frequency and ΔG# is the free energy of activation. When
the ET distance, d, is kept constant, the rate of the ET process
is decided by ΔG0 and the reorganization energy, λ through
the Marcus equation (equation (6)) (17,60).
 2
ΔG # ¼ λ þ ΔG0 =ð4λÞ (6)
Substitution of the above expression into equation (5) gives
the basic relation for ket in terms of ΔG0 and λ:
h  2 i process can be discussed in terms of the mechanism shown in
ket ¼ кel υn exp  λ þ ΔG0 =ð4λRTÞ (7)
According to classical Marcus theory, ET can occur only at the
intersection of the two potential energy surfaces. In such case, a
more effective route for the ET rate is derived from the semiclassical
theory, which can be represented by equation (8).
1=2
∞ 
2 S m
k et ¼ 4π =hjHDA j ð4πλo kT Þ
2
∑ e S =m!
m¼0
h i
exp ðλo þ ΔG° þ mhv Þ2 =4λo kT
In equation (8) HDA is the electronic coupling coefficient
between the redox centers, the reorganization energy λ is
composed of solvational λo and vibrational λi contributions with
s = λi/hν, ν is the high-energy vibrational frequency associated
with the acceptor and m is the density of product vibrational
levels. The terms h and k are Planck’s and Boltzmann’s
constants, respectively
According to Rehm and Weller, the free-energy change of ET
(ΔG°) can be calculated from equation (9) (61-62).
ΔG° ¼ EðD=D þ Þ  EðA=A

 Eoo  e2 =aε
Þ K eq ¼ 4πNd3 =3000 expðw r =RT Þ
where E(D/D+;) is the oxidation potential of donors, E(A/A), the
reduction potential of acceptor, Eo-o the lowest excited state
energy of Ru(II) complexes, and e2/aε is a columbic term.
The ΔG° values thus estimated for different donor and acceptor
pairs in CH3CN are given in the Table 2.
The value of λo can be evaluated classically by using dielectric
continuum model, equation (10).
 
λo ¼ e2 =4πεo ð1=2r D þ 1=2r A –1=dÞ 1=Dop –1=Ds (10)
Where e is the transferred electronic charge, εo is the permittiv-
ity of free space, Dop and Ds are the optical and static dielectric
Scheme 2. Mechanism for the oxidative quenching of *[Ru(NN)3–T]
wileyonlinelibrary.com/journal/luminescence Copyright © 2013 John Wiley & Sons, Ltd.
P. M. Mareeswaran et al.
constants, respectively. The terms rD and rA are the radii of the
electron donor and acceptor, respectively and d is the separation
distance between the donor and acceptor in the encounter
complex. This model is most applicable in cases where the donor
and acceptor are roughly spherical, and their center-to-center
distance (rDA) is large compared with the sum of the sphere radii.
The values of rD and rA can be estimated by the semi-empirical
(PM6 level) molecular model (10.8 Å for [Ru(bpy)3–T]2+; 11.2 Å
for [Ru(dmbpy)3–T]2+ and 12.9 Å for [Ru(dcet)3–T]2+ and for
quinones in the range 2.97–5.0 Å). Because the ΔG0 and λ
values are known, the rate constant for ET from the excited
state of [Ru(NN)3–T]2+ to quinone can be calculated. In
equation (8), HDA = 2 × 103 eV, λ = 0.81–0.92 eV, ν = 1000–1500
cm1 and T = 298 K. These are the optimum values for the reaction,
chosen by a trial and error method (63).
Because quenching occurs via ET, the redox quenching
Scheme 2. By applying steady-state treatments to the short-lived
species in Scheme 2, the following expression (equation (11)) for
the observed bimolecular quenching rate constant, kobs(kq) can
be derived.
k
kq ¼  12  (11)
 1 þ k 12 =k 23 K eq
(8)
where Keq is the equilibrium constant for the formation of the
encounter complex and k12 is the rate constant for the diffusion
process to form the encounter complex. The value of k12 is calcu-
lated from equation (12) (61-63).
k 12 ¼ 2RT=3000η½2 þ r D =r A þ r A =r D f (12)
1 u 2 2
where f = d∫e /kT dr/r with u = ZDZAe /DS[e /1 + Kd] e /r Kd Kr
where K = (8πe2Nη/1000DSkT)1/2, rD and rA are the radii of the
reactants and η is the viscosity of the medium.
The diffusion rate constant, k12, calculated according to
Smoluchowski (64) for non-charged molecules, has a value of
1.9 × 1010 dm3 mol-1 s-1. Keq was estimated using the Fuoss
and Eigen equation (equation (13)) (65).
(9)  
(13)
where w r is the work required to bring the reactants to the
separation distance d. Because we use neutral quenchers
throughout this study, wr is zero. The value of Keq is in the range
5.2–11.1 M-1 for the oxidative quenching of [Ru(NN)3–T]2+ with
quinones. Keq values given in Table 2 are close to the binding
constant values obtained from absorption and emission
techniques (Kabs and Kem
a a ) in Table 1. Because the values of k12
and Keq are known, the value for k23, the rate constant for the
process of ET in the encounter complex, can be calculated from
the observed kq values using equation (11).
In order to treat the dynamic quenching process in terms of ther-
modynamic function (ΔG0), we correlated the ET rate constant, k23,
2+
with quinones.
Luminescence 2013
A photophysic approach
-1 -1 0 2+
Figure 5. Plot of log k23, M s vs ΔG , eV for the oxidative quenching of [Ru(NN)3–T]
complexes with quinones.
values estimated from the kq values with the free energy change
(ΔG0) of the electron transfer process (equation (7)). The plot of
log k23 vs ΔG0 is shown in Fig. 5 and the ET rate constant increases
with increasing the driving force (ΔG0) of the ET reaction and at-
tains saturation at high ΔGo values (0.4 eV). The values of k23
(ket) can also be calculated using semiclassical theory from equa-
tion (8). The experimental k23 values along with the calculated ket
(solid line) values were plotted against ΔG° values (Fig. 5) for all
[Ru(NN)3–T]2+ complexes. Figure 5 shows that the rate constants
for ET reaction of chosen redox system are in accordance with
Rhem–Weller model.
Conclusion
The tyrosine–reaction center–quinone system in PSII is success-
fully mimicked by studying the ET reaction of [Ru(NN)3–T]2+
complexes with quinones. Modification of periphery of the 2,2′-
bipyridine ligands affects the photophysical properties and
hence, the ET properties of [Ru(NN)3–T]2+ complexes. The
binding constant values obtained from absorption and emission
techniques (Kabs
a and Kem
a ) and equilibrium constant values (Keq)
obtained from equation (13) established the interaction of
quinones with [Ru(NN)3–T]2+ complexes. The quenching rate
constants are varied with respect to the nature of the (elec-
tron releasing and withdrawing) substituents. The plot of
log k23 vs ΔG0 shows that the ET process from [Ru(NN)3]2+
carrying a tyrosine moiety with quinones is in accordance
with the Rhem–Weller model.
Acknowledgements
We sincerely thank Prof. P. Ramamurthy, National Center for
Ultrafast Processes, University of Madras, Taramani, Chennai for
his help in time resolved measurements. We sincerely thank Dr
M. Vairamani, IICT, Hyderabad for his help in HR-MS.
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