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PAPER
Cite this: Photochem. Photobiol. Sci.,
2014, 13, 272
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New cyclometallated Ru(II) complex for potential
application in photochemotherapy?†
Bryan A. Albani,a Bruno Peña,b Kim R. Dunbar*b and Claudia Turro*a
In an effort to create a molecule that absorbs further into the optimum window for photochemotherapy
(PCT), the new cyclometallated complex [Ru(biq)2( phpy)](PF6) (1, biq = 2,2’-biquinoline, phpy− = deprotonated 2-phenylpyridine) was synthesized, characterized and compared to the known photoactive
complexes [Ru(biq)2(bpy)](PF6)2 (2, bpy = 2,2’-bipyridine) and [Ru(biq)2( phen)](PF6)2 (3, phen = 1,10-phenanthroline), both of which undergo exchange of one biq ligand when irradiated with red light in coordinating solvents. Excited state ligand dissociation in 2 and 3 is believed to be related to the steric
hindrance afforded by the presence of two coordinated biq ligands. The ligand exchange quantum yield
of 2 is ∼2-fold greater than that of 3, which was shown to be cytotoxic when irradiated with visible light.
Received 15th September 2013,
Accepted 5th November 2013
Cyclometallation results in a red shift of the MLCT absorption maximum of 1 by ∼100 nm relative to those
DOI: 10.1039/c3pp50327e
of 2 and 3, but, although 1 exhibits a distorted octahedral geometry, photoinduced ligand exchange does
not occur. DFT calculations were used to aid in our understanding of the lack of photochemistry of 1
www.rsc.org/pps
which is explained by the destabilization of the eg(σ*) orbitals upon cyclometallation.
Introduction
Ruthenium(II) polypyridyl complexes with extended aromatic
ligands have been shown to interact with DNA as chemotherapeutic agents and molecular light switches through intercalation and electrostatic interactions.1–4 Recent studies indicate
that certain Ru(II) complexes have the ability to undergo photoinduced ligand exchange forming covalent bonds with DNA in
a manner akin to cisplatin, such that these lesions may result
in cell death. Unlike traditional photodynamic therapy (PDT)
agents that rely on the generation of singlet oxygen for action,
these photo-cisplatin analogs achieve cell death via mechanisms that are independent of oxygen; in order to differentiate
the two methods, the latter is referred to as photochemotherapy
(PCT).5–7
PCT involving transition metal complexes has generally
focused on the exchange of monodentate ligands upon
irradiation.5,8,9 The photoinduced ligand exchange of bidentate ligands bound to ruthenium(II), however, is well documented for sterically strained complexes including those with
ligands such as 2,2′-biquinoline (biq).10 For example, the
a
Department of Chemistry and Biochemistry, The Ohio State University, Columbus,
OH, USA. E-mail: turro.1@osu.edu
b
Department of Chemistry, Texas A&M University, College Station, TX, USA.
E-mail: dunbar@mail.chem.tamu.edu
† Electronic supplementary information (ESI) available: Additional crystal structure and crystallographic data, calculations, 1H NMR data, emission spectra. See
DOI: 10.1039/c3pp50327e
272 | Photochem. Photobiol. Sci., 2014, 13, 272–280
photoinduced exchange of a biq ligand in [Ru(biq)2(bpy)]2+
(bpy = 2,2′-bipyridine) in CH3CN results in the formation of
the intermediate cis-[Ru(biq)(bpy)(CH3CN)2]2+, which can be
used in the synthesis of tris-heteroleptic Ru(II) complexes of
the type [Ru(biq)( phen)(L)]2+ in the presence of a variety
of bidentate ligands, L.10 It was not until decades later that
[Ru(biq)(phen)2]2+ and [Ru(biq)2(phen)]2+ (phen = 1,10-phenanthroline) were shown to exhibit cytotoxicity upon irradiation
with visible light, while being relatively non-toxic under
similar conditions in the dark.11 Both Ru(II) complexes
undergo ligand dissociation in water following the absorption
of visible light to generate the corresponding bis-aqua complexes; the latter species covalently bind to DNA in vitro and
these adducts are believed to result in cell death.6,11
Photoinduced ligand exchange occurs in complexes with
3
LF (ligand field) dd states that are thermally accessible from
the lower-lying energy 3MLCT (metal-to-ligand charge transfer)
state(s).12–15 The thermal population of the metal centered 3LF
state results in electron density on the eg-type orbitals with
Ru–L(σ*) character, thus resulting in ligand dissociation.12–15
The exchange of bidentate ligands, however, is unusual
because both bonds must be cleaved upon MLCT excitation.
Bulky biq ligands that sterically strain the conventional octahedral geometry in Ru(II) complexes are believed to lower the
energy of the 3LF state relative to the 3MLCT state, thus resulting in enhanced photochemistry.6,11
The maximum of the MLCT absorption of [Ru(biq)2( phen)]2+ located at 550 nm in H2O is outside the optimal excitation range for PCT which is 600–850 nm.11 Therefore,
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Fig. 1
Paper
Schematic representations of the molecular structures of 1–3.
biquinoline complexes that are capable of undergoing photochemical ligand exchange, but with lower energy absorption,
are desirable. Cyclometallated Ru(II) complexes have been utilized as light harvesters in solar energy conversion schemes
because their MLCT absorption bands are broader and at
lower energies relative to the diimine analogs.16–18 The present
work focuses on the synthesis and characterization of [Ru(biq)2( phpy)](PF6) (1) ( phpy− = deprotonated 2-phenylpyridine). The photophysical properties and photochemistry of 1
were investigated and compared to those of [Ru(biq)2(bpy)](PF6)2 (2) and [Ru(biq)2( phen)](PF6)2 (3). A schematic representation of the molecular structures of 1–3 is displayed in Fig. 1.
Experimental section
Materials
The starting materials RuCl3·3H2O (Sigma-Aldrich), 2,2′-biquinoline (Acros, TCI), 2,2′-bipyridine (Sigma-Aldrich), 1,10-phenanthroline (Sigma-Aldrich), and ascorbic acid (Sigma-Aldrich)
were used as received without further purification. Ethanol
(Decon Laboratories Inc. 200 proof ) was used as received for
the synthesis of 2 and 3. For the preparation of 1, ethanol
(KORTEP, 200 proof ) was dried over Mg/I2 and was distilled
prior to use. Standard Schlenk-line techniques (N2 atmosphere) were used to maintain anaerobic conditions during
preparation of the compounds. All solvents used for chromatography (EMD Chemicals) were used as received without further
purification. Analytical Thin Layer Chromatography (TLC) was
performed on aluminum-backed sheets coated with aluminum
oxide neutral 60 F254 adsorbent (0.20 mm thickness, EMD
Chemicals). Flash chromatography was carried out with
alumina (activated, basic, Brockmann I) from Sigma-Aldrich.
The compounds [Ru( phpy)(CH3CN)4](PF6),19 Ru(biq)2Cl2,20
2,21 and 321 were prepared following reported procedures.
Instrumentation
The 1H NMR spectrum of 1 was measured on a Varian Inova
500 MHz spectrometer whereas those of 2 and 3 were recorded
on a Bruker 400 MHz DPX ultrashield system. Electrospray
ionization (ESI) mass spectrometry data were collected on a
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Bruker micrOTOF instrument with methanol as the eluent.
Electronic absorption spectral measurements were carried out
using a Hewlett Packard 8453 diode array spectrometer and
electrochemical studies were performed on a BAS CV-50W
voltammetric analyzer. Emission spectra were obtained on a
Horiba Fluormax-4 spectrometer for 2 and 3, and near IR emission in 1 was obtained on a home built instrument utilizing a
germanium detector. Photolysis and quantum yield experiments were carried out using a 150 W Xe short arc lamp
(USHIO) in an upright Milliarc lamp housing unit (PTI)
powered by a LPS-220 power supply (PTI) equipped with a
LPS-221 igniter (PTI). The desired wavelength range was
attained using band-pass filters (Thorlabs, fwhm ∼10 nm) or
3 mm thick (2 mm for 610 nm) long-pass filters (CVI MellesGriot). Gel imaging was performed with a Bio Rad Gel Doc
2000 transilluminator.
[Ru(biq)2( phpy)](PF6) (1)
The ligand 2,2′-biquinoline (100 mg, 0.39 mmol) was added to
a yellow suspension of [Ru( phpy)(CH3CN)4][PF6] (0.10 g,
0.18 mmol) in ethanol (15 mL), and the mixture was refluxed
for 5 h. The resulting dark green solution was reduced to
dryness, and the residue was purified by column chromatography (basic Al2O3, CH3CN–CH2Cl2, gradient from 0% to 25%
CH3CN). The first green band was collected and reduced to
dryness. The solid residue was dissolved with CH2Cl2 (10 mL)
and hexanes (8 mL) was added slowly. The green precipitate
was collected by filtration and washed with CH2Cl2–hexanes
1 : 1 (3 × 20 mL). Yield: 0.089 g (53%). 1H NMR (500 MHz,
CD3CN): δ 8.93 (d, 1H, 3J = 8.5 Hz), 8.84 (d, 1H, 3J = 8.5 Hz),
8.78 (d, 1H, 3J = 9.0 Hz), 8.70 (d, 1H, 3J = 8.5 Hz), 8.64 (d, 1H,
3
J = 9.0 Hz), 8.60 (d, 1H, 3J = 9.0 Hz), 8.28 (d, 1H, 3J = 8.5 Hz),
8.24 (d, 1H, 3J = 9.0 Hz), 8.04 (dd, 1H, 3J = 8.0 Hz, 4J = 1.5 Hz),
7.96 (dd, 1H, 3J = 8.0 Hz, 4J = 1.5 Hz), 7.73 (dd, 1H, 3J = 8.0 Hz,
4
J = 1.5 Hz), 7.62 (d, 2H, 3J = 8.5 Hz), 7.43–7.33 (m, 4H), 7.31
(ddd, 1H, 3J = 8.0 Hz, 3J = 6.5 Hz, 4J = 1.0 Hz), 7.27 (m, 2H),
7.22 (ddd, 1H, 3J = 8.0 Hz, 3J = 6.5 Hz, 4J = 1.0 Hz), 7.13 (d, 1H,
3
J = 8.0 Hz), 7.08 (d, 1H, 3J = 9.0 Hz), 6.94 (m, 2H), 6.88 (ddd,
1H, 3J = 8.5 Hz, 3J = 7.0 Hz, 4J = 1.5 Hz), 6.85–6.79 (m, 3H), 6.66
(ddd, 1H, 3J = 8.5 Hz, 3J = 7.0 Hz, 4J = 1.5 Hz), 6.31 (ddd, 1H,
Photochem. Photobiol. Sci., 2014, 13, 272–280 | 273
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3
J = 7.5 Hz, 3J = 7.5 Hz, 4J = 1.5 Hz), 6.25 (dd, 1H, 3J = 8.0 Hz,
J = 1.0 Hz). Elem. anal. calcd for [Ru(biq)2(phpy)](PF6): C, 61.8%;
N, 7.67%; H, 3.54%. Found: C, 61.4%; N, 7.61%; H, 3.66%.
4
Methods
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1
H NMR spectroscopy was performed in (CD3)2CO (acetone-d6)
or CD3CN and all resonances were referenced to the residual
protonated solvent peak. Cyclic voltammetry experiments were
performed in a three-electrode cell with a Pt working electrode,
a Pt wire auxiliary electrode, and a saturated Ag/AgCl reference
electrode. The samples were dissolved in distilled CH3CN
containing 0.1 M tetrabutylammonium hexafluorophosphate
as the supporting electrolyte, and bubbled with N2 for
10 minutes prior to each measurement. The cyclic voltammetry
data were recorded at a scan rate of 100 mV s−1 with ferrocene
being added to the sample after each measurement to serve
as an internal standard (+0.40 V vs. SCE in CH3CN).22 The
chloride salt of each complex was used for experiments
performed in H2O, which were obtained using an Amberlite
IRA-410 ion exchange resin, prepared by soaking the powder in
a 1 M HCl solution at 50 °C for 3 days, with methanol as the
eluent. Emission spectra were measured at both 298 K and
77 K in CH3CN in a 1 × 1 cm quartz cuvette using an excitation
wavelength corresponding to the maximum of the MLCT
absorption for 2 and 3, and 405 nm for 1. Elemental Analysis
was performed by Atlantic Microlab Inc.
The quantum yields (Ф) for photoinduced ligand exchange
of the biq ligand in H2O were measured for complexes 2 and 3
with 550 nm and 600 nm irradiation wavelengths using the
appropriate band-pass filters.23 The moles of complex reacted
were quantitated using electronic absorption spectroscopy by
monitoring the decrease in MLCT absorption maximum of
each complex as a function of irradiation time (moles reacted
per s) at early irradiation times, and Reinecke’s salt was used
as an actinometer to determine the intensity (Einstein s−1) of
the Xe arc lamp at the desired wavelength.23,24
Dark green single crystals of 1 were grown by slow diffusion
of hexanes into a dichloromethane solution of the compound
in a fine tube. X-ray data were collected at 291 K on a Bruker
APEX II CCD X-ray diffractometer equipped with a graphite
monochromated MoKα radiation source (λ = 0.71073 Å). The
data sets were integrated with the Bruker SAINT software
package.25 The absorption correction (SADABS)26 was based on
fitting a function to the empirical transmission surface as
sampled by multiple equivalent measurements. Solution and
refinement of the crystal structures was carried out using the
SHELX27 suite of programs as implemented in X-SEED.28 The
structure was solved by direct methods with all non-hydrogen
atoms being refined with anisotropic displacement parameters
using a full-matrix least-squares technique on F 2. Hydrogen
atoms were fixed to parent atoms and refined using the riding
model.
The supercoiled pUC18 (Bayou Biolabs) used in the gel electrophoresis mobility shift assays was purified using a standard
QIAprep® Spin Miniprep Kit (QIAGEN). The DNA was bound
to a miniprep spin column, washed with 500 μL PB buffer,
274 | Photochem. Photobiol. Sci., 2014, 13, 272–280
Photochemical & Photobiological Sciences
with 750 μL PE buffer, and extracted from the column with
warm water. The purified DNA was then linearized using a
QIAquick® GelExtraction Kit (QIAGEN). For the linearization,
55 μL of water, 25 μL of pUC18, 10 μL of React 4 Buffer (Invitrogen), and 10 μL Sma1 enzyme (Invitrogen) were added to a
small Eppendorf tube and heated at 30 °C for 1 h and the
enzyme was then deactivated by incubating the sample at
65 °C for 10 minutes. After this procedure, QG buffer (300 μL)
and isopropanol (100 μL) were added to the mixture, was
added to a spin column and washed with 750 μL of PE buffer,
and was then extracted from the column with 40 μL of water.
The agarose gel electrophoresis was carried out using 1× TBE
buffer ( pH = 8.28) at room temperature for one hour at 95 V
powered by an EC 105 voltmeter produced by E-C Apparatus
Corporation. Gels were then stained in ethidium bromide solutions (0.5 μg mL−1) for 30 minutes then soaked in water for
30 minutes.
Calculations were performed with density functional theory
(DFT) using the Gaussian 09 program.29 The B3LYP30–32 functional along with the 6-31G* basis set for H, C, and N33 and
the SDD energy consistent pseudopotentials were used for
Ru.34 Optimization of full geometries was carried out with the
respective programs and orbital analysis was performed in
Gaussview version 3.09.35 Following optimization of the molecular structures, frequency analysis was performed to ensure
the existence of local minima on the potential energy surfaces.
Electronic absorption singlet-to-singlet transitions were calculated using time-dependent DFT (TD-DFT) methods with the
polarizable continuum model (PCM) that mimicked the
solvation effect of CH3CN in Gaussian 09.36
Results and discussion
X-ray crystal structure of 1
The molecular structure of 1 is depicted in Fig. 2 with
crystallographic data being compiled in Tables 1 and S1†
Fig. 2 Thermal ellipsoid plot of the [PF6]− salt of complex 1 (ellipsoids
drawn at 50% probability).
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Table 1 Selected bond distance, angles, and dihedral angles for the
cation [Ru(biq)2( phpy)]+ (1)
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Bond lengths (Å)
Ru1–C1
Ru1–N1
Ru1–N2
Ru1–N3
Ru1–N4
Ru1–N5
Bond angles (°)
2.095(4)
2.087(4)
2.092(3)
2.148(3)
2.091(4)
2.096(3)
C1–Ru1–N1
N2–Ru1–N3
N4–Ru1–N5
N1–Ru1–N3
N3–Ru1–N4
C1–Ru1–N4
78.8(2)
76.8(1)
76.7(1)
90.8(1)
98.3(1)
92.4(2)
Dihedral angles (°)
N2–C20–C21–N3
C19–C20–C21–C22
N4–C38–C39–N5
C37–C38–C39–C40
N2–Ru1–N3–C29
N4–Ru1–N5–C47
−9.9(6)
−11.9(8)
−0.9(6)
0.9(8)
−165.1(4)
166.2(4)
(CCDC 961134). Compound 1 crystallizes in the monoclinic
space group P21/n and there are two interstitial dichloromethane molecules in the asymmetric unit. The coordination
sphere of the metal center consists of five nitrogen atoms and
one carbon atom in a distorted octahedral environment. The
Ru1–C1 bond length of 2.095(4) Å in 1 is longer than the corresponding bond distances in [Ru(bpy)2(phpy)]+, 2.044(1) Å,37 and
in [Ru(phen)2(phpy)]+, 2.036(7) Å,38 which may be attributed to
the steric repulsion between the biq ligands. Three of the Ru–N
bond lengths with the biq ligands, Ru1–N2, Ru1–N4 and
Ru1–N5, are similar (∼2.09 Å) and within the range of those
found in the closely related compound 3 and [Ru(phen)2(biq)]2+,
2.079(2) to 2.0112(3) Å.11 In contrast, the Ru1–N3biq bond
located trans to the C donor atom of phpy− is the longest,
2.148(3) Å, reflecting the strong trans influence of the phenyl
ring of phpy−. The angle between adjacent biq ligands,
N3–Ru1–N4 is 98.3(1)° which is larger than the angles formed
between each biq and phpy−, viz., N1–Ru1–N3 and C1–Ru1–N4,
which are 90.8(1) and 92.4(2)°, respectively (Table 1). The more
obtuse N3–Ru1–N4 angle is likely a consequence of steric
repulsion between the two bulky biq ligands. The biq ligand
trans to the C1 atom of phpy− is twisted about the C–C bond,
N2–C20–C21–N3, −9.9(6)°, whereas such a distortion is not
observed in the other biq ligand, N4–C38–C39–N5, 0.9(6)°
(Table 1). In addition, the quinoline moieties of both biq
ligands are bent by ∼15° out of the plane formed with the
metal center, a distortion that was also observed in 3.11
Electronic absorption, emission, and electrochemistry
The absorption profiles of 2 and 3 are in good agreement
with previously published data (Fig. 3).21 Complex 2
exhibits maxima at 549 nm (ε = 6600 M−1 cm−1), 482 nm (ε =
4800 M−1 cm−1), and 407 nm (ε = 2800 M−1 cm−1) in CH3CN,
and those for 3 are observed at 552 nm (ε = 9600 M−1 cm−1),
480 nm (ε = 7100 M−1 cm−1), and 409 nm (ε = 3900 M−1 cm−1)
in the same solvent. The transitions at ∼410 nm are assigned
as Ru(t2g)→L(π*) (L = bpy, phen) 1MLCT in 2 and 3, respectively, whereas those at ∼480 nm and ∼550 nm are attributed to
Ru(t2g)→biq(π*) transitions.21 Three 1MLCT absorption peaks
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Fig. 3 (a) Electronic absorption spectra for 1–3 in CH3CN and (b) normalized emission spectra of 1 and 2 at 77 K in CH3CN.
are also observed in 1, but are red-shifted as compared to the
corresponding bands in 2 and 3 (Fig. 3a), with Ru(t2g)→phpy−(π*)
absorption maximum at 455 nm (ε = 1700 M−1 cm−1), and
bands associated with Ru(t2g)→biq(π*) transitions at 545 (ε =
2200 M−1 cm−1) and 640 nm (ε = 5200 M−1 cm−1). The red
shift in 1 is attributed to an increase in energy of the highest
occupied molecular orbital (HOMO) resulting from cyclometallation, since the energy of the biq(π*) orbitals is expected to
remain relatively unchanged.16,39 The carbon to metal bond
provides significant ligand character to the HOMO, which is
typically nearly solely metal in character in Ru(II) polypyridyl
complexes.16,39 Emission in the near-IR spectral region is
observed from complex 1 in CH3CN with maxima at 1030 nm
and 980 nm at 298 K and 77 K, respectively (λexc = 405 nm)
shown in Fig. 3b, which is significantly red shifted from that
of 2 and 3 with maxima at 748 nm and 747 nm at room temperature, respectively, and at 740 nm and 735 at 77 K, respectively, in agreement with published results.21
Cyclic voltammetry reveals quasi-reversible metal-centered
oxidation events, E1/2(Ru3+/2+), at +1.44 V vs. SCE for 2 and 3 in
CH3CN, which is typical of Ru(II) polypyridyl complexes.40,41
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In the case of the cyclometallated complex, 1, the observed Ru(III/II)
couple is observed at a less positive potential, with E1/2(Ru3+/2+) =
+0.65 V vs. SCE. This cathodic shift in oxidation potential is
typical of cyclometallated complexes relative to bpy or phen
and results from the increased electron density on the metal
provided by the covalent bonding of the phpy− ligand.39 The
increased electron density on the metal also increases the
π-backbonding to the pyridyl rings of the biq ligands which
leads to a cathodic shift in the sequential ligand centered
reductions for 1 relative to those of 2 and 3.39 Quasi-reversible
reduction waves, assigned as reduction of the biq ligands, are
observed with E1/2(Ru2+/+) = −1.06 and −1.31 vs. SCE for 1 in
CH3CN, whereas the analogous reduction events of the biq
ligands occur at −0.80 V and −1.03 V vs. SCE for 2 and at −0.80 V
and −1.05 V vs. SCE for 3 in the same solvent. A third
reduction process is observed for 2 and 3 in CH3CN with the
values E1/2(Ru2+/+) = −1.59 V and E1/2(Ru2+/+) = −1.56 V vs. SCE,
respectively, assigned to the reduction of the bpy and phen
ligands. The reduction of the phpy− ligand in 1 is not observed
and must occur outside the spectral analysis window for CH3CN.
Photochemistry
The photoreactivity of 1–3 was evaluated by monitoring the
changes to the electronic absorption spectrum of each
complex as a function of irradiation time. As expected based
on prior work, the irradiation of 2 and 3 in H2O and CH3CN
with visible light (λirr ≥ 530 nm or λirr ≥ 630 nm) results in
exchange of one biq ligand with two molecules of coordinating solvent, generating [Ru(biq)(L)(H2O)2]2+ and [Ru(biq)(L)(CH3CN)2]2+ (L = bpy, phen), respectively (Fig. 4 and S6†), but
the complexes are not reactive when kept in the dark under
similar experimental conditions (Fig. S4 and S5†).10,11 In contrast, complex 1 is not photochemically active in CH3CN (λirr ≥
530 nm, Fig. S7†) or H2O based on absorption changes
or when monitored by mass spectrometry as a function of
irradiation time (λirr ≥ 530 nm).
The quantum yield for the exchange of the biq ligand in 2
in H2O with λirr = 550 nm and λirr = 600 nm irradiation were
measured to be 0.068(2) and 0.053(3), respectively.
These values are factors of 3.4 and 2.2 greater than those
measured for 3, Φ550 = 0.020(3) and Φ600 = 0.024(2) at each
wavelength, respectively. A similar trend was observed between
the sterically hindered complexes [Ru(bpy)2(dmbpy)]2+ and
[Ru(bpy)2(dmdpq)]2+ (dmbpy = 6,6′-dimethyl-2,2′-bipyridine,
dmdpq = 7,10-dimethyl-pyrazino[2,3-f ]-1,10-phenanthroline)
in which the exchange of the dmdpq ligand possessing fused
aromatic rings occurred less efficiently than the analogous
dmbpy complex,6 suggesting that less rigid bidentate ligands
enhance the ligand exchange.
Calculations
DFT and TD-DFT calculations were performed to gain a better
understanding of the electrochemistry, photophysical properties, and photochemistry observed for the three complexes.
The DFT calculations reveal metal-based HOMO, HOMO−1,
and HOMO−2 levels representing the dxy, dxz, and dyz orbitals
276 | Photochem. Photobiol. Sci., 2014, 13, 272–280
Fig. 4 Electronic absorption spectral changes of (a) 2 (40 μM) with
increasing irradiation times, tirr, 0, 1, 2, 3, 5, 10, 15, 20, 30, 45, 60, 90,
and 180 min and (b) 3 (15 μM) at tirr = 0, 2, 5, 10, 20, 30, and 60 min in
H2O (λirr ≥ 630 nm).
for complexes 1–3. These HOMOs are calculated at nearly identical energies for 2 and 3, but that of 1 is destabilized by ∼0.6 eV
and exhibits significant phpy− ligand character and electron density on the metal–carbon bond (Fig. 5). The HOMO of
2 was arbitrarily set at 0.0 eV. The differences in the calculated
energies of the HOMOs agree with the cathodic shift in the
experimental oxidation potential of 0.75 V between 1 and 2 or
3. The additional ease in oxidation by ∼0.15 V may be related
to the overall +1 charge of 1 as compared to +2 of 2 and 3
which renders removal of an electron from the former more
favorable. The LUMO and LUMO+1 orbitals of 1–3 are calculated to be localized on the biq ligands and to lie at similar
energies in the three complexes. Although 1 is more difficult
to reduce than 2 and 3 by ∼0.2 V, this difference may also be
related to the overall charge of the complexes.
TD-DFT calculations reveal that the lowest vertical singlet
excited states of 1, 2, and 3 possess significant contributions,
∼88% for 1 and ∼97% for 2 and 3, from HOMO→LUMO transitions, but low oscillator strengths, with maxima at 840 nm
( f = 0.0013), 586 nm ( f = 0.0003), and 587 nm ( f = 0.0004),
respectively (Tables S2–S4†). More intense absorption bands
with f > 0.01 are predicted at 686 nm ( f = 0.027) for 1, at
523 nm ( f = 0.076) for 2, and at 527 nm ( f = 0.086) for 3
calculated to possess 83%, 93%, and 96% contribution
from HOMO−1→LUMO transitions, respectively. These calculated absorption maxima are similar to the experimental
values, 640 nm, 549 nm, and 552 nm, for 1, 2, and 3,
respectively.
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the related cyclometallated complex [Ru(phpy)(bpy)(CH3CN)2]+.42
Upon irradiation, one bond is weakened due to population of
the lower lying energy 3LF state resulting in ligand dissociation
and solvent coordination, but the remaining CH3CN does not
exchange with extended photolysis because the higher-lying
3
LF state is not populated.
Gel mobility assays
Fig. 5 Calculated (a) MO diagrams showing the frontier orbitals and (b)
electron densities of the HOMOs (isovalue = 0.04) of 1 and 2.
In order to understand the lack of photodissociation of the
biq ligand in 1 as compared to 2 and 3, the orbitals and
transitions involved in the process must be considered. As
stated previously, ligand dissociation is believed to occur via
thermal population of the 3LF states from the low-lying 3MLCT
state(s).12–15 Experimental data, calculations, and previous
work all indicate that the HOMO in 1 lies at a higher energy
than those of 2 and 3, but that the energies of the LUMOs
remain relatively unchanged among the three complexes.16 It
is expected that cyclometallation results in a larger gap
between the 3MLCT state and 3LF states because the eg(σ*)
orbitals are destabilized due to the increased covalent interaction provided by the Ru–C bond, significantly raising the
energy of the eg orbitals with Ru–L(σ*) character.16 The eg(σ*)
orbitals in 2 are calculated as the LUMO+9 (dz2) and LUMO+10
(dx2−y2), are relatively close in energy (ΔE = 0.26 eV). In contrast,
the eg(σ*) orbitals in 1 are calculated to be LUMO+10 (dz2) and
LUMO+17 (dx2−y2) with an energy difference of 3.22 eV.
The relative energies of the two eg(σ*) orbitals is related to
the energies of the 3LF states involving the population of each
d-orbital, dz2 and dx2−y2. In order for photodissociation of the
bidentate ligand to take place, both Ru–N(biq) bonds must be
broken. Because the 3LF state associated with the dx2−y2 orbital
lies at a very high energy in 1, it is not likely to be accessible
upon irradiation with visible light. It is proposed that,
although one Ru–N(biq) bond may break upon irradiation, it
quickly re-coordinates to the metal. This explanation is also
consistent with the observed exchange of only one CH3CN in
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Gel electrophoresis mobility shift assays were carried out in
order to compare the photoinduced DNA binding of 2 and 3. It
is well documented that cisplatin thermally binds to linearized
DNA and reduces its migration through an agarose gel in a
concentration-dependent manner.43 The same pattern is
observed for 2 and 3 upon irradiation with low energy light,
but not in the dark (Fig. 6). In Fig. 6, lanes 1 and 8 contain 1 kb
DNA ladder, lanes 2–7 were loaded with 50 μM pUC18 DNA,
and lanes 3–6 contain increasing concentrations of 2 or 3. In
Fig. 6a and 6c, the samples in lanes 3–6 were irradiated for
15 minutes with λirr ≥ 630 nm light prior to loading. It is
evident in Fig. 6a that, as the concentration of 2 is increased,
the DNA mobility decreases, whereas no shift in mobility is
observed when the samples are incubated in the dark for
20 min under similar experimental conditions (Fig. 6b). These
results are indicative of covalent binding of 2 to DNA only
upon irradiation. Fig. 6c and 6d display the results for complex
3 irradiated under the same conditions as 2 (Fig. 6a) and in
the dark, respectively. The reduced effect of 3 as compared to 2
on the DNA mobility can be attributed to the ∼2-fold lower
Ф600 value of the former, such that a smaller amount of the
photoproduct that binds to DNA is formed. Increased DNA
binding was observed for 3 when the irradiation times were
doubled, but it nevertheless remained lower than the effect
observed for 2 (Fig. S8†).
Conclusions
The new cyclometallated complex [Ru(biq)2( phpy)](PF6) (1) was
synthesized and characterized by various methods including
X-ray crystallography. The photophysical electrochemical and
photochemical properties of 1 were compared to those of
known photoactive complexes [Ru(biq)2(bpy)](PF6)2 (2) and
[Ru(biq)2( phen)](PF6)2 (3). Complexes 2 and 3 undergo
exchange of one of the biq ligands when irradiated with λirr ≥
630 nm light in water to generate the corresponding complexes
[Ru(biq)2(bpy)(H2O)2](PF6)2 and [Ru(biq)2( phen)(H2O)2](PF6)2.
The resulting bis-aqua photoproducts covalently bind to
linearized ds-DNA. The quantum yield for ligand exchange for 2,
Φ600 = 0.053(3), was measured to be 2.2-fold greater than that
determined for 3, Φ600 = 0.024(2), at the same irradiation wavelength, 600 nm, thereby lending support to the hypothesis that
less rigid ancillary ligands lead to more efficient biq ligand
exchange. The differences in ligand exchange quantum yields
of 2 and 3 were correlated to the DNA binding ability of the
complexes.
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Fig. 6 Imaged ethidium bromide-stained agarose gels of 50 μM linearized pUC18 plasmid (10 mM phosphate buffer, pH = 7.8) in the presence of
various concentrations of complex: lanes 1 and 8, 1 kb DNA molecular weight standard; lanes 2 and 7, linearized plasmid alone; lanes 3–6, 25, 50,
75, 100 μM of 2 (a) irradiated (λirr ≥ 630 nm, 15 min), (b) incubated in the dark (20 min, 298 K) and 3 (c) irradiated (λirr ≥ 630 nm, 15 min), and (d) incubated in the dark (20 min, 298 K).
Since the compounds [Ru(bpy)3](PF6)2 and [Ru( phen)3](PF6)2 are stable upon irradiation relative to the biq complexes
2 and 3, steric bulk was thought to be a key criteria for photoinduced bidentate ligand exchange. Although the crystal structure of 1 reveals an elongated Ru–N(biq) bond, the complex
does not display photoinduced ligand substitution in coordinating solvents under similar conditions as those used for 2
and 3. The difference in reactivity of the cyclometallated
complex 1 is ascribed to increased energy of the metal-centered 3LF states resulting from the bonding of the strong
σ-donor phpy− ligand, a finding supported by DFT calculations.
Complexes 2 and 3 are good candidates as PCT agents owing
to their covalent DNA binding upon irradiation with light
in the photodynamic window. Although the absorption
maximum of 1 is red-shifted relative to those of 2 and 3, the
lack of photochemistry of the former compound indicates that
the use of cyclometallated Ru(II) complexes may not be a good
strategy for the design of new PCT agents.
Acknowledgements
K.R.D. and C.T. thank the National Science Foundation for
partial support of this work (CHE-1213646) and the Ohio
Supercomputer Center.
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