J. Phys. Chem.

A XXXX, xxx, 000 A

Excitation-Dependent Fluorescence of Triphenylamine-Substituted Tridentate Pyridyl

Ruthenium Complexes

Lixin Xiao,†,‡ Yongqian Xu,§ Ming Yan,† David Galipeau,† Xiaojun Peng,§ and
Xingzhong Yan*,†
Center of Applied PhotoVoltaics, Department of Electrical Engineering and Computer Science, South Dakota
State UniVersity, Brookings, South Dakota 57007, USA, State Key Laboratory of Fine Chemicals, Dalian
UniVersity of Technology, Dalian 116012, People’s Republic of China, and State Key Laboratory for Mesoscopic
Physics and Department of Physics, Peking UniVersity, Beijing 100871, People’s Republic of China
ReceiVed: May 3, 2010; ReVised Manuscript ReceiVed: July 30, 2010

Two polypyridyl ruthenium complexes, bis[4-(N,N′-diphenylamino)phenyl-2,2′:6′,2′′-terpyridine]ruthenium(II)

(1) and bis[4′-(4-{2-[4-(N,N′-diphenylamino)phenyl]ethylene}phenyl)-2, 2′:6′,2′′-terpyridine]ruthenium(II) (2),
have been synthesized. They possess an extended conjugation and strongly coupled electronic states. The
features of these compounds were carefully studied from several respects. Steady-state spectroscopy showed
that the two compounds had strong excitation dependent emission behaviors caused by mixing features of
different electronic states. Femtosecond fluorescence upconversion spectroscopy was also used to investigate
the fluorescence dynamics of the compounds. An ultrafast relaxation time of ∼100 fs of the 1MLCT (metal-
to-ligand charge-transfer) states, which may originate from an ultrafast intersystem crossing to form 3MLCT
states, was found in both samples. However, thermal populated states and vibration associated excited state
interactions were suggested for 1 with excitation at wavelengths below 400 nm, whereas vibrational energy
redistribution with a time scale of few picoseconds was observed in the extended conjugated system of 2.
These compounds will have potential application in both artificial photosynthesis systems and photovoltaic
devices.

Introduction charge transfer, new methods need to be developed for control-

ling the strongly coupled dynamics within photovoltaic
Recently, photovoltaic materials for solar energy conversion materials.21,3 Also, in order to understand the interfacial charge
have attracted much attention worldwide.1-4 Light harvesting transfer processes in dye-sensitized wide-band semiconductors,
in terms of Förster-type hoping model has been intensively the relaxation dynamics of the excited states with the ruthenium
investigated by time-resolved spectroscopy within many pho- sensitizers has to be investigated because that is crucial for
tovoltaic materials.5 Advanced concepts have been also utilized controlling electron injection rates.21,3 Investigations on the
in the interpretation toward the issues of excited-state dynamics, dynamics of excited states of polypyridyl ruthenium complexes
which include how excitons and photoinduced charges migrate are very imperative for understanding their photophysical aspects
and how these processes are controlled in strongly coupled toward high conversion efficiency of solar energy. This will
multichromophoric light harvesting systems.6-8 As ideal light consequentially bring out a variety of applications of the
absorbers, polypyridyl ruthenium complexes are widely used ruthenium complexes in the design of nonlinear optical, electron-
in photovoltaic cells.9 Some polypyridyl ruthenium complexes transfer assemblies, artificial photosynthesis systems, and
have become paradigm complexes for photoinduced redox photochemical energy storage devices.
systems that can convert light energy into chemical energy,10-16 Polypyridyl ruthenium complexes show strong charge-transfer
and for sensitized semiconductors that convert solar energy into transitions between the metal-centered d orbital and the ligand-
electricity.9,17-19 The relaxation of excited states through fast centered π* orbital, normally named as metal-to-ligand charge-
electron transfer is the primary step in charge separation in the transfer (MLCT) transitions.10-16 These MLCT states are
photovoltaic devices fabricated by these ruthenium complexes.20-22 typically the lowest lying excited states since the highest
High conversion efficiency usually results from a fast electron occupied orbitals mainly possess the character from the 4d
injection from dye sensitizers, for example, polypyridyl ruthe- orbital, and the lowest unoccupied states have that from the
nium complexes, to wide band gap semiconductors with little pyridine π* orbitals.10,6 For the dynamics investigation of these
chance for charge transferring backward to the sensitizers.23-25 excited states,29 femtosecond time-resolved transient absorption
Long-distance and long-lived charge separated states are critical (TA) is a conventional method, whereas the time-resolved
in both artificial photosynthesis systems and photovoltaic fluorescence technique is seldom reported.10,30 The TA measure-
devices.24-28 To mimic nature and create highly efficient light ments of the paradigm compound, tris(2,2′-bipyridyl)ruthe-
harvesting materials for efficient long-distance energy and nium(II), showed a large dipole moment in the excited state.
This dipole moment was oriented along the axis from metal to
* To whom correspondence should be addressed. E-mail: xingzhong.yan@ the center of one of the bipyridine units. These behaviors
sdstate.edu. suggested that the excited electron is likely localized on one of
†
South Dakota State University.
‡
Peking University. the three bipyridine ligands, which is the topic of hot debate.10,29
§
Dalian University of Technology. Moreover, it is hard to directly observe the relaxation of the
10.1021/jp1040234  XXXX American Chemical Society
B J. Phys. Chem. A, Vol. xxx, No. xx, XXXX Xiao et al.

Figure 1. Structures of the complexes studied.

TABLE 1: UV-Vis Absorption Maximum, Molecular

singlet state 1MLCT due to extremely weak emission and a rapid Extinction Coefficient, Emission Maximum, and Emission
intersystem crossing (ISC) for forming a triplet state 3MLCT Quantum Yield (O) of the Ligands in CH2Cl2
within 1 ps. Recently, picosecond-time-resolved streak camera
λabsmax (ε, 104/cm-1 M-1)a
technique has provided dynamics information in the tens of
picoseconds time-scale which encompasses some sub-picosec- compounds πtpy-πtpy* πph-πtpy* em
λmax (nm) φ
onds relaxations of the vibronic or electronic levels in the triplet L1 288 (2.09) 356 (1.82) 472 b
0.58b
manifold of ruthenium complexes.30 Thus, femtosecond time- L2 282 (5.83) 385 (1.84) 514 0.55
resolved fluorescence appears to be more suitable to study the a
tpy, denotes trispyridine moiety and ph, denotes the phenyl
excitation relaxation process for the ultrafast response time moiety linked to the trispyridine moiety in the ligand. b Data from
within sub-picoseconds. However, the reported investigations ref 32b.
of the photophysics and photochemistry have been mostly
studied in the polypyridyl complexes with bidentate ligands.10 left. A little acetone was then added to redissolve the residues.
There is scarce investigation regarding to polypyridyl complexes After adding saturated NH4PF6 aqueous solution into the acetone
with tridentate ligands, and the assignment of the origin of the solution, precipitations were formed. These precipitations, which
observed femtosecond emission has not proven straightfor- are crude products, were collected by filtering and were washed
ward.10,31 with water. The crude products were dried and then purified by
To explore charge transfer and its role for achieving efficient silica gel column chromatography with an eluent, CH3CN/H2O/
sunlight conversion in the polypyridyl complexes, new poly- KNO3 saturated aqueous solution (30/1/1, v/v/v). A developed
pyridyl ruthenium complexes with triphenylamine modified red portion was collected and concentrated. To remove the
tridentate ligands have been synthesized, and their early KNO3, saturated NH4PF6 aqueous solution was added into the
photophysical processes have been investigated by femtosecond concentrated solution again. Red precipitations were collected
fluorescence up-conversion technique. As a result, there are and washed with water. These dried red precipitations are pure
extended conjugation and strongly coupled electronic states products. The 1H NMR and mass spectroscopy data were listed
within these new bis-tridentate ruthenium complexes. Their below.
emission behaviors are highly dependent on excitations. These 1 (yield 57%): 1H NMR (400 MHz, δppm, CD3COCD3): 6.10
compounds will have potential application in both artificial (d, J ) 8.4 Hz, 2H), 6.40 (d, J ) 7.6 Hz, 2H), 7.05 (d, J ) 7.6
photosynthesis systems and photovoltaic devices. Hz, 6H), 7.17 (m, 10H), 7.37 (m, 8H), 7.51 (m, 1H), 7.59 (s,
1H), 7.89 (d, J ) 6.0 Hz, 6H), 8.08 (d, J ) 8.4 Hz, 2H), 8.25
Experimental Section
(d, J ) 7.6 Hz, 1H), 8.44 (dd, J ) 6.0 Hz, J ) 6.0 Hz, 1H),
Materials. Two polypyridyl ruthenium complexes, bis[4- 8.61 (d, J ) 7.2 Hz, 2H), 8.72 (m, 2H), 9.17 (d, J ) 8.0 Hz,
(N,N′-diphenylamino)phenyl-2,2′: 6′,2′′-terpyridine]ruthenium 2H), 9.26 (s, 2H), 13C NMR (100 MHz, δppm, CD3COCD3):
(1) and bis[4′-(4-{2-[4-(N,N′-diphenylamino)phenyl]ethylene}- 118.27, 119.37, 122.44, 123.55, 124.38, 124.91, 125.64, 125.92,
phenyl)-2,2′:6′,2′′-terpyridine]ruthenium (2) (Figure 1), were 126.99, 127.30, 128.75, 129.51, 130.58, 137.54, 138.51, 145.80,
synthesized in this work. Ligands, 4-(N,N′-diphenylamino)phe- 147.30, 149.86, 152.55, 154.40, 159.32, 161.06, 168.04, ESI-
nyl-2,2′:6′,2′′-terpyridine (L1) and 4′-(4-{2-[4-(N,N′-diphe- MS (positive): m/z [M2+/2] ) 527 (cal. 1054).
nylamino)phenyl]ethylene}phenyl)-2,2′:6′,2′′-terpyridine (L2), 2 (yield 50%): 1H NMR (400 MHz, δppm, DMSO-d6): 7.01
were synthesized by using the methods in literatures.32,33 (d, J ) 8.8 Hz, 4H), 7.10 (m, 12H), 7.29 (m, 12H), 7.36 (dd,
Their spectral data were list in Table 1. Common solvents J ) 7.2 Hz, J ) 8.4 Hz, 8H), 7.56 (d, J ) 5.6 Hz, 2H), 7.61 (d,
were purified by redistillation. The synthesis protocols of the J ) 8.0 Hz, 2H), 7.95 (d, J ) 8.0 Hz, 4H, H5, H5′′), 8.08 (dd,
two polypyridyl complexes are described below. J ) 6.4 Hz, J ) 5.6 Hz, 4H, H4, H4′′), 8.53 (d, J ) 7.2 Hz, 4H,
RuCl3 · 3H2O (200 mg, 0.77 mmol) was added into EtOH/ H3, H3′′), 9.18 (d, J ) 8.4 Hz, 4H, H6, H6′′), 9.55 (s, 4H, H3′,
CHCl3 (3:1, v/v) solution with 0.77 mmol of ligands. After H5′), ESI-MS (positive): m/z [M2+/2] ) 629 (cal. 1258).
continuous stirring and refluxing for 2 h under nitrogen, the Steady-State Absorption and Emission. Steady-state ab-
mixture was cooled down, and the solvents were removed by sorption was recorded by an Agilent 8352 UV-visible spec-
vacuum evaporation. Brown powder was obtained. A 200 mg trophotometer. Steady-state emission of the polypyridyl ruthe-
portion of this brown powder and 0.45 mmol of ligand were nium solutions was measured by an Edinburgh FL920 spectro-
then mixed together and redissolved in 50 mL of ethanol. This fluorophotometer. The solutions used in these measurements
solution was stirred and refluxed for 24 h. After filtering out were with concentrations in the range from 0.01 to 0.1 mM.
the undissolvable substances in the cool solution, the solvents Electrochemistry Measurements. Electrochemical studies
were removed by rotating evaporation, and solid residuals were of the ruthenium complexes were conducted in anhydrous
Fluorescence of Tridentate Pyridyl Ruthenium Complexes J. Phys. Chem. A, Vol. xxx, No. xx, XXXX C

CH3CN, with 0.1 M Bu4NPF4 as the supporting electrolyte using

a BAS-100W electrochemical workstation at a scan rate of 100
mV/s. A glassy carbon electrode was used as the working
electrode, which was polished with an alumina paste before
analysis. Counter and reference electrodes were composed of
platinum wire and a non aqueous Ag/Ag+ electrode (0.01 M
AgNO3/0.1 M n-Bu4-NPF6 in CH3CN), respectively. The half-
wave potential of ferrocene/ferrocenium redox couple vs the
Ag/Ag+ electrode is 80 mV in CH3CN.34
Fluorescence Up-Conversion Measurements. Time-re-
solved fluorescence measurements for the polypyridyl ruthenium
solutions were carried out by using a femtosecond up-conversion
technique. These solutions used in the measurements were
prepared by dry and deoxygenated dichloromethane (CH2Cl2).
The femtosecond fluorescence up-conversion system used in
this work is a FOG 100 system (CDP, Russia) with a mode- Figure 2. Absorption spectra in CH2Cl2 (inset: an expansion spectrum
locked Ti-sapphire laser (Tsunami, Spectra Physics) source for 2).
pumped by a 10 W CWNd:YVO4 laser (Millennia, Spectra-
Physics). The solutions were excited by the second harmonic absorption is weaker than the peak at 532 nm for 1. This is
light generated by doubling the fundamental light from the very likely due to intramolecular electron transfer from the
mode-locked Ti-sapphire laser with a pulse width of ∼57 fs at conjugated triphenylamine groups to the metal center, as might
a repetition rate of 86 MHz. The center wavelength of the light impede metal to ligand charge transfer. This was consistent with
was tunable from 730 to 860 nm, and the laser spectrum was the results from electrochemistry studies below. Figure 3 shows
monitored by a spectrum analyzer (Ocean Optics). The polariza- the cyclic voltammograms of the two compounds. Two oxida-
tion of the excitation (second harmonic) beam for the anisotropy tion potentials (0.86 and 0.49 V) and one reduction potential
measurements was controlled with a Berek’s plate, as illustrated (-1.60 V) were found for 1. Interestingly, both the oxidation
widely in literature.36 Parallel (Fpar) and perpendicular (Fper) (0.69 and 0.48 V) and reduction (-0.34 and -1.24 V) potentials
polarized fluorescence signals were generated by vertically or were found to be lower for 2 than those for 1. Such a behavior
horizontally polarized excitation, respectively. The isotropic may be due to the increase of the conjugation in 2. During the
fluorescence was calculated by: Fpar+ 2GFper, and fluorescence oxidation of 2, the conjugated triphenyl electron donor could
anisotropy (γ) was then given by: γ) (Fpar - GFper)/(Fpar+ increase the energy level of the t2g orbital of the metal center
2GFper). Here, the G factor was calibrated by measuring the and lower the oxidation potentials. Also, this delocalization
polarized fluorescence decay of perylene in toluene,37 which feature could present at lower reduction potentials. In compari-
gave equal polarized fluorescence intensity after a complete son to 1, two low reduction potentials were found for 2. The
rotation diffusion in tens of picoseconds. The G value was found lowest one at -0.34 V was very likely due to intramolecular
to be ∼1.004 for the system. A rotating sample cell was used charge transfer; the triphenyl donors could transfer electrons to
to avoid possible photodegradation and other accumulative the metal center through the conjugated structure. It seems that
effects. For all the measurements, a concentration of ∼0.1 mM electrons are delocalized in 2 at the ground state. This is
of the two samples in CH2Cl2 has been used. The fluorescence consistent to the observation in the absorption spectrum of 2.
emitted from the sample was collected with an achromatic lens These behaviors will help to create long-distance charge
and directed onto a β-barium borate crystal (BBO). The separated states, which may be used to storage the (light) energy
fundamental light passed through a motorized optical delay line in a chemistry form. In addition, for both complexes, the
and then mixes with the sample emission in a nonlinear crystal absorption spectral features relevant to the MLCT transitions
to generate a sum frequency signal. The signal was dispersed are different from the previous observation with tris(2,2′-
by using a monochromator and detected by a photomultiplier bipyridyl)ruthenium(II) which appears nonseparated broad
tube (Hamamatsu R1527P). The instrument response function double-peak from 400-500 nm (in MeCN).10 This is probably
(IRF) for the system was estimated to be 188 fs at full width at due to the change of the coordinate field, which is associated
half-maximum (fwhm).34 The fluorescence data have been with the geometry change from these tridentate ligands.
deconvoluted with the IRF by using the vFit program (CDP, Figure 4 shows emission spectra of 1 at different excitation
Russia). The smallest χ2 value and a residual fluorescence value wavelengths. The emission was found to be highly excitation
less than 1% were controlled during the fitting and simulation.38 dependent. For an excitation at 375 nm, there was a strong
emission at ∼467 nm, which was mainly from the ligand-
centered πL* states (Table 1). However, the emission from
Results and Discussion 1
MLCT states might not be completely excluded in this case
Steady-State Spectroscopy. Figure 2 shows the absorption because their higher Franck-Condon states could be excited
of the two polypyridyl complexes. The very intense bands below when the excitation is at 375 nm. The excitation of Franck-Condon
400 nm originate from intraligand πL-πL* transitions (Table states was observed for tris(2,2′-bipyridyl)ruthenium(II).10,13 The
1). The absorption shoulder at 405 nm and the peak at 532 nm excitation spectrum revealed that the emission at 467 nm was
of complex 1 can be assigned to MLCT transitions, where an originated from the excitation at wavelengths below 420 nm
electron is promoted from the metal-centered t2g orbital into a (cutoff in Figure 4b). When moving the excitation to 400 nm,
ligand-centered π* orbital.39 In comparison to the complex 1, the intensity of the emission at ∼467 nm was observed to be
there is a MLCT peak at 421 nm with shoulders at 457 and significantly suppressed [intensity dropped from 2.74 × 105
549 nm in the absorption spectrum of the complex 2. These counts/s (cps) to 4.0 × 104 cps], and a new emission band at
shoulders in longer wavelength indicate the absorption features ∼633 nm appeared. Further shifting the excitation to a higher
from the increase of conjugation with the ligands. Their wavelength (lower energy) at 432 nm, the emission band at
D J. Phys. Chem. A, Vol. xxx, No. xx, XXXX Xiao et al.

Figure 3. Cyclicvoltammograms of the two complexes.

Figure 4. Steady-state emission spectra of 1: (a) excitation depended emission, and (b) excitation spectra.

∼467 nm disappeared and only the emission band at ∼633 nm

was left with a substantial intensity (1.30 × 105 cps). The
emission at 467 nm was mainly originated from the ligand-
centered πL* states; and it was rather possible to attribute the
observed 633-nm emission band to the emission of the triplet
metal-to-ligand charge transfer (3MLCT) states, as was con-
firmed by Figure 4b. The excitation spectrum with emission at
633 nm showed an excitation range from 350 to 550 nm (Figure
4b), as indicates that this emission could not completely exclude
the contribution from the excitation below 432 nm (Figure 4b).
In such a case, the ligand-centered πL* states, which can also
be considered as higher-energy 1MLCT states, may take diabatic
processes to relax to lower-energy 1MLCT states, and then take
ISC to relax to 3MLCT states. This was accompanied by a large Figure 5. Optimal structures in CH2Cl2 of the two polypyridyl
ruthenium complexes (Geometry optimization was carried out by Dmol3
distortion in geometry.16 As a result, a large energy differ- software package at the GGA-PBE level with a DNP base set and a
ence7350 cm-1 (201 nm) between the excitation and the PCM description of solvent).
emission was found. This is related to the exchange energy
between the singlet and triplet states. Also, large reorganization
energy due to large distortion for the excited states may not be shapes of the emission spectra at an excitation below 400 nm
excluded. There was extremely weak emission from the excita- were similar to each other, whereas the maximum emission was
tion at 532 nm, that is, the 1MLCT excitation. These observed observed to be suppressed and a shoulder around 589 nm
behaviors above suggest that the electronic system for both the appeared for an excitation at 432 nm. The emission spectrum
ligands and the metal center is somehow isolated, as may be with 432 nm excitation was fitted well by a two-peak Gaussian
associated by the distortion in geometry of the complex 1. This function, which are at 517 nm (19350 cm-1) and 589 nm (16970
agreed with the observation of the high redox potentials and cm-1), respectively (Figure 6b). However, ones should not
was also proven in geometry optimization by using the Dmol3 simply assign the emission band at 517 nm to the emission of
software package at the GGA-PBE level (Figure 5). The phenyl the ligands and the emission band at 589 nm to the emission of
group that connects to the polypyridyl ligand is positioned at a the 3MLCT states. The emission band at 517 nm may consist
twisted angle to the plane of the three nitrogen atoms in the of the contributions from both the ligand (πL*) excited states
ligand. This angle is smaller in 2 due to the more flexibility of (Table 1) and the 3MLCT states, as the excitation spectrum was
a double bond in the ligand. A twisted geometry with 1 could observed covering the absorption range of the πL-πL* transi-
be much easier to be formed after the 1MLCT excitation, and tions and the MLCT transition around 421 nm (Figure 6c). With
the large energy difference should include the contribution from an increased conjugation in the complex 2, there should be a
the structure distortion. large delocalization and a strong electronic coupling between
The emission spectrum of 2 is shown in Figure 6. A single the ligands and metal center in comparison to 1. Thus, the
emission band was observed with a maximum at 517 nm. The emission at 517 nm shows a shoulder at 589 nm, as enjoying a
Fluorescence of Tridentate Pyridyl Ruthenium Complexes J. Phys. Chem. A, Vol. xxx, No. xx, XXXX E

Figure 6. Steady-state emission spectra of 2: (a) emission spectra at different excitation, (b) fitted spectra (violet) for the emission spectrum for
the excitation at 432 nm, and (c) excitation spectrum with emission at 517 nm.

Figure 7. Fluorescence decay curves of 1 (royal) and 2 (wine) with excitation at 375 nm and emission 480 nm: (a) fluorescence decay within 18
ps; (b) decay within 1.8 ps [The thick lines were generated via deconvolution with the IRF with two or three exponential decay.]

TABLE 2: Decay Constants for the Fluorescence Decay at Different Wavelengths with an Excitation of 375 nm
emission at 480 nm
long-term decay initial decay emission at 525 nm initial decay
′ ′ ′
τ1/fs τ2/ps τ3/ps τ1 /fs τ2 /ps τ3 /ps τ1′′/fs τ2′′/ps
(A1) (A2) (A3) (A1′) (A2′) (A3′) (A1′′) (A2′′)
1 176 ( 30(0.74) 1.4 ( 0.2 (-0.05) 208 ( 7 (0.21) 100 ( 40 (0.78) 1.0 ( 0.3 (-0.07) 46 ( 2 (0.15) 154 ( 40 (0.75) 228 ( 10 (0.25)
2 100 ( 40 (0.96) 1.0 ( 0.2 (0.03) 52 ( 2 (0.01) 107 ( 40 (0.86) 1.9 ( 0.3 (0.14) N/A 102 ( 30 (0.86) 2.86 ( 0.3 (0.14)

mixing feature of the relaxation from the πL*, 1MLCT, and complex 2. The decay within 2 ps for the complex 2 may be
3
MLCT states. attributed to intramolecular vibrational energy redistribution
Time-Resolved Fluorescence Dynamics. Figure 7 illustrates (IVR) within the 1MLCT excited states. IVR processes were
the fluorescence dynamics at 480 nm of the complexes 1 and 2 observed with a time scale of a few picoseconds in conjugated
with an excitation at 375 nm. These transients can be decon- systems40-42 and were estimated with the same time scale for
voluted with the IRF by using a sum of multiple exponential highly excited molecules.43 The observation here is consistent
functions: I(t))[∑i Ai exp(-t/τi)]XF(t), in which F(t) is a with both cases.
constant term convoluted with the IRF, A is the amplitude, and For the observation of the rebounding component for 1, it
τ is the time constant. The IRF is ∼188 fs (full width at half- was likely originated from the emission of the thermally
maximum) for the measurements. The deconvoluted data by populated 1MLCT states from the relaxed 3MLCT ones (Scheme
using two- or three-exponential functions were listed in Table 1). Moreover, there could be a dynamics controlled for this
2. Ultrafast decay components within ∼100 fs were found in process. If considering a pseudo-equilibrium between the
1
the fluorescence dynamics for the both complexes. This ultrafast MLCT and 3MLCT states; an equilibrium can be given as: K
component can be assigned to the decay of the 1MLCT ) (gs/gT)e-∆E/kT, where g denotes the degeneracy and ∆E
emissions due to an ultrafast intersystem crossing to form presents the energy difference between the emission and the
3 3
MLCT states, as is consistent with the observation of the time- MLCT states. At the case for the emission of 480 nm for 1, a
scale in 100-300 fs for tris(2,2′-bipyridyl)ruthenium(II).10,29c,e K value of 2.5 × 10-11 could be given (Assuming that molecular
However, there is significant difference between the two conformations remain the same during the ISC process, the
complexes. For the complex 1, this ultrafast decay was followed degeneracy may be considered as a constant). This value
by a rebounding time with a time scale of <1.5 ps and a negative indicates that there was very less probability for giving out
amplitude of 0.05-0.07. This feature has been observed both delayed fluorescence. Thus, the observation suggests there
in the relative long-term and short-term decay, which will be should be relatively stable 3MLCT states with energy sublevels
discussed in latter text. In addition, there is another slow decay close to 480 nm, which was populated by thermal energy.
component with a time scale much greater than the observation Because the emission at 480 nm is on the spectral blue edge of
3
range. Compared to 1, except for the ultrafast decay with MLCT emission spectrum, there is small energy gap between
amplitude of ∼0.86, no rebounding component but a relatively the sublevels of the triplet and singlet states, which is a thermal
slow decay with a time scale of <2 ps was observed for the population processes. The thermal population was very likely
F J. Phys. Chem. A, Vol. xxx, No. xx, XXXX Xiao et al.

SCHEME 1: Energy Level Diagram and Related

Photoinduced Processes in 1a

a
Thermal population of the excited states with time scale of 1-1.4
ps was observed within the emission of a tridentate pyridyl ruthenium Figure 9. Fluorescence decay curves of 1 (blue) and 2 (red) with
complex. excitation at 375 nm and emission 525 nm [The thick lines were
generated via deconvolution with the IRF with two-exponential
decay].

the same during an ISC process, as agrees to the observation of

platinum complexes.44
There are two components for the dynamics at an emission
of 525 nm for the both complexes (Figure 9). An ultrafast
component with a time scale from 100 to 150 fs and a relatively
slow decay were observed as the dominated processes for the
two complexes. However, complex 1 possesses a longer decay
of 228 ps than that of 2.9 ps for the complex 2. The observed
emission at 525 nm is originated from the relaxation of 1MLCT
states. The ultrafast process is due to the intersystem crossing
from 1MLCT to3MLCT states. The decay of 2.9 ps time-scale
for the complex 2, which is similar to the corresponding decay
at the emission of 480 nm, can be assigned to the IVR processes
that lead to vibrational cooling in the system as well. The
Figure 8. Depolarization curves of 1 (royal lines) and 2 (wine lines)
with excitation at 375 nm and emission 480 nm (Dot lines for guiding
relatively slow component for the complex 1 may be originated
eyes). from a twisted intramolecular charge transfer (TICT) states,45,46
and demonstrated a relatively long-lived 1MLCT states. This
agrees with the assumption for the formation of the thermal
associated by IVR processes to accelerate the energy migration populated states above (Scheme 1). The dynamics differences
and shows a time scale within several picoseconds.39-43 The of the complexes observed at emission of 525 nm reflect the
observation of the long time decay within the dynamics of 1 structure features: complex 1 possesses relatively isolated ligands
(Figure 7) could be then attributed to the lifetime of these stable from the metal-center due to the twist structure, whereas
relaxed 3MLCT states, which was far beyond the observation complex 2 has more delocalized structure.
range. Such long lifetime likely originates from the increase of With excitation at 400 nm, the fluorescence dynamics at
the stability of the relaxed 3MLCT states due to structure emission 480 and 525 nm of both samples were observed to be
distortion and symmetry breaking from D3h to D3V. A twisted similar to those with excitation at 375 nm. However, when
structure (Figure 5) should be formed. The emission behaviors moving the excitation to 436 nm, both the complexes showed
above are highly depended on the twisted structure of 1, which weak signal with ultrafast decay in the IRF ∼188 fs at both the
showed more complicate dynamics, as a result of the relative emission of 480 and 525 nm. This suggested that a direct
stable and localized excitations. excitation of the 1MLCT states could ease a formation of non-
The anisotropy decays for the two complexes were insignifi- irradiative states, such as charge separated states, which are very
cant. Figure 8 shows an example within 1.8 ps decay. Interest- useful in photovoltaic and photosynthetic devices. Long-distance
ingly, the residual value of the anisotropy is larger than 0.3, and long-lived charge separated states are critical in both
indicating that there is a large orientated dipole moment of the artificial photosynthesis systems and photovoltaic devices.24-28
excited states. This agrees with the strong charge transfer from To know the photophysics of 3MLCT states, measurements
metal-to-ligand to form intramolecular charge separated states. with excitation at 420 nm have been carried out, and observation
In this case, the oriented dipole moment was suggested to be has been set on the emission at a longer wavelength of 633 nm
along the axis from the metal to the center of one of the as well. The fluorescence and anisotropy decay of the 3MLCT
ligands.12,14 On the other hand, the anisotropy decay may be emission at 633 nm (excitation at 420 nm) for 1 are shown in
dominated by the ISC process within a time scale less than the Figure 10, and weak upconversion signals were observed for
IRF. The observed behavior above indicate that the orientation the complex 2 at the similar condition. For complex 1, there
of transition dipoles and the molecular conformations remain are two ultrafast energy transfer processes with time scales of
Fluorescence of Tridentate Pyridyl Ruthenium Complexes J. Phys. Chem. A, Vol. xxx, No. xx, XXXX G

Figure 10. Fluorescence decay (a) and depolarization (b) of 1 with excitation at 420 nm and emission 650 nm [inset of (b) shows polarized
fluorescence decay] [The fluorescence dynamics was deconvoluted with the IRF. This shows a three-exponential function: 1, τ1 106 fs (-0.30), τ2
1.2 ps (-0.30),τ3 349 ps (0.40). The depolarization showed a residual value of 0.27 and decay time of 170 ps].

106 fs and 1.2 ps. The one with time scale of 106 fs may be Acknowledgment. Support for this project was from the
assigned to the intersystem crossing from 1MLCT to 3MLCT NSF-MRI Program (ECCS Grant No. 0723114), NSF-EPSCoR
states; the other one of 1.2 ps possibly originates from the Grant No. 0554609, NASA-EPSCoR Grant No. NNX09AU83A,
thermal populated states with association of intermolecular and the State of South Dakota. L.X. also acknowledges support
collision processes or solvation from any lower energy 3MLCT from the National Basic Research program of China (grant
states (Scheme 1), which agrees with the observation of the 2009CB930504).
emission at 480 nm with excitation at 375 nm. In the first case,
this is dominated by the spin crossover process of the Ru
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