Cyclometalated ruthenium complexes of 1,2,3-triazole-containing ligands: Synthesis, structural studies, and electronic properties

Article abstract of DOI:10.1002/cjoc.201201170

Six bis-tridentate and two tris-bidentate cyclometalated ruthenium complexes with a 1,2,3-triazole-containing ligand have been prepared and characterized. Single-crystal X-ray analyses of complexes [(MeOptpy)Ru(Budtab)] (PF₆) and [(Mebip)Ru(Bud

Full text of DOI:10.1002/cjoc.201201170

FULL PAPER
DOI: 10.1002/cjoc.201201170
Cyclometalated Ruthenium Complexes of 1,2,3-Triazole-
containing Ligands: Synthesis, Structural Studies, and
Electronic Properties
,a,b
Wenwen Yanga and Yuwu Zhong∗
a Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Photochemistry,
Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China
b State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing, Jiangsu 210093, China
Six bis-tridentate and two tris-bidentate cyclometalated ruthenium complexes with a 1,2,3-triazole-containing
ligand have been prepared and characterized. Single-crystal X-ray analyses of complexes [(MeOptpy)Ru(Budtab)]-
(PF6) and [(Mebip)Ru(Budtab)](PF6) are presented, where MeOptpy is 4'-p-methoxyphenyl-2,2':6',2''-terpyridine,
Budtab is the 2-deprotonated form of 1,3-di(N-n-butyl-1,2,3-triazol-4-yl)benzene, and Mebip is bis(N-methyl-ben-
zimidazolyl)pyridine. The electronic properties of these complexes are probed by spectroscopic and electrochemical
analyses. Time-dependent density functional theory calculations have been performed to assist the assignment of
the absorption spectra.
Keywords 1,2,3-triazole, click reaction, ruthenium, cyclometalated complex
with 1,3-di(1,2,3-triazol-4-yl)benzene (dtabH),[13] which
coordinates to the ruthenium atom in a NCN binding
mode after the loss of a proton of the benzene ring. In
addition, some cyclometalated di-ruthenium complexes
with 1,2,3-triazole-containing bridging ligand have been
synthesized and these complexes display considerable
metal-metal electronic coupling.[14] Herein, we present
the syntheses of six bis-tridentate ruthenium complexes
(4－9, Scheme 1) with dtabH and two tris-bidentate
complexes (12 and 13, Scheme 2) with a 1,2,3-triazole-
containing ligand. These complexes allow the system-
atic modulation of their spectroscopic and electro-
chemical properties. Structural studies have been carried
out on the basis of single-crystal X-ray analyses of 7
and 9. In addition, time-dependent density functional
theory (TDDFT) calculations have been performed to
elucidate the electronic absorption of these complexes.
Introduction
Cyclometalated ruthenium complexes are formed
when an organic ligand undergoes intramolecular meta-
lation to give rise to a chelate ring containing a σ Ru－
C bond.[1] Recently, the uses of cyclometalated ruthe-
nium complexes in mixed-valence chemistry,[2] near-
infrared electrochromism,[3] and dye-sensitized solar
cells[4] have received much interest. Two important fea-
tures of these complexes are low RuII/III potentials and
wide absorption spectrum. In addition, their electronic
properties are strongly dependent on the auxiliary
ligands.[5] To further expand the use of cyclometalated
ruthenium complexes in various optoelectronic applica-
tions, it would be of interest and importance to design
and synthesize new complexes with tunable spectro-
scopic and electrochemical properties.
On the other hand, the mild copper-catalyzed al-
kyne-azide 3＋2 cycloaddition (the CuAAC “click”
reaction) allows the ready access to 1,4-disubstituted
1,2,3-triazole moieties,[6] and this leads to tremendous
research activities in the coordination chemistry of these
heterocycles.[7] Up to date, various metal complexes,
such as ruthenium,[8] silver,[9] copper,[10] rhenium,[11]
and iridium[12] complexes coordinating with 1,2,3-tri-
azole-containing ligands have been disclosed. We pre-
viously reported the syntheses and electronic properties
of some bis-tridentate heterolepic ruthenium complexes
Results and Discussion
Complexes 4－9 were synthesized as outlined in
Scheme 1. Three dtabH pro-ligands 1－3 were prepared
by click reactions of 1,3-diethynylbenzene with 1-
n-butylazide, 4-t-butylphenylazide, or 1-benzylazide in
good yields (see the Experimental section for details).
The synthesis of compound 1 has been described previ-
ously.[13] The reaction of [(ttpy)RuCl3] (ttpy＝4'-tolyl-
*
E-mail: zhongyuwu@iccas.ac.cn; Tel.: 0086-010-62652950; Fax: 0086-010-62559373
Received November 27, 2012; accepted January 3, 2013; published online January 28, 2013.
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/cjoc.201201170 or from the author.
Dedicated to Professor Guoqiang Lin on the occasion of his 70th birthday.
†
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329

Yang & Zhong
FULL PAPER
2,2':6',2''-terpyridine) with AgOTf gave an intermediate
with the Cl atoms replaced by solvent molecules (ace-
tone in this case), which was then treated with 1, 2, or 3,
followed by anion exchange with KPF6, to give the de-
sired cyclometalated complexes 4, 5, and 6 respectively.
Similar procedures were previously used for the synthe-
sis of a number of cyclometalated ruthenium com-
plexes.[2,4,5,15] Complex 4 has been reported in a previ-
ous paper.[13] By using the same procedure, complexes 7
－ 9 were synthesized from [(MeOptpy)RuCl3],
[(CF3ptpy)RuCl3], or [(Mebip)RuCl3] with pro-ligand 1,
where CF3ptpy is 4'-p-trifluoromethylphenyl-2,2':6',2''-
terpyridine, MeOptpy is 4'-p-methoxyphenyl-2,2':6',2''-
terpyridine,[16] and Mebip is bis(N-methylbenzimid-
azolyl)pyridine.[5a] These auxiliary ligands with differ-
ent electronic nature were deliberately selected to
change the electronic properties of the resulting com-
plexes.
The synthesis of tris-bidentate complexes 12 and 13
is shown in Scheme 2. Pro-ligands 10 and 11 were pre-
pared by click reactions of phenylacetylene or 4-chloro-
phenylacetylene with 1-n-butylazide. The reaction of 10
or 11 with [(bpy)2RuCl2] (bpy＝2,2'-bipyridine) in the
presence of AgOTf, followed by anion exchange with
KPF6, afforded the desired complexes 12 and 13, re-
spectively.
Scheme 1 Syntheses of bis-tridentate complexes 4－9
N
N
N
N
N
N
R
RN3
R
click conditions
1: R = n-Bu, 99%
2: R = 4-t-butylphenyl, 99%
3: R = Bn, 83%
(PF6)
N
AgOTf 1, 2, or 3
KPF6
N
N
N
N
N
Ru
N
N
N
N
N
N
Ru
Cl
R
R
Cl
Cl
[(ttpy)RuCl3]
4: R = n-Bu, 37%
5: R = 4-t-butylphenyl, 16%
6: R = Bn, 22%
R
R
(PF6)
N
Ru
AgOTf
1
KPF6
N
N
N
N
N
N
N
N
N
N
N
Ru
n-Bu
Bu-n
Cl
Cl
Cl
7: R = MeO, 59%
8: R = CF3, 48%
R = OMe, [(MeOptpy)RuCl3]
R = CF3, [(CF3ptpy)RuCl3]
(PF6)
N
N
N
N
N
N
N
N
AgOTf
1
KPF6
N
Ru
N
N
N
N
N
N
Ru
Cl
N
Bu-n
n-Bu
Cl
Cl
[(Mebip)RuCl3]
9, 41%
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Cyclometalated Ruthenium Complexes of 1,2,3-Triazole-containing Ligands
Scheme 2 Syntheses of tris-bidentate complexes 12 and 13
(PF6)
n-Bu
N N
N
N
(1) [Ru(bpy)2Cl2], AgOTf
(2) KPF6
1-n-BuN3
N
N
N
N
Ru
click conditions
N
N
n-Bu
R
R
R
10: R = H, 72%
11: R = Cl, 94%
12: R = H, 12%
13: R = Cl, 21%
Single crystals of complexes 7 and 9 were obtained
by slow diffusion of petroleum ether into their solutions
in chloroform. Their thermal ellipsoid plots obtained
after X-ray diffraction analysis are shown in Figure 1.
The crystallographic data and selected bond lengths and
angles are given in Tables 1 and 2. The Ru－C bonds of
two complexes (2.00 and 1.99 Å for 7 and 9, respec-
tively) are slightly shorter than other Ru－N bonds. The
binding angles of C(1)－Ru－N(4), C(1)－Ru－N(5),
N(1)－Ru－N(2), and N(1)－Ru－N(3) are comparable,
in the range of 77.3°－78.3°.
Table 1 Crystallographic data
7
9
Empirical formula
C40H40N9ORuF6P
908.85
C39H40N11RuF6P
908.86
Formula weight
Space group
P2(1)/c
P2(1)/n
Crystal system
Monoclinic
12.042(2)
13.769(3)
23.770(5)
90.00
Monoclinic
11.003(2)
22.669(5)
15.711(3)
90.00
a/Å
b/Å
c/Å
α/(°)
β/(°)
γ/(°)
V/Å3
Z
90.19(3)
93.72(3)
90.00
90.00
3941.0(14)
3910.6(13)
4
4
R1＝0.0470
wR2＝0.1044
R1＝0.0507
wR2＝0.1071
R1＝0.0600
wR2＝0.1202
R1＝0.0674
wR2＝0.1247
Final R indices
R Indices (all data)
Table 2 Selected bond lengths (Å) and angles (°)
7
9
Ru－C(1)
2.00
2.02
2.07
2.08
2.05
2.09
77.6
77.4
78.0
78.3
1.99
2.05
2.05
2.06
2.06
2.09
77.6
77.3
77.6
77.4
Ru－N(1)
Ru－N(2)
Ru－N(3)
Ru－N(4)
Ru－N(5)
C(1)－Ru－N(4)
C(1)－Ru－N(5)
N(1)－Ru－N(2)
N(1)－Ru－N(3)
Figure 1 Thermal ellipsoid plots with 30% probability for the
X-ray crystal structures of (a) 7 and (b) 9. Hydrogen atoms and
RuII/III processes for the prototype complex
[Ru(tpy)2](PF6)2 (tpy＝2,2':6',2''-terpyridine) and com-
plex 4 occur at ＋1.32 and ＋0.53 V (vs. Ag/AgCl),
respectively.[13] When the methyl group in 4 is replaced
by methoxy or trifluoromethyl group (in complexes 7
and 8, respectively), the RuII/III potential changes to
＋0.51 and ＋0.55 V, respectively (Figure 2). This re-
flects the electron-donating nature of the methoxy group
and the electron-withdrawing nature of the trifluoro-
counter anions ( PF－ ) are omitted for clarity.
6
The electronic properties of above complexes were
studied by cyclic voltammetric analysis. Due to the
presence of the anionic carbon ligand, the oxidation of
the metal site of cyclometalated ruthenium complexes
usually takes place at a much lower potential than
non-cyclometalated counterparts.[2,4,5] For instance, the
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Yang & Zhong
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methyl group. Complex 9 with the electron-donating
ligand Mebip[5a] displays the RuII/III process at ＋0.40 V.
Due to limited solubility in the presence of the electro-
lyte, no satisfactory cyclic voltammogram (CV) has
been recorded for complex 6. The RuII/III potentials for
the tris-bidentate complexes 12 and 13 are ＋0.51 and
＋0.60 V (vs. Ag/AgCl), respectively. All bis-tridentate
complexes (4, 5, 7－9) exhibit a NNN ligand-based re-
duction wave in the range of 1.48－1.62 V. However,
two cathodic waves are evident in the CV for complexes
12 and 13, as a result of the reduction of two bpy
ligands. These CVs are provided in the Figures S1－S6
in the Supporting Information (SI). All electrochemical
data are collected in Table 3.
plexes,[1,2,4,5] and this feature has made cyclometalated
ruthenium complexes very useful for dye-sensitized
solar cells.[4] The absorption spectrum of complex 4 has
been reported previously.[13] The MLCT absorption
maximum (λmax) of 4 is 497 nm. In fact, all bis-tri-
dentate complexes studied in this paper (4－9) have a
very similar λmax (Figures S7 and S8, SI). In comparison,
the MLCT transitions of the well-known noncyclome-
talated prototype complex [Ru(tpy)2](PF6)2 locate in a
relatively higher-energy region (λmax＝475 nm).[13] On
the other hand, the tris-bidentate complexes 12 and 13
have MLCT transitions at even lower-energy region
than the bis-tridentate complexes 4－9 (Figure S9). For
instance, the λmax of the MLCT transitions of complexes
12 and 13 are 547 and 536 nm, respectively. These ab-
sorption data are summarized in Table 4.
Table 4 Absorption dataa
Compound
λmax/nm [ε/(105 L•mol−1•cm−1)]
4
5
6
7
8
314 (0.35), 366 (0.17), 497 (0.12), 541 (0.098)
315 (0.35), 374 (0.24), 494 (0.11), 533 (0.10)
316 (0.26), 368 (0.14), 497 (0.091), 539 (0.078)
315 (0.43), 366 (0.19), 498 (0.13), 540 (0.11)
317 (0.33), 376 (0.20), 499 (0.14), 544 (0.11)
299 (0.30), 333 (0.30), 348 (0.41), 383 (0.071),
497 (0.14)
9
12
13
295 (0.53), 357 (0.12), 479 (0.061), 548 (0.092)
295 (0.56), 353 (0.13), 470 (0.062), 537 (0.091)
Figure 2 Cyclic voltammograms of 9, 7, 4, and 8 at a glassy
carbon in CH3CN.
[Ru(tpy)(dpb)]＋ 315 (0.37), 372 (0.086), 423 (0.095), 499 (0.14)
[Ru(tpy)2]2
[Ru(bpy)3]2
b
＋
b
307 (0.78), 475 (0.17)
＋
c
Table 3 Electrochemical dataa
285 (0.65), 354 (0.051), 420 (0.087), 455 (0.11)
a Measured in CH3CN. b See refs. 4c and 13. c See ref. 2j.
Compound
E1/2 (anodic)/V
＋0.53
E1/2 (cathodic)/V
−1.53
4
To gain insight into the difference of the absorption
spectra between bis-tridentate and tris-bidentate com-
5
＋0.56
−1.51
plexes, TDDFT calculations were perfromed on the op-
7
＋0.51
−1.56
＋
timized structures of [(tpy)Ru(Medtab)]
and
8
＋0.55
−1.48
[(bpy)2Ru(Metab)]＋, where Medtab and Metab are the
2-deprotonated forms of 1,3-di(N-methyl-1,2,3-triazol-
4-yl)-benzene and (N-methyl-1,2,3-triazol-4-yl)benzene,
respectively. They serve as model compounds for bis-
tridentate and tris-bidentate complexes, respectively.
Figure 3 shows the absorption spectra of 4 and 12
and the TDDFT-predicted excitations, where the latter
are at slightly higher energies relative to the experimen-
tally obtained spectra. This phenomenon is commonly
observed in TDDFT results of most cyclometalated ru-
thenium complexes.[2,4,5] One of the reasons is that we
did not take the solvent effect into account in our calcu-
lation. However, the shape of the predicted excitations
correlates well with the experimental data. The major
predicted excitations are delineated in Table 5 along
with the oscillator strength (f) and dominant transitions
and orbital contributions. Corresponding frontier mo-
lecular orbital involved in these excitations are given in
Figures 4 and 5. From these data, the absorption peaks
9
＋0.40
−1.62
12
＋0.51
−1.57, −1.83
−1.54, −1.79
−1.51
13
＋0.60
[Ru(tpy)(dpb)](PF6)b
[Ru(bpy)2(ppy)](PF6)b
＋0.56
＋0.50
−1.56, −1.82
−1.22, −1.46
−1.29, −1.49, −1.73
b
[Ru(tpy)2](PF6)2
＋1.32
b
[Ru(bpy)3](PF6)2
＋1.32
a Potentials are reported as E1/2 (vs. Ag/AgCl). b See refs. 4c and
13. dpb＝1,3-di(2-pyridyl)benzene. ppy＝2-phenylpyridine. The
potential vs. Ag/AgCl was derived from the potential vs. NHE by
subtracting 0.20 V.
One appealing feature of cyclometalated ruthenium
complexes is that the metal-to-ligand charge transfer
(MLCT) transitions usually locate in a lower-energy
region than noncyclometalated complexes. This has
been evidenced in a large number of such com-
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Cyclometalated Ruthenium Complexes of 1,2,3-Triazole-containing Ligands
between 440 and 640 nm of the bis-tridentate complex 4
can be assigned to MLCT transitions toward the NNN
ligand (the S5 and S6 excitations). However, the absorp-
tion in the region between 320 and 440 nm is a result of
MLCT transitions toward both NNN and NCN ligands.
For instance, the lowest unoccupied molecular orbital
(LUMO)＋4 and LUMO＋5 orbitals associated with the
NCN ligand segments are involved in the predicted S14
and S17 excitations for [(tpy)Ru(Medtab)]＋.
The situation for the tris-bidentate complex is
somewhat different. The absorption bands between 440
and 640 nm of complex 12 can be assigned to the
Figure 3 Electronic absorption spectra of (a) 4 and (b) 12 in CH3CN and TDDFT-predicted excitations of (a) [(tpy)Ru(Medtab)]＋ and
(b) [(bpy)2Ru(Metab)]＋. The left and right axes are associated with the absorption spectra and predicted data, respectively.
Table 5 TDDFT resultsa
Sn E/eV E/nm
f
Dominant transition (Contribution)b
3
4
5
6
2.28 543.7 0.0103
HOMO−1→LUMO (89%)
2.44 507.5 0.0031
2.51 494.2 0.0404
2.77 446.9 0.0888
HOMO−2→LUMO (40%); HOMO−1→LUMO＋1 (57%)
HOMO−2→LUMO＋1 (92%)
HOMO−2→LUMO (41%); HOMO−1→LUMO＋1 (39%)
HOMO→LUMO＋4 (88%)
[(tpy)Ru(Medtab)]＋
14 3.49 355.7 0.0487
15 3.51 353.5 0.0048
16 3.54 349.8 0.0584
17 3.59 345.8 0.0229
HOMO−2→LUMO＋2 (94%)
HOMO−1→LUMO＋2 (81%)
HOMO→LUMO＋5 (66%)
1
3
5
6
1.98 625.9 0.0047
2.28 543.2 0.0105
2.46 504.8 0.0763
2.66 466.0 0.0527
HOMO→LUMO (68%)
HOMO−1→LUMO (73%)
HOMO−1→LUMO＋1 (51%)
HOMO−2→LUMO (37%); HOMO−2→LUMO＋1 (34%)
HOMO−3→LUMO＋1 (16%); HOMO−1→LUMO＋2 (22%)
HOMO−1→LUMO＋3 (79%)
13 3.23 384.1 0.0386
15 3.35 369.8 0.0162
16 3.47 357.2 0.0273
17 3.50 354.6 0.0125
18 3.55 349.6 0.0329
19 3.56 348.3 0.015
21 3.61 343.2 0.0292
HOMO−1→LUMO＋4 (71%)
[(bpy)2Ru(Metab)]＋
HOMO−2→LUMO＋3 (59%)
HOMO−2→LUMO＋4 (41%); HOMO−1→LUMO＋5 (26%)
HOMO−4→LUMO (44%); HOMO−2→LUMO＋4 (24%)
HOMO−2→LUMO＋5 (23%); HOMO→LUMO＋10 (24%)
HOMO−2→LUMO＋3 (11%); HOMO−2→LUMO＋4 (8%)
HOMO−2→LUMO＋10 (11%); HOMO−1→LUMO＋5 (16%)
HOMO−1→LUMO＋6 (29%); HOMO→LUMO＋7 (28%)
24 3.75 330.9 0.0762
29 3.89 318.2 0.0144
a Computed at the level of theory of TDDFT/B3LYP/LanL2DZ/6-31G*/vacuo. b The actual percent contribution＝(configuration coeffi-
cient)2×2×100%.
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Yang & Zhong
FULL PAPER
excitations associated with the absorption between 310
and 440 nm for 12 are rather complex (from S13 to S29
excitations). These excitations include the MLCT tran-
sitions toward both the bpy and phenyltriazole segments
(associated with the LUMO＋6 and LUMO＋7 orbitals)
and the metal-centered transitions associated with the
LUMO＋10 orbital.
At last, it should be mentioned that no distinct emis-
sion has been detected for all of these complexes (4－9,
12, and 13) in acetonitrile at room temperature. Emis-
sion of cyclometalated ruthenium complexes,[4c] either
with bis-tridentate or tris-bidentate coordination mode,
is usually very weak. This is caused by the destabiliza-
tion of the HOMO which provides non-radiative path-
ways to the ground state.
Conclusions
In summary, a series of bis-tridentate and tris-bi-
dentate complex containing the 1,2,3-triazole moiety
has been successfully prepared. By changing the auxil-
iary co-ligands, the electronic properties of these com-
plexes can be modulated. The MLCT absorption
maxima of tris-bidentate complexes locate in a rela-
tively lower-energy region with respect to the bis-tri-
dentate complexes. TDDFT results suggest that the
MLCT absorption in the visible region is largely based
on the noncyclometalating ligand segment (NNN or NN
ligand). The MLCT transitions associated with the cyc-
lometalating ligand segment (NCN or NC ligand) locate
in a relatively higher-energy region.
Figure 4 Molecular orbitals involved in the predicted excita-
tions for [(tpy)Ru(Medtab)]＋ in Table 5. All orbitals have been
computed at an isovalue of 0.04 e/bohr3. Hydrogen atoms have
been omitted for clarity. All orbitals are positioned with the same
structure orientation.
Experimental
General information
Compounds 1 and 4 were prepared according to pre-
vious procedures.[13] NMR spectra were recorded in the
designated solvent on a Bruker Avance 400 MHz spec-
trometer. Mass data were obtained with a Bruker Dal-
tonics Inc. Apex II FT-ICR or Autoflex III MALDI-
TOF mass spectrometer. The matrix for matrix-assisted
laser desorption ionization time-of-flight (MALDI-TOF)
measurement is α-cyano-4-hydroxycinnamic acid. Mi-
croanalysis was carried out using a Flash EA 1112 or
Carlo Erba 1106 analyzer at the Institute of Chemistry,
Chinese Academy of Sciences.
Preparation of 1,3-di(N-p-tert-butylphenyl-1,2,3-tri-
azol-4-yl)-benzene (2)
Figure 5 Molecular orbitals involved in the predicted excita-
tions for [(bpy)2Ru(Metab)]＋ in Table 5. All orbitals have been
computed at an isovalue of 0.04 e/bohr3. Hydrogen atoms have
been omitted for clarity. All orbitals are positioned with the same
structure orientation.
To a mixture of 14 mL of ethanol and 6 mL of water
mixture were added 4-tert-butylbromobenzene (1.71 g,
8.0 mmol), N,N'-dimethylethylenediamine (106 mg, 1.2
mmol), CuI (152 mg, 0.8 mmol) and sodium L-ascor-
bate (79.2 mg, 0.4 mmol). To the resulting suspension
was added 260 mg of NaN3 (4.0 mmol). A blue color
appeared in a minute. The mixture was heated to reflux
for 3 h. The color of the mixture turned yellow slowly.
The mixture was cooled to room temperature, followed
MLCT transitions toward the bpy ligands (the S5 and S6
excitations) and the absorption peak at 547 nm has the
major character of the highest occupied molecular or-
bital (HOMO)−1→LUMO＋1 excitation. The predicted
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Cyclometalated Ruthenium Complexes of 1,2,3-Triazole-containing Ligands
by the addition of 1,3-diethynylbenzene (126 mg, 1.0
mmol). The resulting system was stirred for 24 h at
room temperature. The solvent was removed under re-
duced pressure, followed by the addition of 50 mL of
dichloromethane. The insoluble species was removed by
filtration. The filtrate was washed with water and brine
and dried over MgSO4. After purification through flash
column chromatography on silica gel (eluent: dichloro-
methane/ethyl acetate, V∶V＝1∶1), 628 mg of com-
pound 2 was obtained as a white solid in 99% yield. 1H
NMR (400 MHz, CDCl3) δ: 1.39 (s, 18H), 7.52－7.58
(m, 1H, overlapped), 7.57 (d, J＝8.3 Hz, 4H), 7.73 (d,
J＝8.4 Hz, 4H), 7.94 (d, J＝7.7 Hz, 2H), 8.29 (s, 2H),
8.46 (s, 1H); EI-HRMS calcd for C30H32N6 476.2688,
found 476.2693.
V∶V＝20∶1) to give 16.5 mg of complex 3 in a yield
of 16%. H NMR (400 MHz, CD3CN) δ: 1.24 (s, 18H),
1
2.51 (s, 3H), 7.05 (t, J＝6.1 Hz, 2H), 7.35 (d, J＝8.8 Hz,
4H), 7.39 (t, J＝5.1 Hz, 3H), 7.45 (d, J＝8.8 Hz, 4H),
7.52 (d, J＝7.9 Hz, 2H), 7.73 (t, J＝7.5 Hz, 2H), 7.93 (d,
J＝7.5 Hz, 2H), 8.07 (d, J＝8.1 Hz, 2H), 8.50 (d, J＝
8.1 Hz, 2H), 8.59 (s, 2H), 8.88 (s, 2H); MALDI-MS m/z:
900.2 ([M–PF6]＋ ). Anal. calcd for C52H48F6N9PRu•
H2O: C 58.75, H 4.74, N 11.86; found C 58.83, H 4.57,
N 11.98.
Synthesis of complex [(ttpy)Ru(Bndtab)](PF6) (6)
To 10 mL of dry acetone were added [(ttpy)RuCl3]
(53.0 mg, 0.10 mmol) and AgOTf (77.0 mg, 0.30 mmol).
The system was refluxed for 3 h before cooling to room
temperature. The mixture was filtered to remove the
insoluble AgCl precipate. The purple-black filtrate was
concentrated to dryness. To the residue were added
ligand 3 (39.2 mg, 0.10 mmol), 8 mL of DMF, and 8
mL of t-BuOH. The mixture was heated to reflux in a
sealed tube for 24 h. After cooling to room temperature,
the solvent was removed under reduced pressure. The
residue was dissolved in proper amount of methanol.
After adding of an excess of KPF6, the resulting pre-
cipitate was collected by filtering and washing with wa-
ter and Et2O. The obtained solid was subjeted to flash
column chromatography on silica gel (eluent: CH2Cl2/
CH3CN, V∶V＝15∶1) to give 21.4 mg of complex 6
Preparation of 1,3-di(N-benzyl-1,2,3-triazol-4-yl)-
benzene (3)
To a mixed solvent of 12 mL of acetone and 3 mL of
water were added sodium azide (260 mg, 4.0 mmol) and
benzyl bromide (1.37 g, 8.0 mmol) at room temperature.
The resulting mixture was refluxed for 24 h. The bottom
layer of benzyl bromide disappeared and a top layer of
benzyl azide formed, which was subsequently isolated
using a separatory funnel. Around 0.45 mL of benzyl
azide was obtained, which was used for the next trans-
formation with further purification. A mixture of
1,3-diethynylbenzene (126 mg, 1.0 mmol), benzyl azide
(1.10 g, 8.0 mmol), sodium ascorbate (39.2 mg, 0.20
mmol), and CuSO4•5H2O (5.0 mg, 0.020 mmol) in a
mixed solvent of ethanol and water (20 mL, V∶V＝1∶
1) was stirred at room temperature for 24 h. The sol-
vents were removed under vacuum. The residue was
subjected to flash column chromatography on silica gel
(eluent: dichloromethane/ethyl acetate, V∶V＝15∶1)
1
in 22% yield. H NMR (400 MHz, CD3CN) δ: 2.49 (s,
3H), 5.20 (s, 4H), 6.87 (d, J＝7.1 Hz, 4H), 6.99 (t, J＝
3.4 Hz, 2H), 7.14－7.23 (m, 6H), 7.29 (t, J＝4.1 Hz,
3H), 7.48 (d, J＝7.9 Hz, 2H), 7.70 (t, J＝8.0 Hz, 2H),
7.81 (d, J＝7.5 Hz, 2H), 8.00 (d, J＝8.1 Hz, 2H), 8.06
(s, 2H), 8.42 (d, J ＝ 8.0 Hz 2H), 8.80 (s, 2H);
MALDI-TOF-MS m/z: 816.2 ([M–PF6]＋). Anal. calcd
for C40H36F6N9PRu: C 57.50, H 3.78, N 13.12; found C
57.15, H 3.81, N 12.95.
1
to give 326 mg of 3 in a yield of 83%. H NMR (400
MHz, CDCl3) δ: 5.57 (s, 4H), 7.15－7.44 (m, 11H),
7.72 (s, 2H), 7.77 (d, J＝7.7 Hz, 2H), 8.17 (s, 1H); 13C
NMR (100 MHz, CDCl3) δ: 147.8, 134.5, 131.1, 129.4,
129.2, 128.9, 128.1, 125.3, 122.8, 119.8, 54.3; EI-
HRMS calcd for C24H20N6 392.1755, found 392.1749.
Synthesis of complex [(MeOptpy)Ru(Budtab)](PF6)
(7)
This complex was prepared according to the same
procedure for the synthesis of 6, from [(MeOptpy)RuCl3]
(54.7 mg, 0.10 mmol), AgOTf (77.0 mg, 0.3 mmol), and
ligand 1 (32.4 mg, 0.10 mmol). In this procedure, 53.7
Synthesis of complex [(ttpy)Ru(t-BuC6H4dtab)](PF6)
(5)
1
To 10 mL of dry acetone were added [(ttpy)RuCl3]
(53.0 mg, 0.1 mmol) and AgOTf (77.0 mg, 0.3 mmol).
The system was refluxed for 3 h before cooled to room
temperature. The mixture was filtered to remove the
insoluble AgCl precipate. The purple-black filtrate was
concentrated to dryness. To the residue were added
ligand 2 (47.6 mg, 0.10 mmol), 2 mL of DMF, and 10
mL of t-BuOH. The mixture was heated to reflux in a
sealed tube for 24 h. After cooling to room temperature,
the solvent was removed under reduced pressure. The
residue was dissolved in proper amount of methanol.
After adding an excess of KPF6, the resulting precipitate
was collected by filtering and washing with water and
Et2O. The obtained solid was subjected to flash column
chromatography on silica gel (eluent: CH2Cl2/CH3CN,
mg of complex 7 was isolated in a yield of 59%. H
NMR (400 MHz, CD3CN) δ: 0.63 (t, J＝7.4 Hz, 6H),
0.89－0.95 (m, 4H), 1.50－1.57 (m, 4H), 3.94 (s, 3H),
4.03 (t, J＝7.1 Hz, 4H), 6.98 (t, J＝6.5 Hz, 2H), 7.19 (d,
J＝8.7 Hz, 2H), 7.28 (d, J＝5.4 Hz, 2H), 7.33 (t, J＝7.5
Hz, 1H), 7.66 (t, J＝7.5 Hz, 2H), 7.83 (d, J＝7.5 Hz,
2H), 8.01－8.09 (m, 4H), 8.41 (d, J＝8.1 Hz, 2H), 8.79
(s, 2H); MALDI-TOF-MS m/z: 764.3 ([M–PF6]＋). Anal.
calcd for C40H40F6N9OPRu: C 52.86, H 4.44, N 13.87;
found C 53.19, H 4.65, N 13.92.
Synthesis of complex [(CF3ptpy)Ru(Budtab)](PF6)
(8)
This complex was prepared according to the same
procedure for the synthesis of 6, from [(CF3ptpy)RuCl3]
Chin. J. Chem. 2013, 31, 329—338
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335

Yang & Zhong
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(58.4 mg, 0.10 mmol), AgOTf (77.0 mg, 0.30 mmol),
and ligand 1 (32.4 mg, 0.10 mmol). In this procedure,
45.1 mg of 8 was isolated in a yield of 48%. H NMR
(400 MHz, CD3CN) δ: 0.63 (t, J＝7.4 Hz, 6H), 0.89－
0.95 (m, 4H), 1.51－1.55 (m, 4H), 4.02 (t, J＝7.1 Hz,
4H), 7.02 (t, J＝6.5 Hz, 2H), 7.26 (d, J＝6.5 Hz, 2H),
7.31 (d, J＝6.3 Hz, 1H), 7.68 (t, J＝7.4 Hz, 2H), 7.82 (d,
J＝7.5 Hz, 2H), 8.00 (d, J＝8.2 Hz, 2H), 8.06 (s, 2H),
8.33 (d, J＝8.1 Hz, 2H), 8.47 (d, J＝8.1 Hz, 2H), 8.90
(s, 2H); MALDI-TOF-MS m/z: 802.3 ([M–PF6]＋). Anal.
calcd for C40H37F9N9PRu: C 50.74, H 3.94, N 13.31;
found C 51.03, H 4.36, N 12.92.
([M]＋). Anal. calcd for C12H14ClN3: C 61.15, H 5.99, N
17.83; found C 61.21, H 6.04, N 17.96.
1
Synthesis of complex [(bpy)2Ru(Butab)](PF6) (12)
To 10 mL dry acetone were added [Ru(bpy)2Cl2]•
2H2O (156 mg, 0.30 mmol) and AgOTf (156 mg, 0.60
mmol). The system was refluxed for 3 h before cooling
to room temperature. The mixture was filtered to re-
move insoluble AgCl precipitate. The filtrate was con-
centrated to dryness. To the residue were added ligand
10 (37.4 mg, 0.20 mmol), 10 mL of DMF, and 10 mL of
t-BuOH. The mixture was refluxed in a sealed tube for
24 h. After cooling to room temperature, the solvent
was removed under reduced pressure. The residue was
dissolved in proper amount of methanol. After adding
an excess of KPF6, the resulting precipitate was col-
lected by filtering and washing with water and Et2O.
The obtained solid was subjected to flash column chro-
matography on silica gel (eluent: CH2Cl2/CH3CN, V∶V
＝10∶1) to give 14 mg of complex 12 in a yield of
Synthesis of complex [(Mebip)Ru(Budtab)](PF6) (9)
This complex was prepared according to the same
procedure for the synthesis of 6, [(Mebip)RuCl3] (54.6
mg, 0.10 mmol), AgOTf (77.0 mg, 0.30 mmol), and
ligand 1 (32.4 mg, 0.10 mmol). In this procedure, 36.8
1
mg of complex 9 was isolated in a yield of 41%. H
NMR (400 MHz, CD3CN) δ: 0.54 (t, J＝7.4 Hz, 6H),
0.78－0.88 (m, 4H), 1.39－1.47 (m, 4H), 3.93 (t, J＝7.2
Hz, 4H), 4.44 (s, 6H), 6.32 (d, J＝8.2 Hz, 2H), 6.87 (t,
J＝7.7 Hz, 2H), 7.24 (t, J＝7.7 Hz, 2H), 7.51 (d, J＝8.3
Hz, 2H), 7.82 (s, 2H), 7.98 (d, J＝7.4 Hz, 2H), 8.18 (t,
J＝8.1 Hz, 1H), 8.60 (d, J＝8.1 Hz, 2H); ESI-MS m/z:
764.5 ([M–PF6]＋). Anal. calcd for C39H40F6N11PRu: C
51.54, H 4.44, N 16.95; found C 51.31, H 4.68, N 16.54.
1
12%. H NMR (400 MHz, CD3CN) δ: 0.79 (t, J＝7.3
Hz, 3H), 1.04－1.14 (m, 2H), 1.67－1.76 (m, 2H), 4.19
(t, J＝6.9 Hz, 2H), 6.25－6.29 (m, 1H), 6.72－6.76 (m,
1H), 6.80－6.83 (m, 1H), 7.20－7.24 (m, 3H), 7.34 (t,
J＝6.5 Hz, 1H), 7.47 (d, J＝7.4 Hz, 1H), 7.75－7.95 (m,
7H), 8.00 (s, 1H), 8.19 (d, J＝5.6 Hz, 1H), 8.29－8.34
(m, 3H), 8.38 (d, J＝8.1 Hz, 1H); ESI-MS m/z: 614.4
([M–PF6]＋). Anal. calcd for C32H30F6N7PRu•0.5H2O: C
50.07, H 4.07, N 12.77; found C 50.05, H 3.87, N 12.62.
Synthesis of 1-n-butyl-4-phenyl-1,2,3-triazole (Bu-
tabH, 10)[17]
Synthesis of complex [(bpy)2Ru(Cl-Butab)](PF6) (13)
A mixture of phenylacetylene (494 mg, 4.8 mmol),
butyl azide (0.6 mL, 6.0 mmol), sodium ascorbate (0.3
mmol, 59.4 mg), and CuSO4•5H2O (7.5 mg, 0.030
mmol) in a 1∶1 mixture of t-BuOH and H2O (10 mL)
was stirred at room temperature for 24 h. The solvents
were removed under vacuum. The residue was subjected
to flash column chromatography (eluent: petroleum
ether/ethyl acetate, V∶V＝5∶1) to give 649 mg of 10
This complex was prepared according to the same
procedure for the synthesis of 12, from [Ru(bpy)2Cl2]•
2H2O (156 mg, 0.30 mmol), AgOTf (156 mg, 0.60
mmol), and ligand 11 (47.0 mg, 0.20 mmol). In this
procedure, 23.7 mg of complex 13 was isolated in a
1
yield of 21%. H NMR (400 MHz, CD3CN) δ: 0.79 (t,
J＝7.3 Hz, 3H), 1.05－1.08 (m, 2H), 1.68－1.72 (m,
2H), 4.19 (t, J＝6.9 Hz, 2H), 6.18 (s, 1H), 6.83 (d, J＝
8.2 Hz, 1H), 7.23－7.26 (m, 3H), 7.34 (t, J＝6.5 Hz,
1H), 7.44 (d, J＝8.0 Hz, 1H), 7.82－7.86 (m, 6H), 7.94
(t, J＝7.0 Hz, 1H), 8.03 (s, 1H), 8.17 (d, J＝5.6 Hz, 1H),
8.32－8.39 (m, 4H, overlapped); ESI-MS m/z: 648.3
([M–PF6]＋ ). Anal. calcd for C32H29ClN7Ru•Et2O: C
49.86, H 4.53, N 11.31; found C 49.41, H 4.24, N 11.80.
1
in a yield of 72%. H NMR (400 MHz, CDCl3) δ: 0.98
(t, J＝7.4 Hz, 3H), 1.37－1.43 (m, 2H), 1.92－1.96 (m,
2H), 4.41 (t, J＝7.2 Hz, 2H), 7.30－7.36 (m, 1H),
7.40－7.45 (m, 2H), 7.74 (s, 1H), 7.84 (d, J＝7.7 Hz,
2H); EI-MS m/z: 201 ([M]＋).
Synthesis of 4-(N-n-butyl-1,2,3-triazol-4-yl)-chloro-
benzene (Cl-ButabH, 11)
Electrochemical measurements
A mixture of 4-chlorophenylacetylene (136 mg, 1.0
mmol), butyl azide (125 mg, 1.3 mmol), sodium ascor-
bate (12 mg), and CuSO4•5H2O (5 mg) in a 1∶1 mix-
ture of t-BuOH and H2O (10 mL) was stirred at room
temperature for 24 h. The solvents were removed under
vacuum. The residue was subjected to flash column
chromatography on silica gel (eluent: petroleum
ether/ethyl acetate, V∶V＝5∶1) to give 230 mg of 11
All CV measurements were taken using a CHI620D
potentiostat with one-compartment electrochemical cell
under an atmosphere of nitrogen. All measurements
were carried out in 0.1 mol•L−1 Bu4NClO4 in indicated
solvents at a scan rate of 100 mV/s. The working elec-
trode was a glassy carbon with a diameter of 0.3 mm.
The electrode was polished prior to use with 0.05 μm
alumina and rinsed thoroughly with water and acetone.
A large area platinum wire coil was used as the counter
electrode. All potentials are referenced to a Ag/AgCl
electrode in saturated aqueous NaCl without regard for
1
in a yield of 94%. H NMR (400 MHz, CDCl3) δ: 0.98
(t, J＝7.4 Hz, 3H), 1.36－1.42 (m, 2H), 1.89－1.97 (m,
2H), 4.40 (t, J＝7.2 Hz, 2H), 7.39 (d, J＝8.0 Hz, 2H),
7.73 (s, 1H), 7.76 (d, J＝8.0 Hz, 2H); EI-MS m/z: 235
336
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© 2013 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chin. J. Chem. 2013, 31, 329—338

Cyclometalated Ruthenium Complexes of 1,2,3-Triazole-containing Ligands
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the liquid junction potential.
Spectroscopic measurements
All optical ultraviolet-visible absorption spectra
were obtained using a TU-1810DSPC spectrometer
from Beijing Purkinje General Instrument Co. Ltd. at
room temperature in the solvents noted, with a conven-
tional 1.0 cm quartz cell.
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Computational methods
DFT and TDDFT calculations were carried out using
the B3LYP exchange correlation functional,[18]
implemented in the Gaussian 03 program package.[19]
The electronic structures of complexes were determined
using a general basis set with the Los Alamos effective
core potential LANL2DZ basis set for ruthenium, and
6-31G* for other atoms in vacuo.[20]
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X-ray crystallography
A single crystal of 7 or 9 was mounted on a glass fi-
ber and transferred into the cold nitrogen stream. The
X-ray diffraction data were collected using a Rigaku
Saturn 724 diffractometer on a rotating anode (Mo Kα
radiation, λ＝0.71073 Å). The structure was solved by
direct methods using SHELXS-97 and refined aniso-
tropically on F2 with SHELXL-97.[21] All hydrogen at-
oms were located in their idealized positions, with
methyl C－H bond length 0.98 Å and the aromatic C－
H bond length 0.95 Å, and included in the refinement
using a riding model approximation. CCDC 910894
(complex 7) and CCDC 910892 (complex 9) contain the
supplementary crystallographic data for this paper.
These data can be obtained free of charge from the
Cambridge Crystallographic Data Center via www.ccdc.
cam.ac.uk/data_request/cif.
Acknowledgement
This work is supported by the National Natural Sci-
ence Foundation of China (Nos. 21002104, 21271176,
and 91227104), the National Basic Research (973 pro-
gram) of China (No. 2011CB932301), and Institute of
Chemistry, Chinese Academy of Sciences (“100 Talent”
Program and No. CMS-PY-201230). Changjiang Yao
and Longzhen Sui of the same research group are ac-
knowledged for preparing the single-crystal samples and
compounds 10 and 11, respectively.
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© 2013 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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