Cyclometalated Osmium-Amine Electronic Communication through the p-Oligophenylene Wire

Article abstract of DOI:10.1021/acs.inorgchem.5b01828

A series of bis-tridentate cyclometalated osmium complexes with a redox-active triarylamine substituent have been prepared, where the amine substituent is separated from the osmium ion by a p-oligophenylene wire of various lengths. X-ray crystallographic

Full text of DOI:10.1021/acs.inorgchem.5b01828

Article
pubs.acs.org/IC
Cyclometalated Osmium−Amine Electronic Communication through
the p‑Oligophenylene Wire
Jun-Jian Shen, Jiang-Yang Shao, Zhong-Liang Gong, and Yu-Wu Zhong*
Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Photochemistry, Institute of Chemistry, Chinese
Academy of Sciences, Beijing 100190, China
*
S Supporting Information
ABSTRACT: A series of bis-tridentate cyclometalated osmium
complexes with a redox-active triarylamine substituent have
been prepared, where the amine substituent is separated from
the osmium ion by a p-oligophenylene wire of various lengths.
X-ray crystallographic data of complexes 3(PF ) and 4(PF )
6
6
with three or four repeating phenyl units between the osmium
ion and the amine substituent are presented. These complexes
show two consecutive anodic redox couples between +0.1 and
+
0.9 V vs Ag/AgCl, with the potential splitting in the range of 300−390 mV. A combined experimental and theoretical study
suggests that, in the one-electron-oxidized state, the odd electron is delocalized for short congeners and localized on the osmium
component for long congeners. The electronic coupling parameter (V ) was estimated by the Marcus−Hush analysis. The
ab
distance dependence plot of ln(V ) versus the osmium−amine geometrical distance (R ) gives a negative linear relationship
ab
ab
−1
with a decay slope of −0.19 Å , which is slightly steeper with respect to the previously reported ruthenium−amine series with
the same molecular wire. DFT calculations with the long-range-corrected UCAM-B3LYP functional gave more reasonable results
for the osmium complexes with respect to those with UB3LYP.
INTRODUCTION
used to probe the long-range electronic communication
through a p-oligophenylene molecular wire. p-Oligopheny-
■
11
Photoinduced electron transfer occurs ubiquitously in natural
lene is an important molecular wire that has received much
systems and optoelectronic devices. One useful method to1
attention in photoinduced electron/energy transfer processes.
12
probe this fundamental process is mixed-valence chemistry,
However, the synthesis and studies of oligophenylene
derivatives with more than four repeating phenyl units are
which normally involves the synthesis of a bridged molecule
containing two identical redox-active termini and performs the
13
limited. It is well known that the electronic coupling of
inorganic mixed-valent compounds is greatly dependent on the
intervalence charge transfer (IVCT) analysis on the mixed2-
valent state generated by one-electron oxidation or reduction.
1
,2
metal species and coordination environment.
We are
This analysis has been able to yield important parameters, such
as reorganization energy (λ) and electronic coupling parameter
Vab) of the involving electron transfer process. This field has
interested in knowing the change of the metal−amine long-
range electronic coupling properties upon replacing the
cyclometalated ruthenium with the cyclometalated osmium
ion. A previous study has shown that strong coupling is present
(
been receiving continuous attention since the pioneering work
3
by Creutz and Taube and recently gained renewed interest due
14
between osmium and amine through a short phenyl bridge.
The use of osmium complexes in mixed-valent chemistry has
to the potential uses of mixed-valent molecules in molecular
4
5
6
electronics, electrochromism, and information storage.
15
been known, although it has received less attention with
respect to its second-row analogue ruthenium. Osmium
complexes generally have more inert metal−ligand bonds and
stronger spin−orbit coupling relative to ruthenium complexes.
This makes the optoelectronic properties of osmium complexes
Later studies have shown that the theories and analytical
methods of mixed-valent chemistry can be applied for the
analysis of common redox-active donor−acceptor systems
provided that the transition dipole lies along the donor−
7
acceptor axis and the donor−acceptor overlap can be ignored.
16
significantly different from those of ruthenium complexes. We
present herein the synthesis and electronic coupling studies of a
series of cyclometalated osmium−triarylamine hybridized
In this way, the concept of mixed-valence chemistry has been
greatly expanded, and any two redox-active motifs, either
inorganic or organic, can be used to build such nonsymmetric
8
complexes 1(PF ) −5(PF ), where the osmium ion and the
mixed-valent compounds in the broad sense. We previously
used the combination of cyclometalated ruthenium and
triarylamine to build nonsymmetric donor−acceptor systems.
The obtained complexes showed strong electronic coupling and
appealing electrochromism in the near-infrared (NIR) region.
Recently, we found that these two redox components can be
6 2
6
amine nitrogen atom are separated by the p-oligophenylene
9
wire of various lengths (Scheme 1).
1
0
Received: August 11, 2015
©
XXXX American Chemical Society
A
DOI: 10.1021/acs.inorgchem.5b01828
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Article
Scheme 1. Synthesis of 1(PF ) −7(PF )
6
2
6
RESULTS AND DISCUSSION
■
Synthesis and Single-Crystal Structures. Complexes
(PF ) −5(PF ) were prepared as outlined in Scheme 1. The
1
6
2
6
11
reaction of the known ligand L1−L5 with [Os(tpy)(H O) ]-
2
3
1
7
(
PF )
(tpy = 2,2′:6′,2″-terpyridine) in ethylene glycol,
6
3
followed by anion exchange using KPF , afforded 1(PF ) −
6
6 2
5
5
(PF ), respectively, in acceptable yield. Complexes 2(PF )−
6
6
(PF ) were isolated with one counteranion. Complex 1(PF )
6
6 2
was isolated as the one-electron-oxidized form with two
+
counteranions. Compound 1 is more readily oxidized than
the other members of the series, as determined by the
electrochemical results discussed below. Complex 1(PF ) is
6
2
1
paramagnetic, and no distinct H NMR signals have been
recorded. On the other hand, satisfactory H NMR spectra have
1
been obtained for complexes 2(PF )−5(PF ). For the purpose
6
6
of comparison, model complexes 6(PF ) and 7(PF ) were
6
6
Figure 1. Thermal ellipsoid diagram (30% probability) of the single-
crystal structure of (a) 3(PF ) and (b) 4(PF ). Hydrogen atoms and
anions are omitted for clarity. Atom color code: carbon, gray; nitrogen,
blue; oxygen, red; osmium, navy.
prepared in which the oligophenylene unit is present but the
triarylamino group is lacking. These complexes were synthe-
sized from ligand L6 or L7, respectively, which were obtained
from the Suzuki coupling of 1,3-di(pyrid-2-yl)bromobenzene
with phenyl boronic acid or 4-biphenyl boronic acid,
respectively.
6
6
comparing the potentials of these waves with the OsIII/II
Single crystals of 3(PF ) and 4(PF ) were obtained by slowly
potential of a model complex, [Os(dpb) (ttpy)](PF ) (+0.36
6
6
6
diffusing n-hexane into their solutions in CH Cl . Figure 1
V; dpb = 1,3-(pyrid-2-yl)benzene; ttpy = 4′-tolyl-2,2′:6′,2″-
2
2
1
8
•+/0
shows the thermal ellipsoid diagrams of the X-ray crystallo-
graphic structures of these two complexes. The osmium ion has
an expected hexacoordinate octahedral configuration. The
triarylamine motifs have a three-wheel propeller configuration.
The Os−C bond of 3(PF ) and 4(PF ) has a length of
terpyridine; Figure S1 in the SI) and the N
potential of L2
11
•
+/0
(+0.70 V; L1−L5 have very similar N
potential), it is
reasonable to assign the first anodic wave of 1(PF ) −5(PF ) to
6
2
6
III/II
•+/0
the Os
process and the second one to the N
process,
III/II
6
6
respectively. Complexes 6(PF ) and 7(PF ) show an Os
6
6
1
.965(5) and 1.978(9) Å, respectively. The geometrical
process at +0.43 and +0.42 V vs Ag/AgCl, respectively (Figure
S2).
distance between the osmium ion and the amine nitrogen
atom is 14.797 and 19.229 Å for 3(PF ) and 4(PF ),
In the cathodic scan, a tpy-based reduction wave can be
observed for all complexes. The comproportionation constant
6
6
respectively. The full crystallographic data are provided in the
Experimental Section and Supporting Information (SI).
Electrochemical Studies. Figure 2 shows the cyclic
voltammograms (CVs) and differential pulse voltammograms
II
III
•+
III
K for the equilibrium [Os −N] + [Os −N ] → 2[Os −N]
c
5
6
ranges from 1.2 × 10 to 4.1 × 10 for 1(PF ) −5(PF ). This
large comproportionation constant suggests that the one-
electron-oxidized form [Os −N] has good thermodynamic
stability, which will be beneficial for the following spectroelec-
6
2
6
III
(
DPVs) of 1(PF ) −5(PF ). The electrochemical data are
6
2
6
summarized in Table 1. Complex 1(PF ) displays two anodic
6
2
redox processes at +0.21 and +0.60 V vs Ag/AgCl, with a
trochemical measurements.
potential splitting (ΔE) of 390 mV. Complexes 2(PF )−5(PF )
Spectroscopic Studies. The fact that complex 1(PF ) was
6
6
6 2
show similar two redox waves. However, both waves shift to a
slightly more positive region. In addition, the potential splitting
isolated as the odd-electron form is also supported by its
absorption spectrum, which shows an intense charge transfer
transition at 950 nm. This band decreases upon either one-
electron oxidation or one-electron reduction by stepwise
electrolysis at a transparent indium−tin−oxide (ITO) glass
becomes smaller (ΔE = 320, 310, 300, and 300 mV for 2(PF ),
6
3
(PF ), 4(PF ), and 5(PF ), respectively), and the difference of
6 6 6
the potential splitting of these four complexes is small. By
B
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Figure 2. CVs (a−e) and DPVs (f) of 1(PF ) −5(PF ) at a glassy carbon disk electrode in 0.1 M Bu NClO /CH Cl . The initial scan starts from 0
6
2
6
4
4
2
2
V and moves toward the positive potential.
Table 1. Electrochemical Data
a
E1/2/V (ΔE /mV)
p
b
c
compound
anodic
cathodic
ΔE (mV)
Kc
6
5
5
5
5
1
2
3
4
5
(PF6)2
(PF6)
(PF6)
(PF6)
(PF6)
+0.21 (180), + 0.60 (200)
+0.40 (230), + 0.72 (240)
+0.45 (200), + 0.76 (190)
+0.45 (200), + 0.75 (210)
+0.44 (190), + 0.74 (200)
+0.36 (70)
−1.59 (180)
−1.59 (210)
−1.56 (200)
−1.58 (200)
−1.57 (180)
−1.48 (80)
390
320
310
300
300
4.1 × 10
2.7 × 10
1.8 × 10
1.2 × 10
1.2 × 10
[Os(dpb) (ttpy)](PF6)
L2
+0.70 (100)
6
(PF6)
(PF6)
+0.43 (120)
−1.57 (120)
−1.56 (110)
7
+0.42 (120)
a
Data in CH Cl . The electrochemical potentials are reported as the E value vs Ag/AgCl. Potentials vs ferrocene+/0 can be estimated by
2
2
1/2
subtracting 0.45 V. ΔE refers to the peak-to-peak potential separation of each chemically reversible process. The relatively large ΔE values of
p
p
b
1
(PF ) −5(PF ) are likely due to slow electron transfer kinetics under the current measurement conditions. The potential splitting of two anodic
6
2
6
waves. K = 10ΔE(mV)/59.
c
c
electrode (Figure 3). This phenomenon has been observed for
is possibly due to aminium-targeted charge transfer transitions.
The appearance of some weak absorption at 2400 nm was
observed in Figure 4a and 4b. These absorptions are very likely
caused by the Os d−d transitions.
During the oxidative spectroelectrochemical measurements
related phen-1,4-diyl-bridged ruthenium or osmium−amine
9
,14
hybridized complexes
and forms the basis for theirs
10
III
20
applications in NIR electrochromism.
Figure 4 shows the absorption spectral changes of 2(PF )−
6
4
(PF ) upon one-electron (single) and the second one-electron
of 3(PF ) and 4(PF ) (Figure 4c−f), the appearance of the
6
6
6
(
(
double) oxidations. In the single-oxidation step of 2(PF6)
potential was increased from +0.40 to +0.65 V vs Ag/AgCl),
DACT absorption can also be observed in the single-oxidation
2
+
step, which decreases upon double oxidation. For complex 4 ,
the DACT band is rather weak and severely overlaps with the
higher energy side of the visible absorptions. The decrease of
the DACT band upon double oxidation can be clearly
distinguished as shown by the enlarged spectral changes in
the NIR region in the inset of Figure 4f. No distinct NIR
absorptions were observed when the model complexes 8(PF6)
the metal-to-ligand charge transfer (MLCT) transitions in the
visible decreased and new NIR absorptions around 1160 nm
appeared (Figure 4a). The latter NIR transition is attributed to
the donor-to-acceptor charge transfer (DACT) transitions in
2
+
the odd-electron state (2 ). In the double-oxidation step
potential was increased from +0.65 to +1.0 V), the NIR
(
transitions decreased and two absorption bands at 700 and 900
nm appeared (Figure 4b). The peak at 700 nm is characteristic
and 9(PF ) were subjected to oxidative electrolysis (Figure S3).
6
In addition, when ligand L2 was subjected to similar oxidative
•
+
19
•+
of the N -localized transitions of triarylamine compounds.
This peak was also observed for 3(PF ) and 4(PF ) after
electrolysis, the N -localized transitions at 750 nm appeared
11
(Figure S4). The absorptions with wavelength longer than
900 nm are negligible. These results support the assignment of
6
6
3+
double oxidation (Figure 4d and 4f). The peak at 900 nm of 2
C
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2+
osmium−amine electronic coupling in 5 must be very weak
and difficult to estimate by spectroscopic analysis.
2+
2+
The DACT bands of 1 −4 are displayed in Figure 5a as a
2
+
̃
function of wavenumbers (υ). The DACT band of 4 was
Figure 3. Absorption spectral changes of 1(PF ) upon one-electron
6
2
oxidation (a) or reduction (b) in CH Cl upon stepwise oxidative
2
2
electrolysis at an ITO glass electrode.
2
+
2+
Figure 5. (a) DACT transitions of 1 −4 in CH Cl as a function of
2
2
2+
wavenumbers. For complex 4 , the Gussian-deconvoluted data is
2
+
2+
2
+
the above NIR absorptions of 2 −4 to DACT absorptions.
used. (b) Gaussian fitting of the NIR absorption spectra of 4 . The
black curve is the experimental data. The blue and green curves are the
deconvoluted data. The blue curve is the deconvoluted DACT band of
Some oligo-triarylamines are known to give NIR absorption
21
bands in their oxidized forms, which are attributable to
intervalence charge transfer transitions between amine centers.
This does not disagree with the interpretations of our results.
2+
4
. The red curve is the sum of the deconvoluted data.
For the longer congener 5(PF ), no distinct DACT band can
derived by Gaussian fitting of its NIR absorptions (Figure 5b).
6
2+
2+
be observed upon one-electron oxidation (Figure S5). Probably
a very weak DACT band is buried inside the higher energy side
For complexes 2 −4 , the DACT bands are symmetric.
However, the DACT band of 12+ is nonsymmetric, with the
lower energy side slightly narrower relative to the higher energy
2
+
of the visible absorptions of 5 . However, the degree of
Figure 4. Absorption spectral changes of 2(PF ) (a,b), 3(PF ) (c,d), and 4(PF ) (e,f) upon single (a,c,e) and double oxidation (b,d,f) in CH Cl
2
6
6
6
2
upon stepwise oxidative electrolysis at an ITO glass electrode. The applied potential was referenced versus Ag/AgCl. (Inset in f) Enlarged plots in
the NIR region.
D
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side. As discussed in the Introduction, the Marcus−Hush
the osmium−amine series. Another possibility for the steeper
slope of the osmium series is that the osmium series complexes
may have a larger tunneling energy gap with respect to the
2+
theory of mixed-valence chemistry should be applicable to 1 −
2
+
4
. The electronic coupling parameter V was thus calculated
ab
−1
2+
2+
2+
2+
25
to be 2310, 960, 460, and 190 cm for 1 , 2 , 3 , and 4 ,
respectively, according to Vab = (μ υ
ruthenium series. The tunneling energy gap is difficult to
22
̃
max)/eRab, where μge is
determine; however, the redox state of cyclometalated osmium,
cyclometalated ruthenium, and the bridging oligophenylene
increases in an ascending order. This means that the energy gap
between osmium and the bridge should be larger with respect
to that between ruthenium and the bridge, which will lead to a
larger tunneling energy gap for the osmium series relative to the
ruthenium series.
ge
the transition dipole moment of the DACT band, e is the
elementary charge, and Rab is the diabatic electron transfer
distance which was taken to be the DFT-calculated Os−N
geometrical distance (Table 2). This equation is applicable to
the CT band of any shape, and μ can be calculated from the
ge
23
integrated absorbance of the CT band.
It should be noted that R may be much shorter with respect
ab
a
to the geometrical distance between redox sites due to a high
degree of charge delocalization. This means that the calculated
Vab values are underestimated. However, this may have little
influence on the comparison of the decay slope between two
series because both series complexes were studied using the
same method. The decay slopes of both ruthenium and osmium
Table 2. Parameters for NIR Charge Transfer Transitions
b
Vab (cm−1
)
c
υ
̃max (cm−1)
εmax (M−1 cm−1
)
Rab (Å)
12+
22+
32+
42+
10 530
8650
9510
9630
9550
8600
2970
1030
6.1
10.5
14.8
19.2
2310
960
460
190
−1
series are comparable to the attenuation factor (β = 0.46 Å )
a
On the basis of the spectroelectrochemical results in CH Cl .
of the oligophenylene wire determined by charger transfer
2
2
b
c
12e
Estimated by the DFT-optimized Os−N geometrical distance. V
dynamics by Wasielewski and co-workers. Note that the β
ab
values calculated by (μ υ
̃
)/eR .
value determined by charger transfer dynamics and the γ value
ge max
ab
determined by electronic coupling differ by a factor of 2,
−1
Figure 6 shows the distance dependence plot of ln(V )
ab
namely, the β value of 0.46 Å corresponds to a γ value of 0.23
2+
2+
−1
versus R of 1 −4 , where the four data can be well fitted to a
ab
Å .
DFT Studies. DFT calculations are known to provide useful
information on the spin density distributions of mixed-valent
compounds. We first performed the geometrical optimization
2+
2+
of 1 −4 on the level of theory of UB3LYP/LANL2DZ/6-
3
1G*/CPCM (see details in the Experimental Section). The
left panel of Figure 7 shows the Mulliken spin density
distributions (α−β) and segmental analysis of these com-
2
+
2+
pounds optimized with this method. Compounds 1 and 2
show delocalized spin density distributions. To our surprise, the
spin density of 32+ and 4 are more biased toward or localized
on the triarylamine segment. This result seems contradicting
with the above electrochemical findings, which suggest that the
2+
+
+
one-electron oxidation of 1 −4 is more likely associated with
III/II
the Os
process. In addition, we found that no electron
paramagnetic resonance (EPR) signals could be recorded for
Figure 6. Distance dependence plot of ln(V ) as a function of Rab (Å)
2+
2+
ab
1 −4 either at room or low temperature. This also suggests
2+ 2+
from data in Table 2. The data was fitted to a linear equation with a
that 1 −4 are dominated by or have a large contribution
from the Os(III) forms because common Os(III) complexes
are known not to show distinct EPR signals due to the strong
−1
2
slope of −0.19 Å and adjusted R of 0.99.
−1
15
negative linear equation with a decay slope (−γ) of −0.19 Å .
This suggests a tunneling-dominated electron-transfer mecha-
nism. Such a linear relationship is well known for a series of
related donor−acceptor compounds with a tunneling-domi-
spin−orbital coupling effect.
Being aware of the fact that DFT results are significantly
dependent on the calculation method, we used the long-range-
26
corrected version of B3LYP, CAM-B3LYP functional, to
12
2+
2+
nated superexchange mechanism. Note that the decay slope
reperform geometrical optimization of 1 −4 . The results
2+
2+
of the 1 −4 series is slightly steeper with respect to the
obtained with UCAM-B3LYP show reasonable spin density
2
+
previously reported ruthenium−amine series with the same
distributions (right panel of Figure 7), where compounds 1
1
1
2+
2+
molecular wire, where the decay slope was calculated to be
are delocalized and the spin density of 2 −4 are more biased
toward or localized on the osmium component. These results
make us question the reliability of the previously reported DFT
−
1
−
0.14 Å . We conjecture that this difference is caused by the
different redox asymmetry of these two series compounds. As
1
1
has been discussed in the electrochemical analysis, the
calculations on the ruthenium−amine series compounds,
cyclometalated osmium model complex [Os(dpb) (ttpy)](PF )
where UB3LYP was used and the spin density of long
congeners was also found to localize on the triarylamine
segment. Although the EPR results gave consistent information
in this case, we are interested to know whether the use of
UCAM-B3LYP will make a difference. The spin density
distributions of three of the ruthenium−amine compounds
calculated with UCAM-B3LYP are shown in Figure S6, which
indeed gives very similar information with respect to those
6
III/II
shows the Os
process at +0.36 V vs Ag/AgCl, while the
•
+/0
N
process of L1−L5 occurs at +0.70 V. In contrast, the
corresponding cyclometalated ruthenium model complex
III/II
[
Ru(dpb) (tpy)](PF ) shows the Ru
process at +0.56
6
2
4
V. This suggests that the osmium−amine series compounds
have larger redox asymmetry relative to the ruthenium−amine
series compounds, which may lead to the steeper decay slope of
E
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Inorganic Chemistry
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2+
2+
Figure 7. DFT-calculated spin density distributions and segmental analysis of 1 −4 by using the UB3LYP (left) or UCAM-B3LYP (right)
functional.
calculated with UB3LYP. These results suggest that DFT
calculations in some circumstances are highly dependent on the
functional and method used. Theoretical results alone may lead
to incorrect information. It would be better to combine both
experimental and theoretical data for the interpretation of a
specific system.
EXPERIMENTAL SECTION
■
Synthesis. NMR spectra were recorded in the designated solvent
on a Bruker Avance 300 or 400 MHz spectrometer. Spectra are
reported in ppm values from residual protons of deuterated solvent.
Mass data were obtained with a Bruker Daltonics Inc. Autoflex III
MALDI-TOF mass spectrometer (Germany). The matrix for MALDI-
TOF measurement is α-cyano-4-hydroxycinnamic acid. Microanalysis
was carried out using a Thermo Scientific Flash EA 1112 analyzer
(USA) at the Institute of Chemistry, Chinese Academy of Sciences.
CONCLUSION
■
[
Os(tpy)(H O) ](PF ) was prepared according to the known
2 3 6 3
17
In summary, the electronic communication between cyclo-
metalated osmium and redox-active triarylamine through the p-
oligophenylene molecular wire has been investigated. Electro-
chemical and spectroelectrochemical measurements suggest
that the osmium component was oxidized prior to the amine
oxidation. The electron transfer from the neutral amine site to
the oxidized osmium(III) component occurs via a tunneling-
procedure. Ligands L1−L5 were prepared according to a previous
1
1
report.
Synthesis of Complex 1(PF ) . To 7 mL of dry ethylene glycol
6
2
were added [Os(tpy)(H O) ](PF ) (68.4 mg, 0.075 mmol) and
2
3
6 3
ligand L1 (23.0 mg, 0.050 mmol). The mixture was refluxed for 1 h
under microwave heating (power = 600 W). After cooling to room
temperature, an excess of aq. KPF6 was added. The resulting
precipitate was collected by filtrating and washing with water and
Et O. The obtained solid was subjected to flash column chromatog-
raphy on silica gel (eluent: acetone/H O/aq. KNO , 100/5/1),
−1
dominated mechanism with a decay slope of −0.19 Å , which
is slightly steeper with respect to the previously reported
ruthenium−amine series with the same molecular wire. This
difference is possibly caused by the relative larger redox
asymmetry or larger tunneling energy gap of the osmium−
amine series compounds. In addition, DFT calculations with
UCAM-B3LYP gave more reasonable results for the osmium
complexes with respect to those with the UB3LYP functional.
This suggests that the choice of functional is important for
obtaining useful information consistent with experimental
findings.
2
2
3
followed by anion exchange using KPF , to give 28.0 mg of complex
6
1
[
(PF ) in 48% yield as a brown solid. MALDI-MS (m/z): 883.5 for
6 2
2+
M − 2PF ] . Anal. Calcd for C H F N O P Os·3H O: C, 44.08,
H, 3.37, N, 6.85. Found: C: 44.37, H, 3.07, N, 7.02.
6
45 35 12
6
2
2
2
Synthesis of Complex 2(PF ). This complex was prepared from
6
[
Os(tpy)(H O) ](PF ) and ligand L2 as a red solid in 58% yield
2
3
6 3
using the similar procedure for the synthesis of complex 1(PF )
eluent for column chromatography: acetone/CH Cl , 5/1). H NMR
6
2
1
(
(
6
2 2
400 MHz, acetone-d ): 3.84 (s, 6H), 6.67 (td, J = 6.5, 1.2 Hz, 2H),
6
.05−7.05 (m, 6H), 7.07 (t, J = 6.6 Hz, 2H), 7.10−7.20 (m, 6H), 7.28
(d, J = 5.6 Hz, 2H), 7.60 (td, J = 7.6, 1.6 Hz, 2H), 7.71 (td, J = 8.0, 1.6
F
DOI: 10.1021/acs.inorgchem.5b01828
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Article
Hz, 2H), 7.80−7.95 (m, 3H), 8.49 (d, J = 8.0 Hz, 2H), 8.70 (d, J = 8.4
Synthesis of Complex 6(PF ). To a mixture of 2 mL of DMF and
6
Hz, 2H), 8.74 (s, 2H), 9.00 (d, J = 8.0 Hz, 2H). MALDI-MS (m/z):
3 mL of ethylene glycol were added [Os(tpy)Cl ] (0.10 mmol, 53 mg)
3
+
9
5
59.2 for [M − PF ] . Anal. Calcd for C H F N O POs·H O: C,
and ligand L6 (0.10 mmol, 31 mg). The mixture was refluxed under
microwave heating for 30 min at a power of 375 W and then another
10 min at a power of 600 W. After cooling to room temperature, an
6
51 39
6
6
2
2
4.64; H, 3.69; N, 7.50. Found: C, 54.61; H, 3.59; N, 7.64.
Synthesis of Complex 3(PF ). This complex was prepared from
6
[
Os(tpy)(H O) ](PF ) and ligand L3 as a red solid in 73% yield
excess of aqueous KPF was added. The resulting precipitate was
2
3
6
3
6
using the similar procedure for the synthesis of complex 1(PF )
collected by filtering and washing with water and Et O. The crude
solid was purified through flash column chromatography on silica gel,
6
2
2
1
(
(
eluent for column chromatography: acetone/CH Cl , 5/1). H NMR
2
2
400 MHz, acetone-d ): 3.83 (s, 6H), 6.70 (td, J = 6.4, 1.2 Hz, 2H),
followed by anion exchange using KPF , to give 57 mg of 6(PF ) in
6
6
6
1
6
7
.92−7.05 (m, 8H), 7.08 (td, J = 6.6, 1.2 Hz, 2H), 7.12−7.18 (m, 4H),
65% yield as a red solid. H NMR (300 MHz, acetone-d ): δ 6.67 (t, J
6
.30 (d, J = 6.0 Hz, 2H), 7.62 (td, J = 8.0, 1.6 Hz, 2H), 7.67 (d, J = 8.8
= 6.3 Hz, 2H), 7.00 (d, J = 5.7 Hz, 2H), 7.10 (t, J = 6.0 Hz, 2H),
7.35−7.45 (m, 3H), 7.60 (d, J = 7.8 Hz, 2H), 7.63 (d, J = 7.8 Hz, 2H),
7.71 (td, J = 7.8, 1.5 Hz, 2H), 7.88 (t, J = 7.8 Hz, 1H), 8.03 (d, J = 7.2
Hz, 2H), 8.51 (d, J = 8.4 Hz, 2H), 8.71 (d, J = 8.1 Hz, 2H), 8.82 (s,
2H), 9.01 (d, J = 7.8 Hz, 2H). MALDI-MS (m/z): 732.2 for [M −
Hz, 2H), 7.72 (td, J = 7.6, 1.6 Hz, 2H), 7.84−7.92 (m, 3H), 8.13 (d, J
8.4 Hz, 2H), 8.55 (d, J = 8.4 Hz, 2H), 8.72 (d, J = 8.0 Hz, 2H), 8.86
s, 2H), 9.02 (d, J = 8.0 Hz, 2H). MALDI-MS (m/z): 1035.2 for [M −
=
(
+
PF ] . Anal. Calcd for C H F N O POs·H O: C, 57.18; H, 3.79; N,
7
6
57 43
6
6
2
2
+
.02. Found: C, 57.13; H, 3.66; N, 7.26.
PF ] . Anal. Calcd for C H F N POs·H O: C, 49.72; H, 3.16; N,
6
37 26
6
5
2
Synthesis of Complex 4(PF ). This complex was prepared from
7.84. Found: C, 50.10; H, 3.23; N, 7.68.
6
[
Os(tpy)(H O) ](PF ) and ligand L4 as a red solid in 70% yield
Synthesis of Complex 7(PF ). This complex was prepared from
2
3
6
3
6
using the similar procedure for the synthesis of complex 1(PF )
(
(
[Os(tpy)Cl ] (0.10 mmol, 53 mg) and ligand L7 (0.10 mmol, 38 mg)
6
2
3
1
eluent for column chromatography: acetone/CH Cl , 5/1). H NMR
as a red solid in 71% yield (67 mg of product was obtained) using the
2
2
1
300 MHz, acetone-d ): 3.83 (s, 6H), 6.70 (t, J = 6.3 Hz, 2H), 6.90−
similar procedure for the synthesis of complex 6(PF ). H NMR (300
6
6
7
.20 (m, 14H), 7.31 (d, J = 5.4 Hz, 2H), 7.62 (m, 4H), 7.72 (t, J = 7.2
MHz, acetone-d ): δ 6.70 (td, J = 6.6, 1.5 Hz, 2H), 7.00−7.15 (m,
6
Hz, 2H), 7.79 (d, J = 8.4 Hz, 2H), 7.84−7.92 (m, 3H), 7.97 (d, J = 8.1
Hz, 2H), 8.19 (d, J = 8.4 Hz, 2H), 8.56 (d, J = 8.1 Hz, 2H), 8.72 (d, J
4H), 7.30 (d, J = 5.7 Hz, 2H), 7.42 (t, J = 4.5 Hz, 1H), 7.55 (t, J = 7.5
Hz, 2H), 7.62 (td, J = 7.5, 1.5 Hz, 2H), 7.72 (td, J = 7.8, 1.5 Hz, 2H),
7.80−7.86 (m, 2H), 7.86−7.95 (m, 3H), 8.18 (d, J = 8.4 Hz, 2H), 8.56
=
8.1 Hz, 2H), 8.89 (s, 2H), 9.02 (d, J = 7.8 Hz, 2H). MALDI-MS (m/
+
z): 1111.6 for [M − PF ] . Anal. Calcd for C H F N O POs·H O:
C, 59.43; H, 3.88; N, 6.60. Found: C, 59.46; H, 3.82; N, 6.88.
(d, J = 8.1 Hz, 2H), 8.71 (d, J = 8.1 Hz, 2H), 8.87 (s, 2H), 9.01 (d, J =
6
63 47
6
6
2
2
+
8.1 Hz, 2H). MALDI-MS (m/z): 808.3 for [M − PF
for C43 POs·2H
52.34; H, 3.44; N, 6.74.
] . Anal. Calcd
6
Synthesis of Complex 5(PF ). This complex was prepared from
H
30
F
N
6
5
2
O: C, 52.28; H, 3.47; N, 7.09. Found: C,
6
[
Os(tpy)(H O) ](PF ) and ligand L5 as a red solid in 65% yield
2
3
6 3
using the similar procedure for the synthesis of complex 1(PF )
X-ray Crystallography. The X-ray diffraction data were collected
using a Rigaku Saturn 724 diffractometer on a rotating anode (Mo Kα
radiation, 0.71073 Å) at 173 K. The structure was solved by direct
6
2
1
(
(
7
7
=
eluent for column chromatography: acetone/CH Cl , 5/1). H NMR
2 2
300 MHz, acetone-d ): 3.82 (s, 6H), 6.71 (t, J = 7.2 Hz, 2H), 6.90−
6
2
7
28
.20 (m, 14H), 7.31 (d, J = 5.7 Hz, 2H), 7.55−7.65 (m, 4H), 7.65−
.80 (m, 4H), 7.84 (d, J = 5.1 Hz, 2H), 7.84−7.92 (m, 3H), 7.95 (d, J
method using SHELXS-97 and refined with Olex2. The structure
graphics were generated using Olex2. Crystallographic data for 3(PF
(CCDC: 1403263): C57 OsP, M = 1179.14, monoclinic,
space group P /c1, a = 14.214(3) Å, b = 15.470(3) Å, c = 24.639(5)
)
6
5.1 Hz, 2H), 8.00 (d, J = 5.1 Hz, 2H), 8.21 (d, J = 8.4 Hz, 2H), 8.57
H F N O
43 6 6 2
(
8
d, J = 8.4 Hz, 2H), 8.72 (d, J = 8.1 Hz, 2H), 8.90 (s, 2H), 9.02 (d, J =
2
1 1
+
3
.1 Hz, 2H). MALDI-MS (m/z): 1187.3 for [M − PF ] . Anal. Calcd
Å, α = 90°, β = 99.784(2)°, γ = 90°, U = 5339.2(19) Å , T = 173 K, Z
= 4, 42 007 reflections measured, radiation type Mo Kα, radiation
wavelength 0.71073 Å, final R indices R1 = 0.0573, wR2 = 0.1302, R
indices (all data) R1 = 0.0649, wR2 = 0.1346. Crystallographic data for
6
for C H F N O POs·H O: C, 61.42; H, 3.96; N, 6.23. Found: C,
69
51
6
6
2
2
6
1.00; H, 3.47; N, 6.39.
Synthesis of Ligand L6. To a suspension of 1,3-di(pyrid-2-
yl)bromobenzene (311 mg, 1.0 mmol), Pd(PPh ) (58 mg, 0.050
4(PF OsP)·5(CH
2935.10, monoclinic, space group P 2 /c1, a = 52.130(18) Å, b =
1 1
) (CCDC: 1403264): 2(C63
H
47
F
6
N
O
2
Cl ), M =
2 2
3
4
6
6
mmol), and K CO3 (690 mg, 5.0 mmol) in a mixed solvent of
2
degassed THF/H O (18 mL/2 mL) was added phenylboronic acid
8.757(2) Å, c = 26.681(9) Å, α = 90°, β = 93.943(4)°, γ = 90°, U =
2
3
(
146 mg, 1.2 mmol). The mixture was stirred at 90 °C for 12 h. The
12151(7) Å , T = 173 K, Z = 4, 106 506 reflections measured,
solvent was evaporated under reduced procedure. The crude product
was purified through column chromatography on silica gel (eluent:
CH Cl /EtOAc, 15/1) to give 200 mg of 3,5-di(pyrid-2-yl)-1,1′-
radiation type Mo Kα, radiation wavelength 0.71073 Å, final R indices
R1 = 0.0885, wR2 = 0.1535, R indices (all data) R1 = 0.1040, wR2 =
0.1598. It should be mentioned that single crystals of 3(PF
4(PF ) were obtained after several attempts by slowly diffusing n-
hexane into their solutions in CH Cl . No solvate of water was found
) and
2
2
6
1
biphenyl (L6) as a pale yellow solid in 65% yield. H NMR (300 MHz,
6
CDCl ): δ 7.25−7.35 (m, 2H), 7.39 (t, J = 7.5 Hz, 1H), 7.48 (t, J = 7.5
2
2
3
Hz, 2H), 7.75−7.85 (m, 4H), 7.91 (d, J = 7.8 Hz, 2H), 8.31 (d, J = 1.5
on the crystal structures. However, the samples for elemental analysis
were directly obtained after column chromatography where water was
added in the eluent. It is reasonable to compensate the microanalysis
data with water solvate.
Hz, 2H), 8.60 (t, J = 1.5 Hz, 1H), 8.75 (d, J = 4.2 Hz, 2H). 13C NMR
(
1
75 MHz, CDCl ): δ 120.84, 122.39, 124.49, 126.42, 127.43, 127.58,
3
28.79, 136.79, 140.47, 140.96, 142.38, 149.74, 157.19. EI-MS: 308 for
+
[
M] .
Synthesis of Ligand L7. To a suspension of 1,3-di(pyrid-2-
yl)bromobenzene (311 mg, 1.0 mmol), Pd(PPh ) (58 mg, 0.050
Spectroscopic Measurement. Absorption spectra were recorded
on a PE Lambda 750 UV/vis/NIR spectrophotometer at room
temperature. Spectroelectrochemical measurements were performed in
a thin layer cell (optical length 0.2 cm), in which a transparent ITO
glass electrode (<10 Ω/square) was set in the indicated solvent that
3
4
mmol), and K CO3 (690 mg, 5.0 mmol) in a mixed solvent of
2
degassed THF/H O (18 mL/2 mL) was added 4-biphenylboronic acid
2
−5
(
238 mg, 1.2 mmol). The mixture was stirred at 90 °C for 12 h. The
contained the compound to be studied (about 5 × 10 M) and 0.1 M
Bu NClO as the supporting electrolyte. A platinum wire and Ag/AgCl
solvent was evaporated under reduced procedure. The crude product
was purified through column chromatography on silica gel (eluent:
CH Cl /EtOAc, 15/1) to give 212 mg of 3,5-di(pyrid-2-yl)-1,1′:4′,1′′-
4
4
in saturated aqueous NaCl was used as the counter electrode and
reference electrode, respectively. The cell was put into the
spectrometer to monitor the spectral change during electrolysis.
Electrochemical Measurement. All electrochemical measure-
ments were taken using a CHI 660D potentiostat with a one-
compartment electrochemical cell under an atmosphere of nitrogen.
2
2
1
terphenyl (L7) as a pale yellow solid in 55% yield. H NMR (300
MHz, CDCl ): δ 7.25−7.35 (m, 2H), 7.37 (t, J = 7.2 Hz, 1H), 7.48 (t,
3
J = 7.2 Hz, 2H), 7.68 (d, J = 7.2 Hz, 2H), 7.71 (d, J = 8.1 Hz, 2H),
7
.81 (td, J = 7.5, 1.8 Hz, 2H), 7.87 (d, J = 8.1 Hz, 2H), 7.92 (d, J = 7.8
Hz, 2H), 8.36 (d, J = 1.5 Hz, 2H), 8.61 (s, 1H), 8.76 (d, J = 4.8 Hz,
All measurements were carried out in CH
2
Cl
Bu NClO as the supporting electrolyte at a scan rate of 100 mV/s
4 4
2
containing 0.1 M
H). 13C NMR (75 MHz, CDCl ): δ 120.87, 122.43, 124.58, 126.28,
n
2
1
1
3
27.10, 127.42, 127.51, 127.79, 128.87, 136.82, 139.82, 140.40, 140.54,
(for cyclic voltammetry). The working electrode was a glassy carbon
disk electrode (d = 3 mm). The electrode was polished prior to use
+
40.71, 141.82, 149.77, 157.17. EI-MS: 384 for [M] .
G
DOI: 10.1021/acs.inorgchem.5b01828
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Article
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 Ag/AgCl electrode in saturated aqueous
NaCl without regard for the liquid junction potential. Potentials vs
2013, 52, 5663. (j) Hildebrandt, A.; Lang, H. Organometallics 2013, 32,
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+
/0
ferrocene can be deduced by subtracting 0.45 V.
Computational Methods. DFT calculations were carried out
1
̈
5697. (c) Volker, S. F.; Renz, M.; Kaupp, M.; Lambert, C. Chem. -
29
26
using the B3LYP or CAM-B3LYP exchange correlation functional
and implemented in the Gaussian 09 program package. The electronic
structures of complexes were determined using a general basis set with
the Los Alamos effective core potential LanL2DZ basis set for osmium
Eur. J. 2011, 17, 14147. (d) Barlow, S.; Risko, C.; Odom, S. A.; Zheng,
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30
and 6-31G* for other atoms. No symmetry constraints were used in
the optimization (nosymm keyword was used). Solvent effects
(
CH Cl ) are included in all calculations with the conductor-like
2 2
31
polarizable continuum model (CPCM). Frequency calculations have
been performed with the same level of theory to ensure the optimized
geometries to be local minima. All orbitals have been computed at an
3
isovalue of 0.02 e/bohr .
2
014, 53, 1293. (j) Canzi, G.; Goeltz, J. C.; Henderson, J. S.; Park, R.
E.; Maruggi, C.; Kubiak, C. P. J. Am. Chem. Soc. 2014, 136, 1710.
(k) Ou, Y.-P.; Zhang, J.; Xu, M.; Xia, J.; Hartl, F.; Yin, J.; Yu, G.-A.;
Liu, S. H. Chem. - Asian J. 2014, 9, 1152. (l) Zhang, D.-B.; Wang, J.-Y.;
Wen, H.-M.; Chen, Z.-N. Organometallics 2014, 33, 4738. (m) Cheng,
T.; Tan, Y. N.; Zhang, Y.; Zhang, Y. Y.; Meng, M.; Lei, H.; Chen, L.;
Liu, C. Y. Chem. - Eur. J. 2015, 21, 2353.
ASSOCIATED CONTENT
Supporting Information
CVs of L2, [Os(dpb) (ttpy)](PF ), 6(PF ), and 7(PF );
absorption spectral changes of 6(PF ), 7(PF ), L2, and 5(PF )
upon oxidative electrolysis; DFT-calculated spin density
distribution of the ruthenium−amine series compounds using
the UCAM-B3LYP functiona;, Cartesian coordinates of DFT-
optimized structures; NMR and mass spectra of new
compounds; X-ray crystallographic data of 3(PF ) and 4(PF )
in cif format. The Supporting Information is available free of
charge on the ACS Publications website at DOI: 10.1021/
acs.inorgchem.5b01828.
■
*
S
6
6
6
6
6
6
(
(
3) Creutz, C.; Taube, H. J. Am. Chem. Soc. 1969, 91, 3988.
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6
2
(
Hohloch, S.; Sommer, M. G.; Schweinfurth, D.; Ehret, F.; Braunstein,
P.; Sarkar, B. Organometallics 2013, 32, 7366. (c) Das, H. S.;
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B. Chem.Eur. J. 2014, 20, 4334. (d) Nie, H.-J.; Zhong, Y.-W. Inorg.
Chem. 2014, 53, 11316.
CVs of L2, [Os(dpb) (ttpy)](PF ), 6(PF ), and 7(PF );
absorption spectral changes of 6(PF ), 7(PF ), L2, and
6
6
6
6
6
5
(PF ) upon oxidative electrolysis; DFT-calculated spin
6
(
6) (a) Simao, C.; Mas-Torrent, M.; Crivillers, N.; Lloveras, V.; Artes,
J. M.; Gorostiza, P.; Veciana, J.; Rovira, C. Nat. Chem. 2011, 3, 359.
b) Terada, K.; Kanaizuka, K.; Iyer, V. M.; Sannodo, M.; Saito, S.;
density distribution of the ruthenium−amine series
compounds using the UCAM-B3LYP functiona;, Carte-
sian coordinates of DFT-optimized structures; NMR and
mass spectra of new compounds (PDF)
X-ray crystallographic data of 3(PF ) in cif format (CIF)
X-ray crystallographic data of 4(PF ) in cif format (CIF)
(
Kobayashi, K.; Haga, M.-a. Angew. Chem., Int. Ed. 2011, 50, 6287.
(c) Cui, B.-B.; Mao, Z.; Chen, Y.; Zhong, Y.-W.; Yu, G.; Zhan, C.; Yao,
J. Chem. Sci. 2015, 6, 1308.
6
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AUTHOR INFORMATION
Corresponding Author
E-mail: zhongyuwu@iccas.ac.cn.
■
*
(8) (a) Ceccon, A.; Santi, S.; Orian, L.; Bisello, A. Coord. Chem. Rev.
2
004, 248, 683. (b) Bernhardt, P. V.; Bozoglian, F.; Macpherson, B. P.;
Notes
Martinez, M. Coord. Chem. Rev. 2005, 249, 1902. (c) Wheatley, N.;
Kalck, P. Chem. Rev. 1999, 99, 3379. (d) Vahrenkamp, H.; Gei, A.;
Richardson, G. N. J. Chem. Soc., Dalton Trans. 1997, 3643. (e) Bublitz,
G. U.; Laidlaw, W. M.; Denning, R. G.; Boxer, S. G. J. Am. Chem. Soc.
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
(
1
998, 120, 6068. (f) Ratera, I.; Sporer, C.; Ruiz-Molina, D.; Ventosa,
We thank the National Natural Science Foundation of China
grants 91227104, 21271176, 21472196, 21501183, and
1221002), the Institute of Chemistry, Chinese Academy of
Sciences (grant PY-2015-24), and the Strategic Priority
Research Program of the Chinese Academy of Sciences
N.; Baggerman, J.; Brouwer, A. M.; Rovira, C.; Vesciana, J. J. Am.
Chem. Soc. 2007, 129, 6117. (g) Heckmann, A.; Lambert, C. J. Am.
Chem. Soc. 2007, 129, 5515. (h) Halpin, Y.; Dini, D.; Ahmed, H. M. Y.;
Cassidy, L.; Browne, W. R.; Vos, J. G. Inorg. Chem. 2010, 49, 2799.
2
(i) Sixt, T.; Sieger, M.; Krafft, M. J.; Bubrin, D.; Fiedler, J.; Kaim, W.
(
grant XDB 12010400) for funding support.
Organometallics 2010, 29, 5511. (j) Das, A.; Scherer, T. M.; Mobin, S.
M.; Kaim, W.; Lahiri, G. K. Chem. - Eur. J. 2012, 18, 11007. (k) Wu, S.-
H.; Shen, J.-J.; Yao, J.; Zhong, Y.-W. Chem. - Asian J. 2013, 8, 138.
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DOI: 10.1021/acs.inorgchem.5b01828
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Inorganic Chemistry
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DOI: 10.1021/acs.inorgchem.5b01828
Inorg. Chem. XXXX, XXX, XXX−XXX