Luminescent rhenium(I) - Gold(I) hetero organometallics linked by ethynylphenanthrolines

Article abstract of DOI:10.1016/j.jorganchem.2004.06.026

The first luminescent rhenium(I)-Gold(I) hetero organometallics, Re{phen-≡-Au(PPh₃)₃Cl (3) and Re{(PPh₃)Au-≡-phen-≡-Au(PPh₃)} (CO)₃Cl (4), have been prepared using the gold(I) complex AuCl(PPh₃) (PPh₃=triphenylphosphine) and the novel rhenium(I) complexes Re(phen-≡-H)(CO)₃Cl (5) (phen-≡-H = 3-ethynyl-1,10-phenanthroline) or Re(H-≡-phen -≡-H)(CO)₃Cl (6) (H-≡-phen-≡-H = 3,8-bis(ethynyl)-1,10-phenanthroline). All the present rhenium(I) complexes 3-6 were revealed to possess a facial configuration (fac-isomer) with respect to the three carbonyl ligands. The main frameworks for these new gold(I) organometallics were constructed by the Au-C σ-bonding (with the η¹-type coordination) between the ethynylphenanthrolines and the Au(I) phosphine unit. Re(I)-Au(I) heterometallics 3 and 4 have shown single phosphorescence from the ³MLCT excited state and this observation can be interpreted in terms of the efficient intramolecular energy transfer from the Au(I) unit to the Re(I) unit.

Full text of DOI:10.1016/j.jorganchem.2004.06.026

Journal of Organometallic Chemistry 689 (2004) 2905–2911
www.elsevier.com/locate/jorganchem
Luminescent rhenium(I)–gold(I) hetero organometallics linked by
ethynylphenanthrolines
a
b,
a
Youhei Yamamoto , Michito Shiotsuka *, Satoru Onaka
a
Department of Environmental Technology, Graduate School of Engineering, Nagoya Institute of Technology,
Gokiso-cho, Showa-ku, Nagoya 466-8555, Japan
b
Department of Socio Science and Engineering, Graduate School of Engineering, Nagoya Institute of Technology,
Gokiso-cho, Showa-ku, Nagoya, Aichi 466-8555, Japan
Received 13 April 2004; accepted 21 June 2004
Available online 22 July 2004
Abstract
The first luminescent rhenium(I)–gold(I) hetero organometallics, Re{phenA„AAu(PPh3)}(CO)3Cl (3) and Re{(PPh3)AuA„A
phenA„AAu(PPh3)}(CO)3Cl (4), have been prepared using the gold(I) complex AuCl(PPh3) (PPh3 =triphenylphosphine) and the
novel rhenium(I) complexes Re(phenA„AH)(CO)3Cl (5) (phenA„AH=3-ethynyl-1,10-phenanthroline) or Re(HA„AphenA
„AH)(CO)3Cl (6) (HA„AphenA„AH=3,8-bis(ethynyl)-1,10-phenanthroline). All the present rhenium(I) complexes 3–6 were re-
vealed to possess a facial configuration (fac-isomer) with respect to the three carbonyl ligands. The main frameworks for these new
gold(I) organometallics were constructed by the Au–C r-bonding (with the g1-type coordination) between the ethynylphenanthr-
olines and the Au(I) phosphine unit. Re(I)–Au(I) heterometallics 3 and 4 have shown single phosphorescence from the 3MLCT ex-
cited state and this observation can be interpreted in terms of the efficient intramolecular energy transfer from the Au(I) unit to the
Re(I) unit.
Ó 2004 Elsevier B.V. All rights reserved.
Keywords: Rhenium; Gold; Hetero organometallics; Ethynylphenanthroline; Phosphorescence
1. Introduction
the supramolecular structures [3–5]. However, photo-
physical explorations so far done for the heteronuclear
Re–M (M=Ru, Os, Zn, Fe, etc.) complexes have dem-
onstrated only several examples of the specific energy
transfer from the other metal unit to the rhenium carbo-
nyl unit [6–8]. On the other hand, interesting lumines-
cent properties have been revealed for gold(I) acetylide
organometallics which have been investigated for the
past decade. Che and coworkers [9] have reported a tan-
talizing phosphorescence for novel gold(I) ethynylarene
organometallics and suggested the potential applications
of these complexes to opt-electronic materials. In addi-
tion, our recent communication on the gold(I) ethynyl-
phenanthroline organometallics, phenA„AAu(PPh3)
(1) and (PPh3)AuA„APhenA„AAu(PPh3) (2), re-
vealed the intense phosphorescence even at an ambient
There has been a growing interest in the design of
multinuclear systems built-up by the photoactive d6
transition-metal complexes owing to the development
of photonic nano-devices [1]. Rhenium(I) tricarbonyl
diimine complexes, Re(L–L)(CO)3X, have been particu-
larly intriguing not only because of their unique photo-
physical properties, but also because of a possible
synthon for the photoactive supramolecular system [2].
Recent studies have exhibited many types of rhenium
tectonics such as molecular wires, squares, and triangles
based on Re(CO)3 units with respect to the diversities of
*
Corresponding author. Tel.: +81527355172; fax: +81527355247.
E-mail address: michito@nitech.ac.jp (M. Shiotsuka).
0022-328X/$ - see front matter Ó 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2004.06.026

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Y. Yamamoto et al. / Journal of Organometallic Chemistry 689 (2004) 2905–2911
Au(PPh3)}(CO)3Cl
(3)
and
Re{(PPh3)AuA„A
Au PPh3 Ph3P Au
Au PPh3
phenA„AAu(PPh3)}(CO)3Cl (4), were synthesized
from the rhenium complexes 5 or 6 and AuCl(PPh3)
(PPh3 =triphenylphosphine) with a 1:1 or 1:2 mol ratio
in THF by adding an excess of amine as a base.
Re(I)–Au(I) organometallics 3 and 4 were obtained in
reasonable yields. These novel rhenium complexes 3–6
have been characterized by 1H NMR, IR, UV–Vis spec-
troscopies, and elemental analysis.
N
N
N
N
(1)
(2)
Au PPh3 Ph3P Au
Au PPh3
N
N
N
N
OC Re Cl
OC CO
OC Re Cl
OC CO
The C„O, C„C, and H–C(„C) stretching frequen-
cies are collated in Table 1 for 1–8. The IR spectra of
Re(I)–Au(I) and Au(I) organometallics 1–4 showed the
characteristic weak m(C„C) band in the region of
2080–2120 cmꢀ1, which is typical for the g1 coordination
of alkynylgold(I) organometallics [2,9,12]. However,
gold(I) compounds 1–4 lack the m(H–C(„C)) bands.
On the contrary, the precursor rhenium(I) complexes
and the phenanthroline ligands 5–8 exhibit the m(H–
C(„C)) stretches in the area of 3140–3190 cmꢀ1. These
data clearly demonstrate the existence of the Au–C
r-bonding with the g1 type coordination between the
ethynylphenanthrolines and Au(I) phosphine complex.
Further, the data of rhenium(I) compounds 3–6 in Table
1 show three strong m(CO) bands in the range between
1860 and 2030 cmꢀ1. The m(CO) pattern of these com-
plexes suggests that the present rhenium(I) derivatives
have a ‘‘C3v’’ symmetry with respect to the three carbo-
nyl ligands, which indicates a facial configuration around
the rhenium center [1,13,14]. Previous studies on all rhe-
nium(I) diimine tricarbonyl halides, Re(CO)3(L–L)X,
have been reported to have a facial configuration as far
as we know (confirmed by NMR and X-ray crystallogra-
phy) [14,15]. The structural characteristics for the present
rhenium(I) compounds, including the Au–C r-bonding
with respect to the ethynylphenanthrolines for all gold(I)
compounds, are further supported by the 1H NMR
measurements discussed below.
(3)
(4)
H
H
H
N
N
N
N
OC Re Cl
OC CO
OC Re Cl
OC CO
(5)
(6)
Chart 1.
temperature (Chart 1) [10]. To the best of our knowl-
edge, there is no report on the synthesis of Re(I)–
Au(I) organometallics containing rhenium tricarbonyl
diimine unit and the luminescent gold(I) unit. Thus,
we were tempted to the synthesis of Re(I)–Au(I) organ-
ometallics, each unit of which has a characteristic lumi-
nescent property. In the present paper, we report on the
synthesis and the unique photophysical properties of the
first hetero organometallics which are constructed from
the luminescent rhenium(I) tricarbonyl unit and the
luminescent gold(I) phosphine unit; both units are
connected by ethynylphenanthrolines as a p-conjugated
ligand. The new entries to this heterometallic systems
are Re{phenA„AAu(PPh3)}(CO)3Cl (3) and Re-
{(PPh3)AuA„AphenA„AAu(PPh3)}(CO)3Cl (4) and
the synthesis of relevant novel precursor rhenium(I)
complexes, Re(phenA„AH)(CO)3Cl (5) and Re-
(HA„AphenA„AH)(CO)3Cl (6) is also described
(Chart 1).
1
The H NMR spectra of 1–6 exhibit well defined sig-
nals with the required numeral aromatic protons for the
phenanthrolines in the range of d=7.60–9.50 ppm. The
phenyl proton signals on the gold(I) compounds 1–4
are observed as multiplets with an exact integration in
the region between 7.40 and 7.70 ppm, while the singlet
2. Results and discussion
2.1. Synthesis and structural study
Table 1
The collected stretching frequencies for compounds 1–8
The precursor rhenium complexes, Re(phenA„AH)-
(CO)3Cl (5) and Re(HA„AphenA„AH)(CO)3Cl (6),
were first prepared by modifying the literature method
[11]. The ligand 3-ethynylphenanthroline, PhenA„AH
(7), or 3,8-bis(ethynyl)phenanthroline, HA„APhen
A„AH (8), and Re(CO)5Cl were heated together in
benzene at 60 °C for several hours. The solvent was par-
tially removed from the reaction mixture and to this was
added n-pentane resulting in precipitation of the yellow
powder 5 or orange solid 6, respectively, in good yields.
Re(I)–Au(I) hetero organometallics, Re{phenA„A
Compounds
mCO (cmꢀ1
)
mC„C
mH–C(„C)
(cmꢀ1
(cmꢀ1
)
)
1
2
3
4
5
6
7
8
2108(w)
2105(w)
2088(w)
2113(w)
2105(w)
2113(w)
2090(w)
2097(w)
2002(s), 1907(s), 1891(s)
2019(s), 1914(s), 1895(s)
2022(s), 1908(s), 1870(sh)
2021(s), 1905(s), 1861(sh)
3182(m)
3188(m)
3146(m)
3175(m)

Y. Yamamoto et al. / Journal of Organometallic Chemistry 689 (2004) 2905–2911
2907
signal assignable to the terminal ethynyl proton disap-
pears. However, this type of proton signals for 5–8 are
clearly observed in the range of d=3.37–3.59 ppm.
The aromatic proton signals of the phenanthroline
ligands shift to the lower field by the coordination with
the present rhenium(I) carbonyl unit. For example, three
sets of signals (H-2,9, H-4,7, and H-5,6) observed at d
9.27, 8.28, and 7.68 for 2 cause the downfield shift (d
9.40, 8.42, and 7.81 ppm) for 4. Similar downfield shifts
upon coordination of the rhenium(I) carbonyl unit are
observed for all the sets of compounds between 8 and
6 or 1 and 3 or 7 and 5 as shown in Table 2. This phe-
nomenon is generally interpreted in terms of the r dona-
tion of the phenanthroline ligand [14]. However, the
upfield shifts are triggered by the coordination of the
gold(I) phosphine unit to the ethynylphenanthroline–
Re(CO)3Cl moiety. For instance, three sets of signals
at d 9.41, 8.60, and 8.00 for 6 move to d 9.40, 8.42,
7.81 ppm for 4. Similar upfield shifts upon coordination
of the gold(I) unit are displayed for almost all the sets of
compounds between 8 and 2 or 7 and 1 or 5 and 3, al-
though the signals assignable to H-2 and H-2,9 proton
show slight downfield shifts. The upfield shift is inter-
preted in terms of the p back donation from Au(I) center
around the Re center (the facial configuration) because
only three sets of signals are observed for the symmetri-
cal diethynylphenanthroline ligand in the rhenium com-
pounds 4 and 6; the signals of the meridional isomer
should show six sets of aromatic proton signals in the
phenanthroline ligand because of the different trans in-
fluence between carbonyl and chloride ligands.
2.2. Photophysical properties
Table 3 culls the numerical data and the quantum
yields for the UV–Vis and emission spectra on the
complexes 1–6. The UV–Vis absorption spectra for 1,
3, and 5 which contain an ethynyl ligand exhibit
a
new intense absorption band assignable to
p–p*(C„C) absorption in the 300–370 nm region com-
pared with the spectra of Re(phen)(CO)3Cl although
weak absorption for MLCT transition should overlap
in this region (Fig. 1). Fig. 2 clearly shows quite similar
intense p–p*(C„C) absorption band for 2, 4, and 6 in
which the two ethynyl groups are attached to the phen-
anthroline skeleton in the 320–390 nm. Further, the as-
signment of p–p*(C„C) transition for these intense
bands is supported by the fact that these bands ob-
served on 1–6 are almost intact upon changing the sol-
vent from DMF to CH2Cl2 because the solvatochromic
1
to the ethynylphenanthroline ligands. Further, these H
NMR data definitely support the ‘‘C3v’’ symmetry
Table 2
The 1H NMR data for compounds 1–8
Compounds
Chemical shift (ppm)
H-2
H-9
H-4
H-7
H-5
H-6
H-3
H–C(„C)
1
3
5
7
9.28
9.44
9.42
9.23
9.16
9.35
9.42
9.21
8.32
8.49
8.61
8.36
8.24
8.47
8.56
8.25
7.79
7.94
8.05
7.82
7.72
7.90
7.99
7.75
7.63
7.80
7.90
7.65
3.57
3.37
H-2,9
H-4,7
H-5,6
H–C(„C)
2
4
6
8
9.27
9.40
9.41
9.24
8.28
8.42
8.60
8.37
7.68
7.81
8.00
7.80
3.59
3.39
Table 3
The photophysical data for compounds 1–6a
Compounds
UV–Vis absorption
kabs (nm) (e, 104 dm3 molꢀ1 cmꢀ1
Emissionb
kem (nm) (Uem, 10ꢀ3
)
)
1
2
3
4
5
6
328 (3.9),
357 (7.5),
349 (2.3),
315 (3.5),
337 (6.1),
334 (2.2),
358 (3.3),
316 (1.8),
326 (1.9),
279 (5.1),
286 (5.9),
284 (2.9),
294 (4.3),
279 (3.9),
283 (2.9),
269 (4.5)
470, 505
501, 543
637 (3.2)
644 (1.8)
655 (2.6)
673 (0.8)
276 (5.5)
268 (2.5)
276 (4.1),
379 (3.7),
269 (4.0)
388 (0.4),
414 (0.3),
335 (1.9),
272 (2.8)
a
UV–Vis and emission spectra were measured in a degassed dichloromethane at room temperature.
b
The quantum yields were determined upon excitation at 450 nm and calculated relative to Re(bpy)Cl(CO)3 (Uem =0.0031 in CH2Cl2) as a
standard.

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Y. Yamamoto et al. / Journal of Organometallic Chemistry 689 (2004) 2905–2911
nm region and this band is characteristic of the
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
Re(d)!L(p*) MLCT transition which has been exten-
sively studied for many kinds of rhenium(I) diimine tri-
carbonyl complexes [16–18]. These MLCT bands for
the diethynyl compounds 4 and 6 tailed to a longer
wavelength area compared with the ethynyl com-
pounds 3 and 5. This tailing should be accounted for
in terms of the more extended electronic delocalization
between the phenanthroline ligands. In addition, the
p–p* transition bands have been red-shifted upon coor-
dination of the rhenium(I) carbonyl group. For exam-
ple, the absorption bands assignable to the p–p*
transitions for 3 at 351, 334 nm shift to 328, 315 nm
for 1. Similar red-shifts are observed for the pair of 4
and 2 as shown in Fig. 2. These red-shifts in p–p* ab-
sorptions are due to the electronic modification of the
phenanthroline ligands, which is induced by the
1
450
400
Wavelength / nm
250
300
350
500
550
600
rhenium(I) carbonyl coordination; H NMR study dis-
cussed above supports the interpretation.
Luminescence spectra of the present rhenium(I) com-
plexes 3–6 were observed as a broad emission around
650 nm in the CH2Cl2 solution at room temperature
as shown in Fig. 3. This type of luminescence is typical
for the phosphorescence from the dp(Re)–p* (diimine)
3MLCT excited state, which has been reported in many
rhenium(I) diimine tricarbonyl complexes [16–18]. Inter-
estingly, the Re(I)–Au(I) organometallics 3 and 4 do not
Fig. 1. UV–Vis absorption spectra of 1 (---), 3 (—), 5 (-–-) and
Re(phen)(CO)3Cl (––) in the degassed CH2Cl2 solution at room
temperature.
0.8
0.7
emit such
a structured band assignable to the
3[p–p*(C„C-phen)] transition originated from the
Au(I) ethynylphenanthroline excited state [10]. The exci-
tation spectra of these hetero organometallics are in ac-
cordance with the absorption spectra, including the
p–p*(C„C) absorption bands for respective derivatives.
These results indicate that the present Re(I)–Au(I)
0.6
0.5
0.4
0.3
0.2
0.1
0
a
c
450
400
Wavelength / nm
250
300
350
500
550
600
b
Fig. 2. UV–Vis absorption spectra of 2 (---), 4 (—), 6 (-–-) and
Re(phen)(CO)3Cl (––) in the degassed CH2Cl2 solution at room
temperature.
d
shift of MLCT band on rhenium diimine complexes is
generally observed [16]. The molar extinction coeffi-
cients for the p–p* bands in the Re(I)–Au(I) hetero
complex 4 are almost twice as those of 3 due to the
doubled number of the Au(I)–ethynyl units. The result
is consistent with our recent communication on the
gold(I) complexes 2 and 1 [10]. Each of the present rhe-
nium(I) complexes 3–6 has a broad band at approxi-
mately 400 nm with a tail extending to the 500–550
500
550
600
650
700
750
800
Wavelength / nm
Fig. 3. Emission spectra of 3 (a), 4 (b), 5 (c) and 6 (d) in the degassed
CH2Cl2 solution at room temperature. These spectra were detected
upon excitation at 450 nm.

Y. Yamamoto et al. / Journal of Organometallic Chemistry 689 (2004) 2905–2911
2909
1
organometallics are susceptible to the efficient intramo-
lecular energy transfer from the Au(I) ethynylphen-
anthroline units to the Re(I) diimine tricarbonyl unit.
Furthermore, the increase of the luminescence quantum
yield between Re(I)–Au(I) organometallics 3 or 4 and
the precursor Re(I) complexes 5 or 6 has been
observed, respectively (Fig. 3). The quantum yield is
increased more than 200% in 4 compared with that of
6, while the relative intensification for 3 is about 120%
against 5 (Table 3). This difference might be investigated
by using the energy gap law, because the wavelength of
emission maxima (kem) for Re(I)–Au(I) organometallics
3 and 4 is observed at high energy relative to that
of these precursor complexes 5 and 6, respectively
(Table 3).
terization of the novel complexes has been done by H
NMR, IR, ESI-MS spectroscopy, and elemental analyses.
The 1H NMR spectra were recorded with a Bruker
AVANCE NMR spectrometer (200 and 600 MHz) at
room temperature and the chemical shifts were referenced
to TMS. IR spectra were obtained on a JASCO FT/IR 460
spectrometer using the KBr-pellet method. Elemental
analyses were carried out at the Center for Organic Ele-
mental Microanalysis, Graduate School of Pharmaceuti-
cal Sciences, Kyoto University. UV–Vis spectra were
recorded on a JASCO V-750 UV/VIS/NIR spectropho-
tometer and the emission spectra were recorded on an
OTSUKA Electronics PTI-5100S spectrophotometer in
a degassed dichloromethane (spectroscopic grade) at
room temperature. The quantum yields on the present
rhenium(I) complexes were determined upon the excita-
tion at 450 nm and calculated relative to Re(bpy)Cl(CO)3
(Uem =0.0031 in CH2Cl2) as a standard [21].
3. Conclusion
The first luminescent rhenium(I)–gold(I) organome-
tallics have been successfully synthesized by linking the
luminescent rhenium(I) tricarbonyl complex unit and
the luminescent gold(I) phosphine complex unit via
ethynylphenanthrolines as a p-conjugated ligand. These
Re(I)–Au(I) organometallics and novel rhenium(I) com-
plexes have a facial configuration with respect to the
three carbonyl ligands, and all gold(I) compounds pos-
sess a linear two-coordination around the Au(I) center.
Re(I)–Au(I) organometallics have shown the single
4.2. Preparation of phenA„AAu(PPh3) (1)
The methanol solution (10 ml) of sodium methoxide
(45 mg, 0.8 mmol) was added to the methanol solution
(20 ml) of AuCl(PPh3) (PPh3 =triphenylphosphine)
(247 mg, 0.5 mmol) and PhenA„AH (102 mg, 0.5
mmol) under Ar. After the mixture was stirred at room
temperature for 1 h, the white precipitate was collected
by filtration with a suction filter and washed with
MeOH, H2O, and ether successively. The powder was
dried at 30 °C under vacuum for 12 h. Yield: 84%
(278 mg). Anal. Calc. for C32H22N2P1Au1H2O: C,
56.48; H, 3.55; N, 4.12. Found C, 56.23; H, 3.45; N,
3
phosphorescence from the dp(Re)–p* (diimine) MLCT
excited state. However, the structured emission from the
3[p–p*(C„Cphen)] excited state on Au(I) ethynylphen-
anthroline unit was not observed. These spectral charac-
teristics are interpreted in terms of the efficient
intramolecular energy transfer from the Au(I) unit to
the Re(I) unit. These heterometallics should be a versa-
tile luminescent scaffolding and a building block for con-
structing multimetallic arrays, which have the potential
applications to further develop into opt-electronic devices
by appropriate design and modification. These studies
are underway in our laboratory.
1
3.90%. IR (cmꢀ1) m(C„C): 2108. H NMR (CDCl3):
d=9.28 (d, J=1.9 Hz, 1H, H-2), 9.16 (dd, J=4.3, 1.6
Hz, 1H, H-9), 8.32 (d, J=1.9 Hz, 1H, H-4), 8.24 (dd,
J=7.6, 1.6 Hz, 1H, H-7), 7.79 (d, J=8.9 Hz, 1H, H-5),
7.72 (d, J=8.9 Hz, 1H, H-6), 7.65–7.40 (m, 16H, H-8
and phenyl-H).
4.3. Preparation of (PPh3)AuA„AphenA„AAu-
(PPh3) (2)
Fifty-seven mg of HA„AphenA„AH (0.25 mmol)
was dissolved in an anhydrous methanol (30 ml) under
argon. This solution was added to the dry THF solution
(30 ml) of AuCl(PPh3) (248 mg, 0.50 mmol) and the mix-
ture was stirred at room temperature. The methanol so-
lution (8 ml) of KOH (157 mg, 2.8 mmol) was added
dropwise to the mixture. After 10 min, a pale-yellow pre-
cipitate appeared in the solution. The precipitate was col-
lected by filtration with a suction filter and washed with
MeOH, H2O, and ether successively. The powder was
dried at 30 °C under vacuum for 5 h. Yield: 88% (252
mg). IR (cmꢀ1) m(C„C): 2109. Anal. Calc. for
C52H36N2P2Au22H2O: C, 52.89; H, 3.41; N, 2.37. Found
C, 53.25; H, 3.23; N, 2.36%. 1H NMR (CDCl3): d=9.27
4. Experimental
4.1. Materials and general measurements
All reactions were carried out under an argon atmos-
phere. Solvents were freshly distilled according to stand-
ard procedure. The starting materials were purchased
from Sigma–Aldrich and used without further purifica-
tion. The rhenium complex ReCl(CO)5 was prepared
according to the literature method [19]. The 3-ethynyl-
1,10-phenanthroline (PhenA„AH) (7) and 3,8-bis(ethy-
nyl)-1,10-phenanthroline (HA„AphenA„AH) (8) were
synthesized by the method of Tor et al. [20]. The charac-

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Y. Yamamoto et al. / Journal of Organometallic Chemistry 689 (2004) 2905–2911
(d, J=1.9 Hz, 2H, H-2,9), 8.28 (d, J=1.9 Hz, 2H, H-4,7),
7.68 (s, 2H, H-5,6), 7.65–7.40 (m, 15H, phenyl-H).
diisopropylamine (0.70 ml) was added to the solution
and stirred at room temperature for 1 day. The solvent
was distilled off under reduced pressure and the residue
was washed with acetonitrile. After drying under vacu-
um, 4 was obtained as orange powders. Yield: 80%
(348 mg). IR (cmꢀ1) m(C„C): 2113(w), m(CO): 2019(s),
1914(s), 1895(s). Anal. Calc. for C35H22N2O3Cl1-
P2Au2Re1: C, 45.54; H, 2.50; N, 1.93. Found C, 45.12;
H, 2.61; N, 2.28%. 1H NMR (CDCl3): d=9.40 (d,
J=1.7 Hz, 2H, H-2,9), 8.42 (d, J=1.7 Hz, 2H, H-4,7),
7.81 (s, 2H, H-5,6), 7.60–7.40 (m, 30H, phenyl-H).
4.4. Preparation of fac-Re(phenA„AH)(CO)3Cl (5)
and fac-Re(HA„A phenA„AH)(CO)3Cl (6)
Precursor Re(I) complexes 5 and 6 were synthesized
by the modification of general literature methods on
Re(L–L)(CO)3Cl (L–L=bpy, phen) from the reaction
of Re(CO)5Cl with L–L. The chelating ligands
PhenA„AH (163 mg, 0.8 mmol) and Re(CO)5Cl (180
mg, 0.5 mmol) in benzene were heated at 60 °C for sev-
eral hours. The solution was concentrated and then 30
mL of n-pentane was added to redissolve the excess lig-
and. The yellow precipitate of 5 was filtered off and
Acknowledgment
This work was supported by The Matsuda Founda-
tionꢀs Research Grant and by Grant-in-Aid for Scientific
Research No. 15750048 from the ministry of Education,
Culture, Sports, Science and Technology, Japan.
dried under vacuum. Yield: 94% (240 mg). IR (cmꢀ1
)
m(C„C): 2105(w), m(CO): 2022(s), 1908(s), 1870(sh),
1
m(H–C(„C)): 3182(m). H NMR (CDCl3): d 9.42 (d,
J=1.6 Hz, 1H, H-2), 9.42 (dd, J=4.9, 1.3 Hz, 1H, H-
9), 8.61 (d, J=1.6Hz, 1H, H-4), 8.56 (dd, J=8.2, 1.3
Hz, 1H, H-7), 8.05 (d, J=8.8 Hz, 1H, H-5), 7.99 (d,
J=8.8 Hz, 1H, H-6), 7.90 (dd, J=8.2, 4.9 Hz, 1H, H-
8), 3.57 (s, 1H, H–C(„C)).
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