Unprecedented luminescent heteropolynuclear aggregates with gold thiolates as building blocks

Article abstract of DOI:10.1021/ic201245q

The reaction of [AuCl(P-N)], in which P-N represents a heterofunctional phosphine ligand, with pentafluorothiophenol, HSC₆F₅, gives the thiolate gold derivatives [Au(SC₆F₅)(P-N)] (P-N = PPh₂py (1), PP

Full text of DOI:10.1021/ic201245q

ARTICLE
pubs.acs.org/IC
Unprecedented Luminescent Heteropolynuclear Aggregates with
Gold Thiolates as Building Blocks
Olga Crespo, M. Concepciꢀon Gimeno,* Antonio Laguna, Fernando J. Lahoz, and Carmen Larraz
Departamento de Química Inorgꢀanica, Instituto de Síntesis Química y Catꢀalisis Homogꢀenea (ISQCH), Universidad de Zaragoza-CSIC,
E-50009 Zaragoza, Spain
S Supporting Information
b
ABSTRACT: The reaction of [AuCl(PÀN)], in which PÀN represents a heterofunc-
tional phosphine ligand, with pentafluorothiophenol, HSC6F5, gives the thiolate gold
derivatives [Au(SC6F5)(PÀN)] (PÀN = PPh2py (1), PPh2CH2CH2py (2), or PPhpy2
(3)). Complex [Au(SC6F5)(PPh2py)] (1) reacts with [Au(OTf)(PPh2py)] in a 1:1 or
1:2 molar ratio to afford the di- or trinuclear species [Au2(μ-SC6F5)(PPh2py)2]OTf (4)
and [Au3(μ3-SC6F5)(PPh2py)3](OTf)2 (5), with the thiolate acting as a doubly or triply
bridging ligand. The reactivity of the mononuclear compounds [Au(SC6F5)(PÀN)]
toward silver or copper salts in different ratios has been investigated. Thus, the treatment
of [Au(SC6F5)(PÀN)] with Ag(OTf) or [Cu(NCMe)4]PF6 in a 1:1 molar ratio gives
complexes of stoichiometry [AuAg(OTf)(μ-SC6F5)(PÀN)] (PÀN = PPh2py (6),
PPh2CH2CH2py (7), or PPhpy2 (8)) or [AuCu(μ-SC6F5)(PÀN)(NCMe)]PF6
(PÀN = PPh2py (9), PPh2CH2CH2py (10), or PPhpy2 (11)). These complexes
crystallize as dimers and display different coordination modes of the silver or copper
center, depending on the present functionalized phosphine ligand. The treatment of [Au(SC6F5)(PPh2py)] with silver and copper
compounds in other molar ratios has been carried out. In a 2:1 ratio, the complexes [Au2M(μ-SC6F5)2(μ-PPh2py)2]X (M = Ag, X =
OTf (12); M = Cu, X = PF6 (13)) are obtained. The same reaction in a 4:3 molar ratio affords the species [Au4M2(μ-SC6F5)3(μ-
PPh2py)4]X3 (M = Ag, X = OTf (14); M = Cu, X = PF6 (15)). The crystal structures of some of these complexes reveal different
interactions among the metallic d10 centers. The complexes display dual emission. The band at higher energy has been attributed to
intraligand (IL) transitions, and the one at lower energy has been assigned to a ligand to metal (LM) charge transfer process. The
latter emission is modulated by the heterometal (silver or copper).
’ INTRODUCTION
emissions are clearly LMCT but enhanced by the presence of
metallophilic interactions. Thiolate ligands are also well estab-
lished for gold, and their complexes have been known for a long
time. They are important in many fields of research. They are
used in medicine as antiarthritic agents and have also shown
antitumoral and anti-HIV activity. In nanoscience they can
act as stabilizers of metal nanoparticles and as precursors for
other sources of materials.6À8 Although gold thiolates of the
form [Au(SR)]n, [Au(SR)(PR3)], or [Au2(μ-SR)(PR3)2]+ are
very numerous,7a triply bridging gold thiolates of the form
[Au3(μ3-SR)L3]2+,7bÀd or heterometallic gold thiolates, are very
scarcely represented.7a Recently, D-penicillaminate gold complexes
have been used as building blocks to form aggregates by forming
S-bridged structures with copper or silver ions;9 pyridine-2-
thiolate gold derivatives also form a tetranuclear goldÀcopper
species,10 and pyridine-4-thiolate leads to heteronuclear com-
plexes with copper and chromium by coordination to the
nitrogen atom of the thiolate unit.11 The aim of this work is to
construct luminescent metal aggregates, starting from the build-
ing blocks of stoichiometry [Au(SC6F5)(PÀN)], which have
The chemistry of polynuclear d10 metal complexes, and group
11 in particular, has attracted a great deal of attention in the past
few years because of the special characteristics they show, such as
their structure and their photoluminescent behavior.1 These two
factors are often affected by the presence of metallic d10 d10
3 3 3
interactions, particularly in the case of gold(I) gold(I) inter-
3 3 3
actions. Aurophilic interactions are similar in strength to hydro-
gen bonds and are attributable to correlation and relativistic
effects.2 Polynuclear gold(I) derivatives generally possess in-
tense, long-lived luminescence in the solid state with emission
energies spanning the visible spectrum. Different excited-
state assignments have been made for these emissions, including
metal-centered (MC), ligand to metal charge transfer (LMCT),
and intraligand (IL), with aggregation through aurophilic inter-
actions thought to play a key role in producing the emissive
state.1,3 Chalcogen ligands are well-known in gold chemistry.
Many of them show interesting luminescent properties, e.g., the
chalcogenolate species [E(AuPPh2py)3M]2+, which have emis-
sions spanning the visible spectra (blue, green, and orange). The
emission energy may be influenced by the chalcogen ligand4 or
the high nuclearity found in some gold(I) sulfide complexes with
diphosphines such as [Au12(μ3-S)4(μ-dppm)6](PF6)4.5 These
Received: June 10, 2011
Published: August 23, 2011
r
2011 American Chemical Society
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ARTICLE
Table 1. Selected Bond Lengths [Å] and Angles [°] for
Complex 3
Au(1)ÀP(1)
Au(1)ÀS(1)
S(1)ÀC(1)
P(1)ÀC(31)
P(1)ÀC(11)
2.2786(11) P(1)ÀC(21)
2.3220(11) N(1)ÀC(15)
1.845(3)
1.355(5)
1.362(5)
1.344(5)
1.351(5)
1.767(3)
1.829(4)
1.831(3)
N(1)ÀC(11)
N(2)ÀC(21)
N(2)ÀC(25)
P(1)ÀAu(1)ÀS(1)
176.90(3)
C(11)ÀP(1)ÀC(21) 101.56(15)
C(15)ÀN(1)ÀC(11) 117.8(3)
C(21)ÀN(2)ÀC(25) 117.3(3)
N(2)ÀC(21)ÀP(1) 112.3(2)
C(1)ÀS(1)ÀAu(1) 109.45(12)
C(31)ÀP(1)ÀC(11) 108.91(16)
C(31)ÀP(1)ÀC(21) 106.19(15)
Figure 1. Structure of complex 3 showing the atom numbering scheme.
Displacement parameter ellipsoids represent 50% probability surfaces.
H atoms are omitted for clarity.
functionalized tertiary phosphines such as 2-pyridil-diphenylpho-
sphine (PPh2py), 2-pyridilethane-diphenylphosphine (PPh2CH2-
CH2py), or bis(2-pyridyl)phenylphosphine (PPhpy2). We have
previously reported reactions of these pentafluorophenyl thio-
late ligands with diphosphines and have shown that they can
bridge two gold(I) or one gold(I) and one gold(III) centers.12 Here
the metalloligands have the nitrogen or nitrogens of the pyridine
units that can be used to coordinate to other metallic centers, and
the sulfur atom of the thiolate ligand can act as a multidentate
coordinating site to afford sophisticated suprastructures with
aurophilic or metallophilic interactions. Thus, reaction with silver
or copper compounds affords heteropolynuclear aggregates,
which are the first examples of simple thiolate ligands bridging
different metals. These complexes exhibit luminescence proper-
ties in the solid state, and the emissive properties of these
compounds have been studied in order to know the influence
of the heterometal (silver or copper) in the emissions. Some of
them are luminescent at both room and low temperature. At
77 K, two bands are observed for most of the complexes. The one
at higher energies has been assigned to IL (monophosphine)
transitions. A 3LMCT (S f Au) origin is proposed for the low
energy band for the metalloligands 1À3. This band is shifted to
lower energies upon coordination of a heterometal. In the
heterometallic complexes, the influence of the heterometal leads
to different energy emissions. The nature of this band has been
proposed as 3LAuMCT (S f AuM).
selection of bond lengths and angles in Table 1. Complex 3
crystallizes as a monomer with no short gold gold interac-
3 3 3
tions. The gold center is linearly coordinated to the thiolate and
the phosphine ligand with the angle PÀAuÀS of 176.90(3)°.
The AuÀS and AuÀP bond distances of 2.3220(11) and
2.2786(11) Å, respectively, are characteristic of this type of
complex as, for example, the pentafluorophenyl thiolate triphe-
nylphosphine gold complex, [Au(SC6F5)(PPh3)].13
In these thiolate gold derivatives, the sulfur atom still has two
electron lone pairs and, consequently, can further coordinate
additional gold fragments. Thus, the reaction of [Au(SC6F5)-
(PPh2py)] with 1 or 2 equiv of [Au(OTf)(PPh2py)] leads to the
dinuclear [Au2(μ-SC6F5)(PPh2py)2]OTf (4) or the trinuclear
[Au3(μ3-SC6F5)(PPh2py)3](OTf)2 (5) species. The 31P{1H}
NMR spectra show a unique resonance for the equivalent
phosphorus atoms at 32.70 and 31.64 ppm, respectively, with a
downfield chemical shift for a further AuPPh2py+ fragment
coordinated to the sulfur atom. This trend has been previously
observed in gold complexes with sulfide bridging ligands.14 The
19F NMR spectra exhibit the three typical resonances for a
pentafluorophenyl ring. The mass spectrum for complex 4 shows
the cation molecular peak [Au2(μ-SC6F5)(PPh2py)2]+ at m/z =
1120 (55%), whereas no peaks of representative fragments are
observed in the mass spectrum of 5.
Complexes [Au(SC6F5)(PÀN)] are very versatile building
blocks in the construction of polynuclear derivatives. They
possess a heterofunctional phosphine ligand that can coordinate
to other metal fragments, and the pentafluorophenyl thiolate
ligand can coordinate more metal centers, as we have observed in
the preparation of the doubly or triply bridging thiolate ligands in
compounds 4 and 5. Therefore the reactions of complexes 1À3
with silver or copper compounds have been studied in different
molar ratios. The reaction of [Au(SC6F5)(PÀN)] with Ag(OTf)
in a 1:1 molar ratio affords complexes with stoichiometry
[AuM(μ-SC6F5)(PÀN)]OTf (PÀN = PPh2py (6), PPh2CH2-
CH2py (7), or PPhpy2 (8)). Complexes 6À8 show only one
resonance in their 31P{1H} NMR spectra, indicating the pre-
sence of either a unique phosphine or equivalent phosphine
’ RESULTS AND DISCUSSION
Synthesis of the Complexes. The reaction of complexes
[AuCl(PÀN)] (PÀN = PPh2py, PPh2CH2CH2py, or PPhpy2)
with pentafluorothiophenol in the presence of potassium carbo-
nate gives the thiolate gold derivatives [Au(SC6F5)(PÀN)]
(PÀN = PPh2py (1), PPh2CH2CH2py (2), or PPhpy2 (3)) in
good yield. The 31P{1H} NMR spectra show one resonance for
1
the phosphorus atom at 36.61, 35.59, and 36.28 ppm. The H
NMR spectra of complexes present the resonances of the
pyridine protons, although some of them are overlapped with
the resonances for the phenyl protons; additionally, complex 2
shows a multiplet for the methylene protons centered at
3.16 ppm. The 19F NMR spectra agree with the presence of a
pentafluorophenyl moiety, and three resonances in a ratio 2:2:1
for the ortho, meta, and para fluorines appear. The liquid
secondary ion mass spectra (LSIMS+) show the molecular peaks
at m/z = 660 (1, 15%), 688 (2, 17%), and 661 (3, 63%).
1
groups. Similarly, the H NMR spectrum presents the typical
resonances arising from the phosphine, and the 19F NMR spectra
show only one type of pentafluorophenyl ring. It is noticeable, in
the case of compound 8 where both pyridine groups are
equivalent, that possibly no coordination of the nitrogen atoms
occurs, both of them are simultaneously bonded to the metal, or
there is a fluxional behavior (Scheme 1). The LSIMS present the
The structure of complex 3 has been established by X-ray
diffraction studies, and the molecule is shown in Figure 1 with a
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ARTICLE
Scheme 1a
a (i) K2CO3, (ii) [Au(OTf)(PPh2py)], (iii) 2 [Au(OTf)(PPh2py)], (iv) Ag(OTf) or [Cu(NCMe)4]PF6, (v) 1/2 Ag(OTf) or [Cu(NCMe)4]PF6, (vi)
4/3 Ag(OTf) or [Cu(NCMe)4]PF6, -M(SC6F5).
can be seen in Figures 2 and 3, respectively. A selection of bond
lengths and angles are collected in Tables 2 and 3. Both
complexes crystallize as dimers with the silver center bonded
to the thiolate, to the nitrogen atoms of the pyridine groups, and
to one of the oxygens of the triflate ligand. These dimeric
structures are probably stabilized by the higher degree of
metallophilic bonding. Complex 6 may be described as a
rhomboidal unit of alternate gold and silver atoms, in which
there are also alternate thiolate and 2-pyridilphosphine ligands
bridging the metallic centers. There are short Au(1) Ag
3 3 3
interactions of 2.9583(5) and 3.1783(5) Å and Au(2)ÀAg
interactions of 3.0545(5) and 3.0481(5) Å. The distance Ag-
(1) Ag(2) is a bit longer, 3.2003(7) Å, but can also be
3 3 3
considered a weak bonding interaction, whereas aurophilic
interactions can be precluded as the Au Au distance is too
3 3 3
long. The gold centers present an almost ideal linear geometry
Figure 2. Structure of complex 6 showing the atom numbering scheme.
with SÀAuÀP angles of 178.14(4) and 175.92(4)°. The silver
Displacement parameter ellipsoids represent 50% probability surfaces.
centers are tricoordinated in an approximately trigonal planar
H atoms are omitted for clarity.
coordination geometry (not taking into account the metallophi-
lic interactions), with the mean deviation for the plane formed by
the four atoms of 0.1 Å, and the deviation of the Ag(1) center out
of the plane formed by their bonding atoms is 0.27 Å. The
structure of complex 8 is slightly different because of the presence
peaks arising at the fragments [AuAg(SC6F5)(PPh2py)]+ at m/z =
767 (30%, 6), [AuAg(SC6F5)(PPh2CH2CH2py)]+ at m/z = 794
(75%, 7), and [AuAg(SC6F5)(PPhpy2)]+ at m/z = 769 (30%, 8).
of two pyridine groups in the phosphine. The four metal centers
form a more asymmetric rhomboidal unit in such a way that one
of the AuÀAg segments has a longer separation. The AuÀAg
distances lie in the range of 3.0961(12)À3.1470(13) Å, with a
With these data, we can propose that the silver center coordinates to
the metalloligand probably through the thiolate and the pyridine or
pyridines of the phosphine ligands, but it is difficult to know if the
metalloligand acts as a chelate or bridging ligand, thus originating
monomeric or dimeric structures, respectively.
very large Au(1) Ag(1) distance of 3.380(1) Å. Now there is
3 3 3
To solve this ambiguity, the crystal structures of complexes 6
and 8 have been determined by X-ray diffraction. The molecules
an aurophilic contact of 3.0534(8) Å, and there is not an
Ag Ag interaction. The silver centers are bonded to the sulfur
3 3 3
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ARTICLE
Table 3. Selected Bond Lengths [Å] and Angles [°] for
Complex 8
Au(1)ÀP(1)
Au(1)ÀS(1)
2.278(3)
2.348(3)
Ag(1)ÀN(3)
Ag(1)ÀO(1)
2.320(9)
2.431(10)
2.451(10)
2.480(3)
2.312(9)
2.405(10)
2.443(9)
2.452(3)
Au(1) Au(2)
3.0534(8) Ag(1)ÀN(4)
3.0961(12) Ag(1)ÀS(1)
2.275(3)
2.336(3)
3 3 3
Au(1) Ag(2)
3 3 3
Au(2)ÀP(2)
Ag(2)ÀN(2)
Ag(2)ÀN(1)
Au(2)ÀS(2)
Au(2) Ag(1)
3.1165(13) Ag(2)ÀO(4)
3.1470(13) Ag(2)ÀS(2)
3 3 3
Au(2) Ag(2)
3 3 3
P(1)ÀAu(1)ÀS(1) 171.68(10)
P(2)ÀAu(2)ÀS(2) 174.30(10)
N(3)ÀAg(1)ÀO(1) 88.0(3)
N(3)ÀAg(1)ÀN(4) 81.9(3)
O(1)ÀAg(1)ÀN(4) 116.7(3)
N(3)ÀAg(1)ÀS(1) 147.3(3)
O(1)ÀAg(1)ÀS(1) 101.5(2)
N(4)ÀAg(1)ÀS(1) 119.5(2)
N(2)ÀAg(2)ÀN(1)
N(2)ÀAg(2)ÀO(4)
N(1)ÀAg(2)ÀO(4)
N(2)ÀAg(2)ÀS(2) 137.6(2)
N(1)ÀAg(2)ÀS(2) 127.7(2)
O(4)ÀAg(2)ÀS(2) 109.2(3)
Au(1)ÀS(1)ÀAg(1) 88.84(10)
Au(2)ÀS(2)ÀAg(2) 82.16(9)
84.6(3)
97.8(3)
86.9(4)
Figure 3. Structure of complex 8 showing the atom numbering scheme.
Displacement parameter ellipsoids represent 50% probability surfaces.
H atoms are omitted for clarity.
Table 2. Selected Bond Lengths [Å] and Angles [°] for
Complex 6a
Scheme 2. Structure of the GoldÀSilver Complexes
Au(1)ÀP(1)
Au(1)ÀS(1)
2.2591(11) Ag(1)ÀN(1)
2.3165(10) Ag(1)ÀO(1)
2.9583(5) Ag(1)ÀS(2)
2.232(4)
2.447(4)
Au(1) Ag(1)
2.4797(11)
3.2003(7)
2.189(4)
3 3 3
Au(1) Ag(2)
3.1782(5) Ag(1) Ag(2)
3 3 3
3 3 3
Au(2)ÀP(2)
2.2583(11) Ag(2)ÀN(2)
2.3223(11) Ag(2)ÀS(1)
3.0481(5) Ag(2)ÀO(4)
3.0545(5)
Au(2)ÀS(2)
2.4078(11)
2.479(4)
Au(2) Ag(1)
3 3 3
Au(2) Ag(2)
3 3 3
31P{1H} NMR spectra show in all the cases one unique
resonance indicating the equivalence of the phosphorus atoms,
and the 19F NMR spectra shows the presence of only one type of
pentafluorophenyl unit. The 1H NMR spectra present, in addi-
tion to the resonances due to the corresponding phosphine
ligand, one singlet assigned to an acetonitrile molecule. The mass
spectra (LSIMS) show the cationic peaks for [AuCu(SC6F5)-
(PPh2py)]+ at m/z = 723 (100%, 9), [AuCu(SC6F5)(PPh2-
CH2CH2py)]+ at m/z = 750 (100%, 10), and [AuAg(SC6F5)-
(PPhpy2)]+ at m/z = 725 (40%, 11). We also propose the
formation of dimers for all these complexes (see Scheme 3), as
has been confirmed by the X-ray diffraction structure of complex
11 (Figure 4, Table 4). Compound 11 consists of a dimeric
structure with a short aurophilic interaction of 3.0028(9) Å. The
gold atoms are found in an almost ideal linear geometry with
angles PÀAuÀS of 177.38(4)° and 177.42(4)°. The copper
atoms are located far from the gold centers, with distances
ranging from 3.461 to 3.708 Å, too long to consider any bonding
interaction. They are bonded to two nitrogen atoms of the
phosphine, to the thiolate sulfur atom, and to one molecule of
acetonitrile, thus rendering a slightly distorted tetrahedral
geometry.
P(1)ÀAu(1)ÀS(1) 178.14(4)
P(2)ÀAu(2)ÀS(2) 175.92(4)
N(1)ÀAg(1)ÀO(1) 87.85(14)
N(1)ÀAg(1)ÀS(2) 154.14(11)
O(1)ÀAg(1)ÀS(2) 112.38(10)
N(2)ÀAg(2)ÀS(1) 166.23(10)
N(2)ÀAg(2)ÀO(4) 89.70(14)
S(1)ÀAg(2)ÀO(4) 100.39(11)
Au(1)ÀS(1)ÀAg(2) 84.54(3)
Au(2)ÀS(2)ÀAg(1) 78.73(3)
a Symmetry transformations used to generate equivalent atoms: #1 Àx +
2, Ày + 2, Àz + 1.
atom of the thiolate, to both pyridine groups, and to one of the
oxygens of the triflate anion. The silver coordination geometry
can be considered as very distorted tetrahedral, not taking into
account the metallophilic interactions. The AgÀN distances
are, for Ag(1), 2.320(9) and 2.451(10) Å, and for Ag(2),
2.312(9) and 2.405(10) Å, which are considerably longer than
those found in complex 6 with a trigonal geometry. The AgÀS
bond lengths are 2.480(3) and 2.452(3) Å, which are more
similar to the longer ones found in complex 6 (2.4797(11) and
2.4078(11) Å).
The structures found for compounds 6 and 8 and the
proposed structure for complex 7 are shown in Scheme 2. As
the phosphine PPh2CH2CH2py has a longer backbone, the
Au Ag distances are probably longer and some Au Au or
Reactions of [Au(SC6F5)(PPh2py)] with other molar ratios of
Ag(OTf) or [Cu(NCMe)4]PF6 have been carried out. When in a
2:1 molar ratio, the reaction affords the trinuclear derivatives
[Au2M(μ-SC6F5)2(μ-PPh2py)2]X (M = Ag, X = OTf (12); M =
Cu, X = PF6 (13)) in high yield. The 31P{1H} NMR spectra show
the presence of equivalent phosphorus atoms, and the 19F and
3 3 3
3 3 3
Ag Ag interactions may be present.
3 3 3
In the same manner, the reaction of [Au(SC6F5)(PÀN)] with
[Cu(NCMe)4]PF6 in a 1:1 molar ratio affords complexes with
stoichiometry [AuCu(μ-SC6F5)(PÀN)(NCMe)]PF6 (PÀN =
PPh2py (9), PPh2CH2CH2py (10), or PPhpy2 (11)). The
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Scheme 3. Structure of the GoldÀCopper Complexes
Table 4. Selected Bond Lengths [Å] and Angles [°] for
Complex 11
Au(1)ÀP(1)
Au(1)ÀS(1)
2.2700(14) Cu(1)ÀN(2)
2.3383(14) Cu(1)ÀS(2)
3.0028(9) Cu(2)ÀN(6)
2.2640(13) Cu(2)ÀN(4)
2.3310(13) Cu(2)ÀN(3)
2.078(4)
2.2726(15)
2.006(5)
2.051(4)
2.078(4)
2.2815(14)
Au(1) Au(2)
3 3 3
Au(2)ÀP(2)
Au(2)ÀS(2)
Cu(1)ÀN(5)
Cu(1)ÀN(1)
2.003(4)
2.039(4)
Cu(2)ÀS(1)
P(1)ÀAu(1)ÀS(1) 177.38(4)
P(2)ÀAu(2)ÀS(2) 177.42(4)
N(5)ÀCu(1)ÀN(1) 107.83(17)
N(5)ÀCu(1)ÀN(2) 105.11(17)
N(1)ÀCu(1)ÀN(2) 95.62(16)
N(5)ÀCu(1)ÀS(2) 108.24(13)
N(1)ÀCu(1)ÀS(2) 119.95(12)
N(2)ÀCu(1)ÀS(2) 118.62(13)
N(6)ÀCu(2)ÀN(4) 106.84(18)
N(6)ÀCu(2)ÀN(3) 110.44(17)
N(4)ÀCu(2)ÀN(3) 95.66(16)
N(6)ÀCu(2)ÀS(1) 105.02(13)
N(4)ÀCu(2)ÀS(1) 122.05(12)
N(3)ÀCu(2)ÀS(1) 116.36(12)
Cu(2)ÀS(1)ÀAu(1) 97.01(6)
Cu(1)ÀS(2)ÀAu(2) 97.91(6)
Figure 4. Structure of the cation of complex 9 showing the atom
numbering scheme. Displacement parameter ellipsoids represent 50%
probability surfaces. H atoms are omitted for clarity.
1H NMR spectra display only one type of pentafluorophenyl ring
or diphenylphosphinopyridine ligand, respectively. It has not
been possible to study these complexes by X-ray diffraction, but
according to the NMR data the proposed structure consists of a
trinuclear derivative, in which the silver or copper atoms are
in a tetrahedral geometry, bonded to a chelate metalloligand
[Au(SC6F5)(PPh2py)] through the pyridine and the sulfur
atoms (see Scheme 1).
Finally, the reaction of [Au(SC6F5)(PPh2py)] with Ag(OTf)
or [Cu(NCMe)4]PF6 in a 4:3 molar ratio has also been carried
out and occurs with the precipation of insoluble M(SC6F5) and
the formation of complexes with stoichiometry [Au4M2
(μ-SC6F5)3(μ-PPh2py)4]X3 (M = Ag, X = OTf (14); M = Cu,
X = PF6 (15)). The 31P{1H} NMR spectrum of 15 shows a
unique resonance, even at low temperature, for the phosphorus
atoms, which indicates the equivalence of the phosphine ligands
or a rapid exchange process in the NMR time scale. More
surprisingly, the 19F NMR spectrum of 15 presents the three
typical resonances (2:2:1 ratio) of equivalent pentafluorophenyl
groups, but the low temperature spectra show a different pattern,
and three different pentafluorophenyl groups, as expected for the
proposed product, were observed. The NMR data for complex
14 show a mixture of products, but the resonances for 14 could
be assigned.
Figure 5. (a) A simplified representation of the molecular structure of
complex 15 (for clarity only the ipso carbon atoms have been repre-
sented for all phenyl rings and for two of the pentafluorophenyl rings).
(b) Schematic representation of the central metal skeleton (all phenyl
rings represented only by their ipso carbon).
collected in Table 5. The structure shows two trinuclear,
structurally different [Au2Cu(SC6F5)(PPh2py)2] units bridged
by a third μ-S-pentafluorophenyl thiolate group, which is bonded
to the two copper atoms. The two trinuclear units consist of
asymmetric Au2Cu triangles with relatively short distances among
The structure of complex 15 has been established by an X-ray
diffraction study, and a simplified representation of the cation is
shown in Figure 5. A selection of bond lengths and angles are
the metals: Au Au in the range of 2.9716(12)À2.9898(11) Å,
3 3 3
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Table 5. Selected Bond Lengths [Å] and Angles [°] for the
represented among chalcogenolate luminescent complexes.15 The
free monophosphines are emissive,10,16 for which we have ob-
served emissions at 314 and 375 at 554 nm (PPh2py) and 443 nm
(PPh2CH2CH2py) at room temperature and 529 (PPh2py),
491 nm (PPh2CH2CH2py), and 499 nm (PPhpy2) at 77 K. These
emissions are very close in energy to those corresponding to the
high energy band displayed at 77 K by complexes 1À3; thus, we
can tentatively propose an intraligand (monophosphine) origin
for this band, modified upon coordination to the gold center. The
gold complexes [AuCl(PÀN)] (PÀN = PPh2py and PPhpy2)
display emissions at 499 nm at 77 K and are not emissive at room
temperature. An IL origin has been assigned to these emissions,17
which show a smaller shift of the emission energy compared with
that found in the free phosphines. The band at lower energies
found in 1 and 2 at 77 K probably arises from 3LMCT (C6F5S f
Au) transitions. The influence of the presence of aurophilic
interactions in the emission energy in thiolate-to-gold charge
transfer transitions has been reported.15a This study concludes
that a red shift of the emission maxima is observed when such
interactions are present. Another conclusion is that the emission
energy, as unique data, is not enough to postulate the presence of
aurophilic interactions.
Cationic Complex of 15
Au(1) Au(2)
2.9898(11) Au(3) Au(4)
2.9716(12)
2.870(2)
2.239(4)
2.148(12)
3.028(2)
2.258(6)
2.329(5)
2.240(5)
2.245(4)
1.988(12)
3 3 3
3 3 3
Au(1) Cu(1)
2.930(2)
2.245(4)
Au(3) Cu(2)
3 3 3
3 3 3
Au(1)ÀP(1)
Au(3)ÀP(3)
Au(1)ÀN(2)
2.110(13) Au(3)ÀN(4)
Au(2) Cu(1)
3.233(2)
2.267(5)
2.317(4)
2.215(5)
2.277(4)
Au(4) Cu(2)
3 3 3
3 3 3
Au(2)ÀP(2)
Au(2)ÀS(1)
Cu(1)ÀS(1)
Cu(1)ÀS(2)
Cu(1)ÀN(1)
Au(4)ÀP(4)
Au(4)ÀS(3)
Cu(2)ÀS(3)
Cu(2)ÀS(2)
1.980(14) Cu(2)ÀN(3)
P(1)ÀAu(1)ÀN(2) 170.4(4)
P(2)ÀAu(2)ÀS(1) 171.93(17)
S(1)ÀCu(1)ÀS(2) 107.63(17)
S(1)ÀCu(1)ÀN(1) 142.3(3)
S(2)ÀCu(1)ÀN(1) 107.7(3)
Au(2)ÀS(1)ÀCu(1) 90.98(15)
Cu(1)ÀS(2)ÀCu(2) 137.3(2)
P(3)ÀAu(3)ÀN(4) 166.3(4)
P(4)ÀAu(4)ÀS(3) 176.23(19)
S(3)ÀCu(2)ÀS(2) 107.50(18)
S(3)ÀCu(2)ÀN(3) 134.2(4)
S(2)ÀCu(2)ÀN(3) 114.6(4)
Au(4)ÀS(3)ÀCu(2) 83.01(17)
The di- and trinuclear gold species [Aux(μ-SC6F5)-
(PPh2py)x](OTf)n (4: x = 2, n = 1; 5: x = 3, n = 2) display
two emissions at low temperature for which we postulate the
origins commented above. A mixed metal centered 5d(dσ*) f
6p(pσ) and 3LMCT S f Au character has been proposed for the
emission at 640 nm observed in [Au2(8-Squin)(PPh3)2]BF4
(Squin = quinoline-8-thiolate).15b A metal-centered contribution
could be also postulated for the low energy emissions found
while the Au Cu exhibits two different separations, one in the
3 3 3
range of 2.870À2.930(2) Å and a second one clearly longer at
3.028À3.233(2) Å. The gold centers are bridged by a k-N,P-
PPh2py ligand, one Au Cu pair is bridged by another k-N,P-
3 3 3
PPh2py ligand, and the second Au Cu side is bridged by a
SC6F5 ligand.
3 3 3
DRUV and Luminescence Studies. The diffuse reflectance
UV (DRUV) spectra of solid samples of complexes 1À15 have
been recorded. All of them display broad bands. In most cases the
band profile shows two maxima, which are not always well-
defined. One of these maxima appears at about 250 nm and the
other at about 350 nm (Table 6). This behavior is illustrated in
Figure 6. In some other cases a third maximum is observed. An
absorption band in dichloromethane solutions at 261 nm in the
UV spectra of PPh2py has been attributed to intraligand π f π
or n f π transitions. The less intense broad shoulders observed
in our complexes include energies that have been assigned to
thiolate IL transitions or 3LMCT transitions in other thiolateÀ
gold complexes.10,15
in 4 and 5, for which the presence of gold gold interactions is
expected.
3 3 3
Heterometallic Complexes. At room temperature almost all
the complexes display emission maxima at λ g 600 nm. At 77 K a
very broad band or two bands are observed (Table 6). Two
emissions have been observed for some compounds upon
changing the excitation energy. Figure 8 illustrates this behavior
for compound 13. When very broad bands are obtained, a unique
maxima and the width of the band are given in Table 6. As two
emissions with different degrees of resolution are generally
present, we will discuss first the one at higher energy and then
the one at lower energy.
For the heterometallic gold/silver and gold/copper com-
plexes, we propose that the emissions at high energy arise from
IL transitions, as discussed above. The band at low energy
appears at lower wavelengths for the copper/gold complexes
compared with the analogous silver/gold complexes of stoichi-
ometry: [Au2M2(μ-SC6F5)2(NCMe)2(μ-PÀN)2] X2 (M = Ag,
X = OTfÀ; M = Cu, X = PF6À). This fact indicates that there is an
influence of the heterometal in the emission energy. As different
emission energies are observed depending on the heterometal
(silver or copper), this fact could serve as a tentative test in order
to know which heterometal has been coordinated.
The excitation and emission spectra of [Au4Ag2(μ-SC6F5)3-
(μ-PPh2py)4](OTf)3 (14) have not been studied, as it is
obtained as a mixture of products. The rest of the complexes
are emissive. They display weak emissions, and some of them are
only luminescent at low temperature. At 77 K two bands are
observed for most of the complexes: an example is shown in
Figure 7. When two maxima are not distinguished, very broad
bands are found. Thus, for the cases in which we have obtained a
lifetime for the two different emissions, they are shown in Table 6.
They lie between 2 and 17 μs, which could point to a phosphor-
escence nature of the emissions. In order to propose an origin for
these emissions, we will first analyze the metalloligands (1À3) as
well as the polygold derivatives (4 and 5), and then we will study
the influence of the heterometal in the polyheterometallic
complexes (6À13 and 15).
The trend may be resumed as follows: in the silver/gold
complexes this band appears at λ > 700 nm, in the red region,
whereas in the copper/gold complexes it is at λ < 650 nm and
results in an orange or pale red emission. We propose a 3LMCT
origin for this band. The crystal structures reveal very different
patterns of metallic interactions; for instance, the structure of
Metalloligands. The emissions observed for complexes
[Au(SC6F5)(PÀN)] (1À3) could be attributed to intraligand
(IL) monophosphine based transitions or ligand (chalcogenolate)
to metal charge transfer (LMCT) transitions. The latter are widely
compound 11 displays aurophilic but not Cu Au interactions.
3 3 3
The silver/gold complexes display more complicated structures,
which involve Ag Ag and Ag Au interactions. Complex 6
3 3 3
3 3 3
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Table 6. Luminescence and DRUV Data for Complexes 1À15
298 Ka
77 Ka
τ (μs)b
DRUV/in nmc
[Au(SC6F5)(PÀN)]
PPh2py (1)
535 (430)
584 (400)
530 (400)
598 (360)
568 (400)
574 (350)
650 (400)
broad band
507 (370)
601 (370)
[230À400] 250, 340
PPh2CH2CH2py (2)
PPhpy2 (3)
12
[210À430] 260; 330
[230À350] 260, 310
[Au2(μ-SC6F5)(PPh2py)2]OTf (4)
broad band
[450À725]
582
17.6, 10
250; 310À450 (br)
370
[Au3(μ3-C6F5)(PPh2py)3](OTf)2 (5)
broad band
[430À650]
501
broad band
465 (320)
588 (379)
240; 310À410 (br)
370
[Ag2Au2(μ-SC6F5)2(OTf)2(μ-PÀN)2]
PPh2py (6)
531 (360)
740 (422)
707 (420)
broad band
584 (350)
658 (400)
[225À430] 250; 330, 400
PPh2CH2CH2py (7)
PPhpy2 (8)
745 (450)
600 (430)
8.5
[210À380] 260; 300
[230À420] 260; 330
[Au2Cu2(μ-SC6F5)2(NCMe)2(μ-PÀN)2](PF6)2
PPh2py (9)
broad band
[450À725]
573
16.6, 7.1
[210À450] 260; 340
PPh2CH2CH2py (10)
PPhpy2 (11)
557 (370)
629 (450)
broad band
557 (370)
635 (450)
broad band
[430À750]
569
[210À400]
[230À530] 260, 340, 410
[AgAu2(μ-SC6F5)2(μ-PPh2py)2]OTf (12)
[210À410] 275; 325
(370À440)
broad band
567 (370)
632 (440)
broad band
583 (400)
658 (425)
[Au2Cu(μ-SC6F5)2(μ-PPh2py)2]PF6 (13)
[Au4Cu2(μ-SC6F5)3(μ-PPh2py)4](PF6)3 (15)
600 (430)
620 (420)
10.9 2.8
12.8, 2.0
[210À450] 260; 335
[210À450] 260; 335
a λMAXIMUM of emission (λMAXIMUM of excitation) in nm. When two maxima are observed the most intense one is shown in bold. When only a very
broad band is observed: [range], maximum of emission and (range of excitation) are shown. b At room temperature. c [Range of the broad band] maxima
observed (that with higher intensity is in bold).
displays Ag Ag interactions, and complex 8 displays Au Au
’ CONCLUSIONS
3 3 3
3 3 3
contacts. Thus, the participation of the heterometal in a concrete
sort of metallic interaction seems not to be the cause of the
different emission maxima. Nevertheless, the influence of the
heterometal is clear, and thus probably the origin of this band is a
chalcogenolate to gold/heterometal charge transfer transition
The metalloligand complexes [Au(SC6F5)(PÀN)] (PÀN =
PPh2py, PPh2CH2CH2py, or PPhpy2) have been prepared and
used as building blocks to construct unprecedented heterome-
tallic aggregates by reaction with silver(I) or copper(I) com-
pounds. In the reactions with a 1:1 molar ratio, these aggregates
are dimers that present an Au2Ag2 or Au2Cu2 core, which allows
the presence of different metallophilic interactions. Other molar
ratios have been used, such as 2:1 or 3:4, giving complexes with
chelate or triply bridging metalloligands as [Au2M(μ-SC6F5)2-
(μ-PÀN)2]X or [Au4M2(μ-SC6F5)3(μ-PÀN)4]X3, respectively.
3
that could be represented as LAuMCT (RS f Au/M). The
presence of silver leads, in general, to emissions at lower energies
than the coordination of copper. As discussed above, in some
occasions one broad emission is observed, which possibly has a
mixture IL and 3LAuMCT (RS f Au/M) character.
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ARTICLE
microsecond range point to a phosphorescent nature of the
luminescence. At 77 K, a very broad band or two bands are
observed for most of the complexes. The one at high energy
probably arises from IL (monophosphine) transitions. A 3LMCT
(S f Au) origin is proposed for the low energy band for the
metalloligands 1À3. In the heterometallic complexes, the influ-
ence of the heterometal leads to different energy emissions. In
general, silver/copper complexes exhibit this band at lower
energies than the homologous copper complexes. This interest-
ing fact may tentatively be used to identify the heterometal in
such species. The nature of this band has been proposed as
3LAuMCT (S f AuM). Although further studies focused on
these systems are required, this work could be the starting point
for preparing intense luminescent heteropolynuclear complexes.
The luminescence of such complexes would depend on the
heterometal, and thus the complexes would serve as a probe or
sensor for the heterometal.
Figure 6. DRUV spectrum of compound 6.
’ EXPERIMENTAL SECTION
Instrumentation. Infrared spectra were recorded in the range of
4000À200 cmÀ1 on a PerkinÀElmer 883 spectrophotometer using
Nujol mulls between polyethylene sheets. C, H, N, and S analyses were
carried out with a PerkinÀElmer 2400 microanalyzer. Mass spectra were
recorded on a VG Autospec, with the LSIMS technique, using nitro-
benzyl alcohol as matrix. NMR spectra were recorded on a Bruker ARX
300 or a Bruker AV 400 spectrometer. Chemical shifts are cited relative
to SiMe4 (1H, external) and 85% H3PO4 (31P, external). DRUV spectra
were recorded with a UnicamUV-4 spectrophotometer equipped with a
Spectralon RSA-UC-40 Labsphere integrating sphere. The solid samples
were mixed with dried KBr and placed in a homemade cell equipped with
a quartz window. The intensities were recorded in KubelkaÀMunk
units: (1 À R)2/2R, where R = reflective index. Steady-state photo-
luminescence spectra were recorded with a JobinÀYvon Horiba Fluo-
rolog FL-3-11 spectrometer using band pathways of 3 nm both for
excitation and emission. Phosphorescence lifetimes were recorded with
a Fluoromax phosphorimeter accessory containing a UV xenon flash
tube. The lifetime data were fit using the JobinÀYvon software
package18 and the Origin 5.0 program.19
Figure 7. Two emission maxima observed in 1.
Starting Materials. The starting materials PPh2CH2CH2py,20
PPhpy2,21 [AuCl(PPh2py)],22 [AuCl(PPh2CH2CH2py)],17 and
[Cu(NCMe)4]PF623 were prepared according to published procedures.
All other reagents were commercially available. [Au(OTf)(PPh2py)]
was prepared from the reaction of [AuCl(PPh2py)] with Ag(OTf) in
dichloromethane and used in situ.
Synthesis of [Au(SC6F5)(PÀN)] (PÀN = PPh2py (1), PPh2CH2CH2py
(2), or PPhpy2 (3)). To a solution of [AuCl(PPh2py)] (0.495 g, 1 mmol),
[AuCl(PPh2CH2CH2py)] (0.523 g, 1 mmol), or [AuCl(PPhpy2)]
(0.497 g, 1 mmol) in 15 mL of dichloromethane under nitrogen
atmosphere were added HSC6F5 (0.14 mL, 1 mmol) and K2CO3 in
excess. The mixture was stirred at room temperature for 2 h. After this
time it was filtered through Celite to remove the precipitate. The
resulting solution was concentrated to 5 mL and Et2O was added, giving
a white solid of 1 (0.262 g, 80%), a white solid of 2 (0.165 g, 49%), or an
orange solid of 3 (0.251 g, 76%). Complex 1: Anal. Calcd. for
C23H19AuF5NPS (MW = 659.36): C, 41.89; H, 2.14; N, 2.12; S, 4.86.
Found: C, 41.56; H, 1.83; N, 2.52; S, 4.46. MS(LSIMS+): m/z = 660
(15%, [Au(SC6F5)(PPh2py)]). 31P{1H} NMR (CDCl3, ppm): 36.6
(s, 2P, PPh2py). 1H NMR (CDCl3, ppm): 8.80 (d, 1H, py, 3JHÀH = 4.6
Hz), 7.91 (t, 1H, py, 3JHÀH = 7.6 Hz), 7.82À7.45 (m, 10 + 1H, Ph + py),
7.39 (m, 1H, py). 19F NMR (CDCl3, ppm): À132.33 (m, 2F, o-F),
À162.48 (t, 1F, p-F, 2JFÀF = 21 Hz), À164.13 (m, 2F, m-F). Complex 2:
Anal. Calcd. for C25H18AuF5NPS (MW = 687.41): C, 43.68; H, 2.64; N,
Figure 8. Emission observed in 13. A broad band (straight line) may
be split into two emissions upon changing the excitation maximum
(λ = 350 nm, dotted line; 450 nm, dashed line).
The complexes display weak emissions, and some of them are
only luminescent at low temperature. At 77 K, two bands are
observed for most of the complexes. The lifetime values in the
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2.03; S, 4.66. Found: C, 43.38; H, 2.77; N, 2.16; S, 4.76. MS(LSIMS+):
m/z = 688 (17%, [Au(SC6F5)(PPh2CH2CH2py)]). 31P{1H} NMR
((CD3)2CO, ppm): 35.6 (s, 2P, PPh2CH2CH2py). 1H NMR
((CD3)2CO, ppm): 8.45 (d, 1H, py, 3JHÀH = 4.8 Hz), 7.89À7.52 (m,
10 + 1H, Ph + py), 7.26 (d, 1H, py, 3JHÀH = 7.8 Hz), 7.16 (m, 1H, py),
3.26À3.06 (m, 4H, CH2). 19F NMR ((CD3)2CO, ppm): À132.91 (m,
2F, o-F), À164.53 (t, 1F, p-F, 2JFÀF = 20.6 Hz), À165.30 (m, 2F, m-F).
Complex 3: Anal. Calcd. for C22H13AuF5N2PS (MW = 660.35); C,
40.01; H, 1.98; N, 4.24; S, 4.84. Found: C, 40.40; H, 2.23; N, 4.32; S,
5.05. MS(LSIMS+): m/z = 661 (65%, [Au(SC6F5)(PPhpy2)]). 31P-
[AgAu(SC6F5)(PPhpy2)]+). 31P{1H} NMR (CDCl3, ppm): 30.8 (s, 2P,
PPhpy2). 1H NMR (CDCl3, ppm): 8.82 (m, 4H, py), 8.20 (m, 4H, py),
7.81À7.62 (m, 10 + 4H, Ph + py), 7.30 (m, 4H, py). 19F NMR (CDCl3,
ppm): À78.58 (s, 6F, CF3SO3), À131.43 (m, 4F, o-F), À158.02 (m, 2F,
p-F), À162.88 (m, 4F, m-F).
Synthesis of [Au2Cu2(μ-SC6F5)2(NCMe)2(μ-PÀN)2](PF6)2 (PÀN =
PPh2py (9), PPh2CH2CH2py (10), or PPhpy2 (11)). To a solution of
[Au(SC6F5)(PPh2py)] (0.066 g, 0.1 mmol), [Au(SC6F5)(PPh2CH2-
CH2py)] (0.068 g, 0.1 mmol), or [Au(SC6F5)(PPhpy2)] (0.066 g,
0.1 mmol) in 15 mL of dichloromethane, distilled and under nitrogen
atmosphere, was added [Cu(NCMe)4]PF6 (0.037 g, 0.1 mmol), and the
mixture was stirred for 30 min. The solution was evaporated to 5 mL, and
Et2O was added, giving a yellow solid of 9 (0.077 g, 88%), hexane was
added, giving a white solid of 10 (0.067 g, 65%), and Et2O was added,
giving a yellow solid of 11 (0.062 g, 72%). Complex 9: Anal. Calcd. for
C50H40Au2Cu2F22N4P4S2 (MW = 1795.80): C, 33.40; H, 2.25; N, 1.56;
S, 3.57. Found: C, 33.05; H, 1.98; N, 1.91; S, 3.72. MS(LSIMS+): m/z =
804 (15%, [AuCu(SC6F5)(PPh2py)(NCMe)2]+), m/z = 723 (100%,
1
{1H} NMR (CDCl3, ppm): 36.3 (s, P, PPhpy2). H NMR (CDCl3,
ppm): 8.75 (d, 2H, py, 3JHÀH = 4.6 Hz), 7.97 (m, 2H, py), 7.86À7.48
(m, 5 + 2H, Ph + py), 7.37 (m, 2H, py). 19F NMR (CDCl3, ppm):
À132.25 (m, 2F, o-F), À162.45 (t, 1F, p-F, 2JFÀF = 19.7 Hz), À164.13
(m, 2F, m-F).
Synthesis of [Au2(μ-SC6F5)(PPh2py)2](OTf) (4). To a solution of
[Au(OTf)(PPh2py)] (0.073 g, 0.12 mmol) in 20 mL of dichloro-
methane was added [Au(SC6F5)(PPh2py)] (0.066 g, 0.1 mmol), and
the mixture was stirred for 1 h. The solution was concentrated to 5 mL,
and the addition of Et2O gave a white solid of 4 (0.112 g, 88%). Anal.
Calcd. for C41H28Au2F8N2P2O3S2 (MW = 1268.66): C, 38.80; H,
2.20; N, 2.20; S, 5.04. Found: C, 38.72; H, 2.03; N, 2.24; S, 4.99.
MS(LSIMS+): m/z = 1120 (55%, [Au2(SC6F5)(PPh2py)2]+). 31P{1H}
NMR (CDCl3, ppm): 32.7 (s, 2P, PPh2py). 1H NMR (CDCl3, ppm):
8.89 (m, 2H, py), 7.88 (m, 2H, py), 7.56À7.44 (m, 20 + 4H, Ph + py).
19F NMR (CDCl3, ppm): À80.07 (s, 3F, CF3SO3), À133.64 (m, 2F,
o-F), À162.38 (m, 1F, p-F), À165.27 (m, 2F, m-F).
1
[AuCu(SC6F5)(PPh2py)]+). 31P{1H} NMR (CDCl3, ppm): 38.8. H
NMR (CDCl3, ppm): 8.43 (m, 2H, py), 8.01 (m, 2H, py), 7.56À7.34
(m, 20 + 4H, Ph + py), 1.97 (m, 6H, CH3). 19F NMR (CDCl3, ppm):
À74.77 (d, 12F, PF6, 1JFÀP = 717 Hz), À130.48 (m, 4F, o-F), À156.04
(m, 2F, p-F), À160.20 (m, 4F, m-F). Complex 10: Anal. Calcd. for
C54H48Au2Cu2F22N4P4S2 (MW = 1880.00): C, 34.50; H, 2.57; N, 2.98;
S, 3.41. Found: C, 34.54; H, 2.16; N, 2.58; S, 3.68. MS(LSIMS+): m/z =
750 (100%, [AuCu(SC6F5)(PPh2CH2CH2py)]+). 31P{1H} NMR
((CD3)2CO, ppm): 35.3. 1H NMR (CDCl3, ppm): 8.26 (m, 2H, py),
7.76À7.20 (m, 20 + 6H, Ph + py), 3.36 (m, 4H, CH2), 3.00 (m, 4H,
CH2), 2.01 (m, 6H, CH3). 19F NMR ((CD3)2CO, ppm): À134.32 (m,
4F, o-F), À161.69 (m, 2F, p-F), À165.00 (m, 4F, m-F). Complex 11:
Anal. Calcd. for C48H32Au2Cu2F22N6P4S2 (MW = 1737.72): C, 31.67;
H, 1.77; N, 4.61; S, 3.52. Found: C, 31.35; H, 1.99; N, 4.06; S, 3.90.
MS(LSIMS+): m/z = 725 (40%, [AuCu(SC6F5)(PPhpy2)]+). 31P{1H}
NMR (CDCl3, ppm): 23.6. 1H NMR (CDCl3, ppm): 8.65 (m, 4H, py),
8.37 (m, 4H, py), 8.07À7.48 (m, 10 + 8H, Ph + py), 2.01 (m, 6H, CH3).
Synthesis of [Au3(μ3-SC6F5)(PPh2py)3](OTf)2 (5). To a solution of
[Au(OTf)(PPh2py)] (0.133 g, 0.22 mmol) in 30 mL of dichloro-
methane was added [Au(SC6F5)(PPh2py)] (0.066 g, 0.1 mmol), and
the mixture was stirred for 1 h. The solution was evaporated to 5 mL, and
Et2O was added, giving a white solid of 5 (0.137 g, 73%). Anal. Calcd. for
C59H42Au3F11N3P3S3O6 (MW = 1877.98): C, 37.71; H, 2.38; N, 2.24;
S, 5.25. Found: C, 37.91; H, 2.49; N, 2.32; S, 5.20. 31P{1H} NMR
(CDCl3, ppm): 31.6 (s, 3P, PPh2py). 1H NMR (CDCl3, ppm): 8.91 (m,
3H, py), 7.90 (m, 3H, py), 7.55À7.47 (m, 30 + 6H, Ph + py). 19F NMR
(CDCl3, ppm): À80.11 (s, 3F, CF3SO3), À133.27 (m, 2F, o-F),
À161.00 (m, 1F, p-F), À164.72 (m, 2F, m-F).
1
19F NMR (CDCl3, ppm): À74.28 (d, 12F, PF6, JFÀP = 715 Hz),
À132.78 (m, 4F, o-F), À158.93 (m, 2F, p-F), À162.81 (m, 4F, m-F).
Synthesis of [AgAu2(μ-SC6F5)2(μ-PPh2py)2]OTf (12). To a solution
of [Au(SC6F5)(PPh2py)] (0.153 g, 0.2 mmol) in 15 mL of dichlor-
omethane was added Ag(OTf) (0.025 g, 0.1 mmol). After 20 min of
stirring, the solution was evaporated to 5 mL and Et2O was added, giving
a white solid of 12 (0.119 g, 76%). Anal. Calcd. for C47H28AgAu2F13N2-
P2O3S3 (MW = 1575.67): C, 35.82; H, 1.79; N, 1.77; S, 6.10. Found:
C, 35.63; H, 1.54; N, 1.50; S, 6.33. 31P{1H} NMR (CDCl3, ppm): 37.9
(s, 2P, PPh2py). 1H NMR (CDCl3, ppm): 8.83 (d, 2H, py, 3JHÀH = 4.58
Hz), 7.93 (t, 2H, py, 3JHÀH = 7.59 Hz), 7.58À7.49 (m, 20 + 4H, Ph +
py). 19F NMR (CDCl3, ppm): À80.05 (s, 3F, CF3SO3), À131.36 (m,
4F, o-F), À158.82 (m, 2F, p-F), À162.41 (m, 4F, m-F).
Synthesis of [Ag2Au2(μ-SC6F5)2(OTf)2(μ-PÀN)2] (PÀN = PPh2py
(6), PPh2CH2CH2py (7), or PPhpy2 (8)). To a solution of [Au(SC6F5)-
(PPh2py)] (0.066 g, 0.1 mmol), [Au(SC6F5)(PPh2CH2CH2py)]
(0.068 g, 0.1 mmol), or [Au(SC6F5)(PPhpy2)] (0.066 g, 0.1 mmol)
in 15 mL of dichloromethane was added Ag(OTf) (0.025 g, 0.1 mmol).
After 20 min of stirring, the mixture was filtered through Celite and the
solution was evaporated to 5 mL. Addition of Et2O gave a white solid of
6 (0.076 g, 75%). Addition of hexane afforded a white solid of 7 (0.052 g,
62%) or a yellow solid of 8 (0.066 g, 70%). Complex 6: Anal. Calcd. for
C48H28Ag2Au2F16N2P2O6S4 (MW = 1832.6): C, 31.45; H, 1.54; N,
1.52; S, 6.99. Found: C, 31.22; H, 1.20; N, 1.50; S, 6.73. MS(LSIMS+):
m/z = 767 (25%, [AgAu(SC6F5)(PPh2py)]+). 31P{1H} NMR (CDCl3,
ppm): 39.0 (s, 2P, PPh2py). 1H NMR (CDCl3, ppm): 8.99 (m, 2H, py),
8.76 (m, 2H, py), 7.84À7.04 (m, 20 + 4H, Ph + py). 19F NMR (CDCl3,
ppm): À80.05 (s, 6F, CF3SO3), À132.84 (m, 4F, o-F), À159.46 (m, 2F,
p-F), À164.60 (m, 4F, m-F). Complex 7: Anal. Calcd. for C54H36Au2-
Ag2F16N2P2O6S4 (MW = 1888.7): C, 33.06; H, 1.92; N, 1.48; S, 6.79.
Found: C, 33.27; H, 2.23; N, 1.65; S, 6.98. (LSIMS+): m/z = 794 (75%,
[AgAu(SC6F5)(PPh2CH2CH2py)]+). 31P{1H} NMR ((CD3)2CO,
Synthesis of [Au2Cu(μ-SC6F5)2(μ-PPh2py)2]PF6 (13). To a solution of
[Au(SC6F5)(PPh2py)] (0.153 g, 0.2 mmol) in 15 mL of dichloro-
methane under nitrogen atmosphere was added [Cu(NCMe)4]PF6
(0.037 g, 0.1 mmol), and the mixture was stirred for 20 min. After this
time, the solution was evaporated to 5 mL and Et2O was added, giving a
yellow solid of 13 (0.107 g, 70%). Anal. Calcd. for C46H28Au2-
CuF16N2P3S2 (MW = 1526.5): C, 36.16; H, 1.83; N, 1.83; S, 4.19.
Found: C, 35.95; H, 1.91; N, 1.71; S, 4.34. MS(LSIMS+): m/z = 1381
(12%, [Au2Cu(SC6F5)2(PPh2py)2]+).31P{1H} NMR((CD3)2CO, ppm):
37.8 (s, 2P, PPh2py). 1H NMR ((CD3)2CO, ppm) 8.67 (m, 2H, py), 8.21
(m, 2H, py), 7.80 (m, 2H, py), 7.74À7.65 (m, 20 + 4H, Ph + py). 19F NMR
((CD3)2CO, ppm): À73.87 (d, 6F, PF6, 1JPÀF = 707 Hz), À134.72 (m, 4F,
o-F), À164.38 (m, 2F, p-F), À166.17 (m, 4F, m-F).
1
ppm): 36.2 (s, 2P, PPh2CH2CH2py). H NMR ((CD3)2CO, ppm):
8.41 (m, 2H, py), 7.78À7.41 (m, 20 + 4H, Ph + py), 7.24 (m, 2H, py),
3.26 (m, 8H, CH2). 19F NMR ((CD3)2CO, ppm): À80.06 (s, 6F,
CF3SO3), À134.32 (m, 4F, o-F), À164.01 (m, 2F, p-F), À166.17 (m,
4F, m-F). Complex 8: Anal. Calcd. for C46H26Au2Ag2F16N4P2-
O6S4 (MW = 1834.56): C, 30.09; H, 1.41; N, 3.05; S, 6.97. Found:
C, 29.88; H, 1.30; N, 2.98; S, 6.50. MS(LSIMS+): m/z = 769 (30%,
Synthesis of [Ag2Au4(μ-SC6F5)3(μ-PPh2py)4](OTf)3 (14). To a solu-
tion of [Au(SC6F5)(PPh2py)] (0.263 g, 0.4 mmol) in 15 mL of dichloro-
methane was added Ag(OTf) (0.077 g, 0.3 mmol), and the mixture was
9541
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Inorganic Chemistry
ARTICLE
Table 7. X-ray Data for Complexes 3, 6, 8, 11, and 15
compound
3
6 1/2 C6H14
8 2.5OEt2
3
3
formula
C22H13AuF5N2PS
660.34
C51H35Ag2Au2F16N2O6P2S4
1875.66
C56H51Ag2Au2F16N4O8.5P2S4
Mr
2019.86
habit
colorless prism
0.20 Â 0.20 Â 0.20
triclinic
pale yellow prism
0.42 Â 0.42 Â 0.34
triclinic
yellow needle
0.35 Â 0.16 Â 0.08
triclinic
crystal size (mm)
crystal system
space group
cell constants:
a (Å)
P1
P1
P1
8.1905(16)
12.172(2)
15.592(3)
62.68(3)
75.69(3)
82.13(3)
1080.3(4)
2
12.1510(19)
14.676(2)
17.507(3)
97.095(2)
107.186(3)
101.797(3)
2862.5(8)
2
12.373(3)
12.731(3)
21.418(4)
92.97(3)
95.28(3)
95.32(3)
3339.0(12)
2
b (Å)
c (Å)
R (°)
β (°)
γ (°)
V (Å3)
Z
Dx (Mg mÀ3
)
2.030
2.176
2.009
μ (mmÀ1
F(000)
T (°C)
2θmax
)
7.035
6.088
5.231
628
1786
1946
À173
50
À173
52
À173
50
no. of refl:
measured
6657
3728
0.33À0.33
0.010
337
16709
10983
0.184À0.231
0.019
752
21757
11474
0.262À0.680
0.036
862
independent
transmissions
Rint
parameters
restraints
wR(F2, all refl)
R(I > 2σ(I))
S
0
0
158
0.050
0.020
1.098
2.05
0.070
0.027
1.007
1.61
0.142
0.059
1.104
4.08
max ΔF (e ÅÀ3
)
compound
11
15 H2O 0.25CH2Cl2
3
3
formula
Mr
C54H43Au2Cu2F22N9P4S2
1944.99
C86H56Au4Cu2F33N4P7S3 H2O 0.25CH2Cl2
3
3
3039.51
habit
yellow prism
0.20 Â 0.17 Â 0.12
triclinic
yellow tiny block
0.04 Â 0.02 Â 0.01
monoclinic
P21/c
crystal size (mm)
crystal system
space group
cell constants:
a (Å)
P1
11.214(2)
15.520(3)
18.755(4)
95.95(3)
92.64(3)
106.43(3)
3104.1(11)
2
20.373(5)
14.817(4)
32.056(8)
90.0
b (Å)
c (Å)
R (°)
β (°)
γ (°)
97.785(5)
90.0
V (Å3)
9588(4)
4
Z
Dx (Mg mÀ3
)
2.081
2.106
μ (mmÀ1
F(000)
T (°C)
2θmax
)
5.671
6.288
1872
5778
À173
50
À123
54
9542
dx.doi.org/10.1021/ic201245q |Inorg. Chem. 2011, 50, 9533–9544

Inorganic Chemistry
ARTICLE
Table 7. Continued
compound
11
15 H2O 0.25CH2Cl2
3
3
no. of refl:
measured
independent
transmissions
Rint
19972
10868
60656
22765
0.787À0.940
0.085
1081
0.396À0.549
0.015
858
parameters
restraints
wR(F2, all refl)
R(I > 2σ(I))
S
0
126
0.069
0.030
1.074
1.80
0.211
0.092
1.106
2.68
max ΔF (e ÅÀ3
)
stirred for 20 min. The AgCl that formed was filtered through Celite, and
the solution was evaporated to 5 mL. Et2O was added giving a white solid
of 14 (0.259 g, 76%). 31P{1H} NMR (CDCl3, ppm): 38.9 (s, 4P,
PPh2py). 1H NMR (CDCl3, ppm): 8.89 (d, 4H, py, 3JHÀH = 4.7 Hz),
7.95 (m, 4H, py), 7.60À7.54 (m, 40 + 4H, Ph + py), 7.37 (m, 4H, py).
19F NMR (CDCl3, ppm): À80.05 (s, 3F, CF3SO3), À135 (m, 6F, o-F),
À157.94 (m, 3F, p-F), À162.25 (m, 6F, m-F).
’ ASSOCIATED CONTENT
S
Supporting Information. Five X-ray crystallographic files,
b
in CIF format, for compounds 3, 6, 8, 11, and 15. This material is
available free of charge via the Internet at http://pubs.acs.org.
’ AUTHOR INFORMATION
Synthesis of [Au4Cu2(μ-SC6F5)3(μ-PPh2py)4](PF6)3 (15). To a solution
of [Au(SC6F5)(PPh2py)] (0.263 g, 0.4 mmol) in 15 mL of dichloro-
methane under nitrogen atmosphere was added [Cu(NCMe)4]-
PF6 (0.111 g, 0.3 mmol). After stirring for 30 min, the mixture was
filtered through Celite. The solution was concentrated to 5 mL, and
addition of Et2O gave a yellow solid of 15 (0.280 g, 86%). Anal. Calcd.
for C86H56Au4Cu2F33N4P7S3 (MW = 3000.31): C, 34.42; H, 1.88; N,
1.86; S, 3.20. Found: C, 34.61; H, 1.81; N, 1.69; S, 3.44. 31P{1H} NMR
((CD3)2CO, ppm): 37.6 (s, 4P, PPh2py). 1H NMR ((CD3)2CO, ppm):
8.71 (m, 4H, py), 8.22 (m, 4H, py), 7.83 (m, 4H, py), 7.74À7.75 (m,
Corresponding Author
*E-mail: gimeno@unizar.es.
’ ACKNOWLEDGMENT
Authors thank CCLRC Daresbury Laboratory for allocation of
synchrotron beam time (AP42) and the Ministerio de Ciencia e
Innovaciꢀon (CTQ2010-20500-C02-01) and (MICINN/FEDER,
CSD2006-0015) for financial support.
40 + 4H, Ph + py). 19F NMR (CDCl3, ppm): 73.00 (d, 18F, PF6, 1JFÀP
=
714 Hz), À130.50 (m, 1F, o-F), À131.66 (m, 3F, o-F), À132.41 (m, 1F, o-
F), À132.91 (m, 1F, o-F), À162.62 (m, 2F, p-F), À156.21 (m, 1F,
p-F), À160.20 (m, 1F, m-F), À160.85 (m, 1F, m-F), À161.38 (m, 1F,
m-F), À161.86 (m, 3F, m-F).
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Inorganic Chemistry
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’ NOTE ADDED AFTER ASAP PUBLICATION
An earlier version of this paper published on the web on
August 23, 2011 contained errors in the chemical formulas for
9544
dx.doi.org/10.1021/ic201245q |Inorg. Chem. 2011, 50, 9533–9544