Polarized Supramolecular Aggregates Based on Luminescent Perhalogenated Gold Derivatives

Article abstract of DOI:10.1021/acs.inorgchem.7b01901

The reaction of [Au(C₆F₅)(tht)] (tht = tetrahydrothiophene) with 1,3,5-triaza-7-phosphaadamantane (PTA) and 3,7-diacetyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane (DAPTA) leads to the formation of [Au(C₆F₅)(pho

Full text of DOI:10.1021/acs.inorgchem.7b01901

Article
pubs.acs.org/IC
Polarized Supramolecular Aggregates Based on Luminescent
Perhalogenated Gold Derivatives
Raquel Gavara,† Andrea Pinto,† Rocío Donamaría,‡ M. Elena Olmos,*,‡ Jose M Lopez de Luzuriaga,†,‡
́
́
and Laura Rodríguez*,†,§
†Departament de Química Inorgan
E-08028 Barcelona, Spain
̀
ica i Organ
̀
ica, Seccio
́
de Química Inorgan
̀
ica, Universitat de Barcelona, Martí i Franques
̀
1−11,
‡Centro de Investigacion
26004 Logrono, Spain
́
en Síntesis Química, Departamento de Química, Complejo Científico Tecnologico, Universidad de la Rioja,
́
̃
̀
§Institut de Nanociencia i Nanotecnologia (IN2UB), Universitat de Barcelona, 08028 Barcelona, Spain
S
* Supporting Information
ABSTRACT: The reaction of [Au(C6F5)(tht)] (tht =
tetrahydrothiophene) with 1,3,5-triaza-7-phosphaadamantane
(PTA) and 3,7-diacetyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]-
nonane (DAPTA) leads to the formation of [Au(C6F5)-
(phosph)] (phosph = PTA, 1; phosph = DAPTA, 2). The
compounds are slightly soluble in water and aggregate at higher
concentrations, giving rise to the formation of needle- and
rodlike structures (1) and well-organized spherical aggregates
(2). Compounds 1 and 2 were reacted with AgPF6, giving rise
to the formation in all cases of luminescent water-soluble 1:1
Au···Ag heterometallic complexes, as evidenced by X-ray crystal
structure determination. The use of different silver salts that
differ on the counterion induces changes in the resulting
luminescence and aggregation morphology.
and optical sensors.9 In the case of gold(I) complexes, because
of the similarity in the energy and directionality between
aurophilic interactions and hydrogen bonds, aurophilicity plays
a key role in the aggregation process in both the solid state and
solution.10 These interactions are observed to be responsible
for the formation of very large structures such as gels, fibers,
and vesicles with intrinsic luminescent properties because of the
presence of a gold atom.11,12
In general, the resulting supramolecular aggregates based on
low-molecular-weight molecules contain, at least, one ligand
with a typical moiety known to induce intermolecular
assemblies.13 Nevertheless, it was recently described by some
of us as the formation of long and well-organized gold(I)
supramolecular structures based on “chemically simple”
molecules containing gold(I) alkynyl units.11,13−15 The
intermolecular assemblies are based on aurophilic contacts,
together with hydrogen bonds and π−π stacking.16 Aurophilic-
induced aggregates are also found for RAu-C6F5 derivatives of
[(C6 F5 Au)(μ-1-(decyloxy)-4-isocyanophenyl)],1 7
[(C6F5Au)2(μ-1,4-diisocyanobenzene)],18 and [(C6F5Au)-
(CNC6H4O(O)CC6H4OC10H21].19 However, to the best of
our knowledge, there is no precedent in the literature about
INTRODUCTION
■
One of the main motivating factors that has provoked the rapid
development of gold chemistry in the last years has been the
characteristic luminescence that many of the gold derivatives
show.1 Relativistic effects have shown to be of enormous
importance in understanding the chemical and physical
properties of the heaviest 6s transition and post-transition
metallic elements, mainly gold.1,2 Probably, the most important
structural consequence of the relativistic effects in gold is the
high tendency to form closed-shell interactions between gold(I)
centers (called aurophilic interactions), which are commonly
responsible for the interesting optical properties.3−6 These
interactions are energetically similar to hydrogen bonds (5−10
kcal mol−1). The formation of noncovalent bonding between
metals (metallophilic interactions) can also be observed with
other metals like silver7 and in heterometallic complexes like
the formation of Au···Ag interactions with strength similar to
that of aurophilic contacts.8
Noncovalent interactions, widely employed in supramolecu-
lar chemistry, are increasingly under investigation as a design
tool to organize different types of molecules into unique
architectures with precisely controlled structures and functions.
The resulting structures have recently attracted significant
research interest because they can be used in diverse
applications, e.g., in logic gates, molecular machines, switches,
Received: July 27, 2017
© XXXX American Chemical Society
A
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low-molecular-weight gold(I) supramolecular aggregates in
water based on Au-C6F5 discrete molecules without any
common ligand expected to induce aggregation.20
the CH2 vibrations of the phosphanes and the CO strong
band in the case of 2.
Their 19F NMR spectra in deuterated acetone display three
nonequivalent fluorine atoms at −116.7 (ortho), −160.8
(para), −164.1 (meta) ppm and very similar signals for 2
(see the Supporting Information, SI), in accordance with the
chemical shift of AuI-C6F5 complexes. Their 31P NMR spectra
show only one signal at ca. −46.8 and −18.3 ppm for 1 and 2,
respectively, shifted from those of the free ligands, confirming
Water is the ideal solvent for synthetic processes from an
economical and ecological industrial point of view. However,
the use of water as the solvent requires the synthesis of reagents
stable and soluble in this medium. One of the most common
strategies for solubilizing metallic derivatives in water involves
the use of ligands with hydrophilic properties. Regarding
gold(I) complexes, phosphane ligands are commonly used
because of the stability of the Au−P bond. Among the many
water-soluble phosphanes currently available, the adamantane-
like phosphane 1,3,5-triaza-7-phosphaadamantane (PTA) and
its derivatives have received special attention because of their
similar reactivity to other alkylphosphanes and their higher air
stability and resistance to oxidation than other water-soluble
phosphanes.21
Taking all of this into consideration, in this work we have
introduced water-soluble phosphanes [PTA and 3,7-diacetyl-
1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane (DAPTA)] as a
second coordination position of a Au-C6F5 moiety in order
to obtain organometallic perhalogenated gold(I) systems with
increasing solubility in water. The reaction of gold(I)
complexes with different silver salts has given rise to the
formation of heterometallic systems that display different
supramolecular structures in water and intrinsic luminescence
that depends on the counterion. Moreover, the resulting
aggregates present a particular alignment that depends on the
polarization angle, comparable to the behavior presented by
lyotropic chromonic liquid crystals (LCLCs).
1
their coordination to the gold centers. Finally, their H NMR
spectra display the typical patterns of the PTA and DAPTA
phosphanes (see the SI).
Once the gold(I) derivatives were obtained and charac-
terized, AgPF6 was added to independent acetonitrile solutions
of 1 and 2 in order to obtain the corresponding heterometallic
complexes (Scheme 2).
a
Scheme 2. Synthesis of Au···Ag Heterometallic Complexes
a
1
The coordination mode of the atoms of /2 the silver cation in the
resulting complex is not determined in this scheme.
Attempts to obtain heterometallic complexes with different
stoichiometries (1:1, 1:2, and 1:3 Au/Ag) were performed by
the addition of 1, 2, and 3 equiv of the silver salt in the
acetonitrile solution reaction. In the case of 1, 1H NMR
titration data indicate a progressive shift of the signals
(intermediate complexes) with increasing amounts of the silver
salt (Figure 1), while similar experiments with complex 2 lead
directly to the formation of the same final product in all cases
(Figure S9). Analysis of the data seems to indicate that in both
cases the addition of increasing amounts of Ag+ gives rise to the
formation of the analogous product, which does not depend on
the stoichiometry of the reaction (gold complex/silver salt).
The chemical shift changes indicate that the formation of the
DAPTA derivative is kinetically faster. On the other hand, PTA
protons display larger downfield shifts in the coordination with
Ag+ than DAPTA signals. This is an indication of a different
coordination mode of the silver cation in the formation of the
heterometallic complexes 3 and 4. The presence of acetonitrile
molecules is observed in all cases, being indicative of the
coordination of this solvent probably for stabilization of the
resulting structures (Figures 1 and S9).
RESULTS AND DISCUSSION
■
Synthesis and Characterization. [Au(C6F5)(PTA)] (1)22
and [Au(C6F5)(DAPTA)] (2) were obtained by the reaction of
[Au(C6F5)(tht)] (tht = tetrahydrothiophene) with an equi-
molar amount of the corresponding phosphane in dichloro-
methane by the direct displacement of the labile tht ligand and
coordination of the phosphorus atom to gold (Scheme 1).
Scheme 1. Synthesis of Complexes 1 and 2
Their 19F and 31P NMR spectra follow the same trend (see
the SI). The formation of the heterometallic species was
definitively confirmed by electrospray ionization mass spec-
trometry (ESI-MS), where the presence of Au···Ag complexes
are clearly detected in all cases (Figures 2 and S12), being
indicative of the stability of this metallophilic interaction in
solution. The presence of acetonitrile molecules within the
heterometallic structure is also evidenced in their ESI-MS
Both complexes were obtained as white solids stable to air
and moisture. Their elemental analyses and spectroscopic data
are in accordance with the proposed stoichiometries (see the
Experimental Section). Their mass spectra show peaks at m/z
522.04 and 594.07 corresponding to 1 + H+ and 2 + H+. Their
IR spectra show signals corresponding to the fragment
[Au(C6F5)] at ca. 1505, 960, and 760 cm−1, together with
1
spectra, as previously observed in their H NMR spectra.
X-ray Crystal Structure Determination. Single crystals of
the monometallic complexes 1 and 2 suitable for X-ray
diffraction were grown from dichloromethane/hexane solu-
tions. They crystallize in the C2/c and P21/c space groups of
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Figure 1. 1H NMR spectra of 1 with increasing amounts of AgPF6 salt. Phosphane region (left) and acetonitrile peak (overlapped with acetone-d6,
right) in acetone-d6.
Figure 2. ESI-MS spectrum of 1·AgPF6 (3).
the monoclinic system, respectively, and complex 2 crystallizes
with half a molecule of water per molecule of compound.
Selected bond lengths and angles are summarized in Table S1
and details of data collection and refinement in Table S2.
Both crystal structures consist of linear [(aryl)Au(PR3)]
molecules, which in the case of complex 1 are associated in
pairs via aurophilic interactions of 3.1173(4) Å (Figures 3 and
Au−C distances are similar to the distances of other reported
27−30
AuI-PTA15,24−26 and AuI-C6F5
complexes. The C−Au−P
angles of 169.3(1)° and 174.7(3)° for 1 and 2, respectively,
indicate some deviation from the usual linear geometry, as
reported for analogous complexes.15,24 In the case of complex
1, this fact is probably caused by the aurophilic interaction.
The two assembled molecules in 1 are twisted in an
orthogonal fashion to avoid steric hindrance with a torsion
angle of 82.81° [C1−Au1−Au2−C2] and are extended in the
3D crystal packing (Figure S14). These Au···Au interactions are
not present in the analogous complex containing a phenyl
group instead of a pentafluorophenyl group.26 The resulting
packing in 1 presents a zigzag orientation, as depicted in Figure
4, where Au···Au contacts are maintained, forming dimers that
produce the resulting zigzag structure (Figure S15).
In the case of 2·0.5H2O, no aurophilic contacts are present,
with Au···Au distances longer than 6 Å. Interestingly, an
unusual C−H···Au hydrogen bond, with a gold atom as the
acceptor, is observed [H···Au = 2.833(1) Å, C···Au = 3.657(14)
Å, and C−H···Au = 144.4°]. A series of additional O−H···O,
C−H···O, and C−H··· hydrogen bonds give rise to a 2D
network (see Table S3 and Figure S16).
The nature and geometry of the heterometallic complexes
could also be verified by crystal X-ray diffraction. Single crystals
suitable for X-ray diffraction were grown successfully for 4
synthesized in 1:1 and 1:2 Au/Ag stoichiometry, both of them
giving rise to identical structures (1:1 complex; Tables S4 and
S5). Complex 4 crystallizes with an acetonitrile, an acetone, and
half a water molecule per molecule of compound. The X-ray
Figure 3. Molecular structures of 1 (left) and 2·0.5H2O (right). Color
code: yellow, gold; orange, phosphorus; gray, carbon; light blue,
nitrogen; red, oxygen; green, fluorine. Hydrogen atoms are omitted for
clarity.
S13). The aurophilic interaction observed in 1 is shorter than
those reported for related gold(I) derivatives with PTA,23−27
which vary from 3.1388(11) Å in [Au{CC−C(Me)(Et)-
OH}(PTA)]27 and 3.457(1) Å in [Au(PTA)2][Au(CN2)]24 or
those in [Au{7-(prop-2-ine-1-yloxy)-1-benzopyran-2-one}-
(DAPTA)]15 [3.1274(4) and 3.1316(4) Å], and it is only
longer than that in [Au({SPh(3,5-Cl2)}(PTA)],24 which
displays a Au−Au distance of 3.0468(10) Å. The Au−P and
C
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Figure 4. Crystal packing representation of 2·0.5H2O (right). Color code: yellow, gold; orange, phosphorus; gray, carbon; light blue, nitrogen; red,
oxygen; green, fluorine. Hydrogen atoms are omitted for clarity.
crystal structure of 4·NCMe·Me2CO·0.5H2O shows hetero-
dinuclear units displaying strong Au···Ag contacts of
2.8160(12) Å, and tetranuclear dications are further formed
thanks to the presence of oxygen-bridging atoms of the
phosphanes (Figures 5 and S17 and Table S4). The Au···Ag
NMR spectrum of complex 3 with respect to that of 4 (upon
coordination with a silver cation) make us expect a shorter
metallophilic Au···Ag contact in this case, which would get the
silver centers closer to the phosphane in 3 than in 4.
Photophysical Characterization. Absorption and emis-
sion spectra of all complexes were recorded in water at a
concentration of ca. 10−4 M, and the results are summarized in
Table 1 and Figure 6.
Table 1. Absorption and Emission Data of Compounds 1−
a
4
absorption λmax, nm
emission [solution, emission [solid,
compound
(ε, M−1 cm−1
)
λmax (nm)]
λmax (nm)]
1
2
3
4
255 (5861)
253 (4850)
255 (9868)
253 (5000)
487
474
541
547
530
530, 649
a
Emission spectra were recorded upon excitation at 375 nm.
Figure 5. X-ray crystal representation of the dimeric units shown in 4·
NCMe·Me2CO·0.5H2O. Color code: yellow, gold; blue, silver; orange,
phosphorus; gray, carbon; light blue, nitrogen; red, oxygen; green,
fluorine. Hydrogen atoms are omitted for clarity.
The absorption profiles display the typical π−π* intraligand
transition of the pentafluorphenyl unit around 250 nm,
together with σ → aπ transitions associated with coordinated
phosphanes at higher wavelengths. Absorption spectra of the
gold complexes 1 and 2 display an additional tail at ca. 300 nm,
which can be assigned to the presence of aurophilic interactions
(σ*Au−Au → π* transition) in solution.16,35 In fact, these bands
at longer wavelength are better observed at higher concen-
trations, indicating that the Au···Ag interactions are more
favored with increasing concentrations.
For the PTA derivatives, the extinction coefficient of the
heterometallic complex (Table 1) is higher than the
corresponding gold(I) precursor, which can be due to an
increase of the solubility when the charged heterometallic
complex is formed. This fact was also observed with other Au/
Ag systems with similar aromatic rings and containing
phosphanes as the secondary ancillary ligand.30
distances are similar to those previously reported for Au/Ag
heterometallic complexes containing the unit Au-C6F5
([Ag2Au2{4-C6F4(4-C6BrF4)}2(CF3CO2)2(μ-L−L)]n, with L−
L = dppm and dppb)31 and shorter than those in other
polymeric Au/Ag structures.32−34 The gold centers display their
usual linear environment, if the metal−metal contacts are not
taken into account, with typical Au−P and Au−C bond lengths.
The silver atoms display a distorted tetrahedral geometry by
coordination to the gold center, to the nitrogen atom of an
acetonitrile molecule, to the oxygen atom of an acetone
crystallization molecule, and to a bridging oxygen atom of the
phosphane. Consequently, this last Ag−O bond distance
[2.416(13) Å] is longer than other one [2.293(10) Å]. The
presence of additional O−H···O, O−H···N, and C−H···O
hydrogen bonds results in a 1D polymer (Figure S17 and Table
S6).
Only the heterometallic complexes show luminescence in
aqueous solution with emission peaks at ca. 530 and 650 nm
that may have their origin on aggregates in solution, according
to the excitation spectra (Figure S18). By contrast, strong
luminescence is observed for all compounds in the solid state
Unfortunately, we were not able to grow single crystals of
complex 3 suitable for X-ray diffraction studies. Nevertheless,
1
the larger downfield shifts in the phosphane protons in the H
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Figure 6. Absorption spectra of complexes 1−4 in water at a concentration of 6.5 × 10−5 M (1 and 3) or 1 × 10−4 M (2 and 4).
Figure 7. Normalized emission spectra of compounds 1−4 upon excitation solids at 375 nm.
upon excitation of the samples at ca. 375 nm (Figures 7 and
S19).
The same emission was observed when the synthesis was
carried out with 1, 2, and 3 equiv of AgPF6, which is additional
evidence of the same resulting heterometallic 1:1 complexes
(Figure S20).
Absorption spectral variations recorded at different concen-
trations are not linear in all cases, in agreement with the
aggregation effect38 (Figures 8 and S21−S23), and indicate very
It can be observed that the gold complexes 1 and 2 display a
broad emission band at ca. 480 nm, which is approximately 70
nm red-shifted in the resulting heterometallic structures 3 and
4. The energies of these bands are in the same range as those
previously described for (terpy)AuC6F5 complexes30 and
heterometallic Au−Ag structures, containing Au···Ag inter-
actions.36 The observed emission bands in complexes 1 and 2
may arise from 3MLCT transitions (gold-to-perfluoroaryl-
3
ligand charge transfer), although a π−π excimeric IL emission
cannot be ruled out because of the possible π−π stacking of the
aromatic ligands in the solid state. In the cases of 3 and 4 and
taking into consideration the observed red shift, the resulting
emissions are likely to arise from ligand-to-metal−metal (Au···
Ag)-to-ligand charge transfer (3MMLCT).36 The triplet
assignment of these bands is due to the large Stokes shift
observed in all cases.
Figure 8. Absorption spectra of 1 at different concentrations in water.
Inset: Representation of the absorption at 255 nm versus
concentration.
Aggregation in Water. The presence of PTA and DAPTA
phosphanes together with fluorine atoms (able to be involved
on hydrogen bonds) and gold/silver metal atoms (able to
establish metallophilic interactions) makes us expect the
possible formation of supramolecular aggregates, as was
previously observed with other organometallic PTA and
DAPTA organometallic gold(I) complexes.11,13−15,37
low critical aggregation concentration (CAC) values: 5 × 10−5
M for gold(I) complexes and slightly higher (1 × 10−4 and 7 ×
10−5 M) for 3 and 4, respectively.
Emission spectra of the heterometallic complexes recorded at
different concentrations follow the same trend, with a deviation
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of the linearity of the emission maxima with increasing
concentrations (Figures S24 and S25) at a similar CAC value.
The formation of large and well-organized supramolecular
aggregates was also evidenced by microscopic techniques.
Optical microscopy images of 1−4 under polarized light are
displayed in Figure 9 and show different types of morphologies:
Figure 11. (left) Fluorescence microscopy image with excitation band
passes: 450−490 nm. (right) TEM image of a 1 × 10−4 M dried
aqueous solution of 3.
the higher resulting entangled aggregates can be better
observed under transmission electron microscopy (TEM).
Very large dendritic structures in the range of micrometer size
are the result of the intermolecular interactions in the
heterometallic complexes (Figure 11, right).
Tuning Shapes and Emission with Counterions. As
previously reported with other gold(I) supramolecular
structures,11,42 counterions can play a direct role on the
resulting emissive properties of complexes. With this goal in
mind, compounds 1 and 2 were treated with different silver
salts, as nitrate and triflate, following the same experimental
procedure previously described for the hexafluorophosphate
derivatives 3 and 4. The corresponding multinuclear NMR
spectra show the correct formation of all the complexes. Two
different trends were observed for the PTA and DAPTA
derivatives. For the first group, the recorded downfield shift of
the phosphane protons depends on the counterion being larger
effect with respect to the gold(I) mononuclear complex 1,
those complexes containing counterions, triflate and hexafluor-
ophophate, able to establish F···H bonds with the complex (see
Figure 12). This is a clear indication about the role of the
counterion in the resulting package. It seems that the anion
with higher solubility in water and without any fluorine atom
(nitrate) can have a weaker interaction with the heterometallic
complex, while triflate and hexafluorophosphate try to avoid
water (hydrophobic effect) and are closely connected to the
corresponding complex by the establishment of F···H bonds.
On the contrary, a significant interaction of the nitrate
counterion is expected for DAPTA derivatives because of the
larger recorded downfield shift. This could be due to the
presence of four possible positions in the nitrate to establish
hydrogen bonds with the complex.
Figure 9. Optical microscopy images of 2-day-old dried samples of ca.
1 × 10−4 M aqueous solutions of 1−4 under polarized light.
from needle- and rodlike structures in compound 1, spherical
aggregates in 2, and dendritic and higher entangled
agglomerates in the case of the heterometallic complexes (as
evidenced by the spherulite profile seen under polarized
light).39,40 That means that the establishment of Au···Ag
contacts favors the global contacts and gives rise to larger
structures. As was previously observed for gold(I) water-soluble
complexes in water, the size of the aggregates increases with
time, as shown in Figure S26.
An unusual behavior was detected for the heterometallic
complexes. The larger aggregates are aligned in different planes,
as observed by changing the polarization angle (Figures 10 and
S26). This long-range orientational order is analogous to that
observed in LCLCs.41 These species have shown promising
applications as polarizing films and security labels, templates for
the controlled assembly of nanostructures, including peptide
amphiphiles, fabrication of microelectronic devices, electro-
optical devices, etc. To the best of our knowledge, this nice
example of an on/off heterometallic supramolecular polarized
organization in water has no precedent in the literature.
Fluorescence microscopy supports these data, and green
emissive aggregates can be observed (Figure 11, left), in
agreement with the previous emission spectra displayed in the
solid state (largest aggregation state; Figure 7). Additionally,
Moreover, their 19F and 31P NMR spectra follow the same
trend (Figures S27−S31). In particular, the fluorine atoms of
the organometallic part of the complexes follow the same trend
Figure 10. Optical microscopy images of a 1 × 10−4 M fresh sample of 3 without polarization (left) and between cross-polarizers using angles of 65°
(middle) and 85° (right). Regions I and II change color with the polarization angle, from yellow to blue and vice versa.
F
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previously observed for the hexafluorphosphate one, with
dendritic-like morphologies. Nitrate complexes induce a change
on the morphology with spherical structures. In general, the
size of the organized nitrate aggregates is smaller than that for
the other complexes. Thus, the effect of the particular
counterion on the resulting aggregates’ size and morphology,
as well as on their intrinsic luminescent properties, has been
evidenced.
CONCLUSIONS
■
The introduction of a water-soluble phosphane (PTA or
DAPTA) as a second coordination ligand of an organometallic
Au-C6F5 moiety gives rise to the formation of water-soluble
perhalogenated complexes 1 and 2. The use of absorption,
emission, and microscopic techniques evidenced the formation
of aggregates at high concentrations.
1
Figure 12. H NMR spectra of heterometallic complexes synthesized
from 1 and AgPF6 (3), AgNO3 (5) and AgOTf (6) in acetone-d6.
Additionally, the resulting aggregates’ size, shape, and
luminescent properties can be modulated by the interaction
with the silver salts with expected Au···Ag metallophilic
contacts, as evidenced by their X-ray crystal structures.
The resulting heterometallic complexes are also soluble in
water and give rise to different aggregate morphologies
depending on the counterion and phosphane. That is, a nitrate
counterion gives rise to smaller and spherical aggregates, while
the use of fluorinated counterions such as hexafluorophosphate
or triflate induces the formation of larger and dendritric
supramolecular structures.
Multinuclear NMR and luminescent studies indicate the
degree of interaction between the different counterions and
compounds 1 and 2, with larger downfield chemical shifts and
more red-shifted emission bands for stronger interactions.
Finally, observation of the samples under optical microscopy
with polarized light shows that the aggregates’ organization
depends on the polarization angle, as observed for LCLCs.
as that detailed for protons, with the p-fluorine atoms most
affected in the formation of the complex.
The emission spectra recorded for the solids are in
agreement with previous facts. In the case of the PTA
derivatives, the nitrate heterometallic complex displays the
largest red shift. A plausible explanation based on all the
recorded data is due to the smaller steric hindrance of the anion
that favors the proximity between gold atoms (or gold/silver
atoms) and, thus, metallophilic contacts (Figure S32). In the
case of the DAPTA complexes, the presence of acetyl units as
additional points to establish hydrogen bonds with the anions
has a direct influence on the recorded emission spectra. In this
way, the presence of triflate and hexafluorophosphate (with
higher number of atoms potentially being involved in the
establishment of weak interactions) results in a more significant
red shift of the emission, in comparison with the presence of
nitrate (Figure 13).
Absorption and emission spectra of the new complexes
recorded at different concentrations present profiles similar to
those recorded for 3 and 4 (Figures S33−S40). Analysis of the
morphology of the resulting aggregates in water has been
performed by looking at the samples under optical microscopy
with polarized light (Figure S41). In the case of the triflate
derivatives, the corresponding pattern is similar to that
EXPERIMENTAL SECTION
■
General Procedures. All manipulations were performed under
prepurified N2 using standard Schlenk techniques. All solvents were
distilled from the appropriate drying agents. The commercial reagents
1,3,5-triaza-7-phosphatricyclo[3.3.1.13.7]decane (PTA; Aldrich 97%),
3,7-diacetyl-1,3,7-triaza-5- phosphabicyclo[3.3.1]nonane (DAPTA;
Aldrich 97%), AgCF3SO3 (AgOTf; Aldrich 98%), silver nitrate
(Panreac, 97%), and silver hexafluorophosphate (Aldrich, 98%) were
Figure 13. Normalized emission spectra of 2 and heterometallic complexes with nitrate, triflate, and hexafluorophosphate silver salts (left). Image of
the solids observed under UV light (right).
G
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used as received. Literature methods were used to prepare [Au(tht)-
(C6F5)]43 and [Au(C6F5)(PTA)] (1).22
([[Au2Ag2(C6F5)2(PTA)2]F]+, calcd m/z 1276.88); 1402.85
([[Au2Ag2(C6F5)2(PTA)2]PF6]+, calcd m/z 1402.84). Anal. Calcd
for C12H12N3F11P2AgAu·0.5CH3CN·H2O: C, 19.22; N, 6.03; H, 1.92.
Found: C, 19.16; N, 5.95; H, 2.04.
Physical Measurements. IR spectra were recorded on a Nicolet
FT-IR 520 spectrophotometer. 1H NMR [δ(TMS) = 0.0 ppm],
31P{1H} NMR [δ(85% H3PO4) = 0.0 ppm], and 19F{1H} NMR
[δ(CFCl3) = 0.0 ppm] spectra were obtained on Varian Mercury 400
and Bruker 400 spectrometers (Universitat de Barcelona). Elemental
Synthesis of [AuAg(C6F5)(DAPTA)]PF6 (4). Solid AgPF6 (21.3 mg,
0.084 mmol) was added to a solution of 2 (50 mg, 0.084 mmol) in
CH3CN (15 mL). The solution was stirred during 1 h and then
evaporated to dryness under vacuum to yield an orange solid.
31P{1H} NMR (acetone-d6, ppm): −17.9 (m, DAPTA), −144.3 (m,
analyses of carbon, hydrogen, and nitrogen were carried out at the
́
Centres Cientifics i Tecnolog
̀
ics de la Universitat de Barcelona.
−
1
PF6 ). H NMR (acetone-d6, ppm): 2.05 (CH3CN, overlapped with
the acetone-d6 signal), 2.09 (m, 6H, COMe), 3.82 (m, 1H, NCH2P),
4.19 (s, 2H, NCH2P), 4.25 (d, J = 14.0 Hz, 1H, NCH2N), 4.45 (m,
1H, NCH2P), 4.86 (m, 1H, NCH2P), 4.99−5.13 (m, 2H, NCH2N),
5.65 (m, 1H, NCH2P), 5.75 (d, J = 14.0 Hz, 1H, NCH2N).19F NMR
(acetone-d6, ppm): −164.0 (m, m-F), −160.4 (t, J = 20.4 Hz, p-F),
Electrospray ionization mass spectrometry in positive-ion mode [ESI-
MS(+)] spectra were recorded on a Fisons VG Quatro spectrometer
(Universitat de Barcelona). Absorption spectra were recorded on a
Varian Cary 100 Bio UV spectrophotometer and emission spectra on a
Horiba-Jobin-Ybon SPEX Nanolog spectrofluorimeter (Universitat de
Barcelona). Fluorescence microscopy was recorded on a Leica DMIRB
fluorescence microscope (Universitat de Barcelona). Optical micros-
copy images were acquired on a Leica ICC50 W microscope
(Universitat de Barcelona). TEM images were recorded with a Tecnai
G2 Spirit microscope.
−
−116.6 (m, o-F), −73.1 (d, J = 530.6 Hz, PF6 ). IR (KBr, cm−1):
ν(CO) 1637; ν(Au-C6F5) 1500, 952, 700; ν(CH2−P) 1454; ν(C−
−
N) 1232; ν(PF6
) 840, 560. ESI-MS(+): m/z 1546.89
([[Au2Ag2(C6F5)2(DAPTA)2]PF6]+, calcd m/z 1546.89). Anal. Calcd
for C15H16AgAuF11N3O2P2·0.5CH3CN: C, 27.65; N, 8.06; H, 2.32.
Found: C, 27.20; N, 8.10; H, 2.43.
Crystallography. Crystals were mounted in inert oil on glass fibers
and transferred to the cold gas stream of a Nonius Kappa charge-
coupled device (CCD; 1) or a Bruker APEX-II CCD diffractometer
(2·0.5H2O and 4·NCMe·Me2CO·0.5H2O) equipped with an Oxford
Instruments low-temperature attachment. Data were collected using
monochromated Mo Kα radiation (λ = 0.71073 Å). Scan types were ω
and ϕ. Absorption effects were treated by semiempirical corrections
based on multiple scans. The structures were solved by direct methods
and refined on F2 using the program SHELXL-97.3 All non-hydrogen
atoms were refined anisotroplically, and hydrogen atoms were
included using the riding model. Selected bond lengths and angles
are collected in Tables S1 and S4, and crystal structures of complexes
1, 2·0.5H2O, and 4·NCMe·Me2CO·0.5H2O are shown in Figures 3
and 5. CCDC 1563994−1563996 contain the supplementary
crystallographic data for this paper.
Synthesis of [AuAg(C6F5)(PTA)]NO3 (5). A similar procedure was
used in the synthesis of 5 with respect to 3 but using AgNO3 instead of
AgPF6 and in a 1:1 ratio (gold precursor/silver salt). Yield: 47%.
1
31P{1H} NMR (acetone-d6, ppm): −45.2. H NMR (acetone-d6,
ppm): 4.55 (s, 6H, NCH2P), 4.64−4.81 (AB q, J = 12.8 Hz, 6H,
NCH2N). 19F NMR (acetone-d6, ppm): −164.9 (m, m-F), −162.8 (t, J
= 21.2 Hz, p-F), −115.3 (m, o-F). IR (KBr, cm−1): ν(Au-C6F5) 1510,
−
947, 791; ν(CH2−P) 1459; ν(NO3 ) 1383; ν(C−N) 1276. ESI-
MS(+). Calcd for C12H12N3F5PAgAu ([M]+): m/z 627.940. Found:
m/z 627.9402. ESI-MS(+): m/z 1276.88 ([[Au2Ag2(C6F5)2(PTA)2]-
F]+, calcd m/z 1276.88). Anal. Calcd for C12H12N4F5O3PAgAu·
0.5CH3CN: C, 21.94; N, 8.86; H, 1.91. Found: C, 22.10; N, 8.93; H,
1.93.
Synthesis of [AuAg(C6F5)(PTA)]OTf (6). A similar procedure was
used in the synthesis of 6 with respect to 5 but using AgOTf instead of
AgPF6. Yield: 77%.
Synthesis and Characterization. Synthesis of [Au(C6F5)(PTA)]
(1). The compound was prepared following a procedure analogous to
that reported in the literature. Yield: 63%.22
1
31P{1H} NMR (acetone-d6, ppm): −47.2. H NMR (acetone-d6,
1
31P{1H} NMR (acetone-d6, ppm): −35.7. H NMR (acetone-d6,
ppm): 4.48 (s, 6H, NCH2P), 4.52−4.72 (AB q, J = 13.0 Hz, 6H,
NCH2N). 19F NMR (acetone-d6, ppm): −164.1 (m, m-F), −160.8 (t, J
= 19.7 Hz, p-F), −116.7 (m, o-F). IR (KBr, cm−1): ν(Au-C6F5) 1504,
947, 743; ν(CH2−P) 1459; ν(C−N) 1237. ESI-MS(+): m/z 522.04
([M + H]+, calcd m/z 522.04). Anal. Calcd: C, 27.65; N, 8.06; H, 2.32.
Found: C, 27.74; N, 7.98; H, 2.40.
ppm): 2.07 (CH3CN, overlapped with the acetone-d6 signal), 4.72 (s,
6H, NCH2P), 4.99−5.09 (AB q, J = 13.2 Hz, 6H, NCH2N). 19F
(acetone-d6, ppm): −163.8 (m, m-F), −157.7 (t, J = 20.8 Hz, p-F),
−
−116.2 (m, o-F), −78.5 (s, CF3SO3 ). IR (KBr, cm−1): ν(Au-C6F5)
−
1508, 947, 700; ν(CH2−P) 1450; ν(CF3SO3 ) 1259. ESI-MS(+) m/z
627.940 ([AuAg(C6F5)(PTA)]+, calcd m/z 627.940), 668.966
([[AuAg(C6F5)(PTA)]CH3CN]+, calcd m/z 668.966), 1404.832
([[Au2Ag2(C6F5)2(PTA)2]OTf]+, calcd m/z 1406.833). Anal. Calcd
for C13H12N4F8O3PSAgAu·0.5CH3CN·H2O: C, 27.90; N, 8.76; H,
2.79. Found: C, 27.84; N, 8.81; H, 2.80.
Synthesis of [Au(C6F5)(DAPTA)] (2). In a typical procedure, solid
DAPTA (144 mg, 0.243 mmol) was added to a solution of
[Au(C6F5)(tht)] (110 mg, 0.243 mmol) in CH2Cl2 (10 mL) and
stirred for 2 h. The solution was concentrated to 5 mL, and then
hexane was added to precipitate a white solid in 65% yield.
Synthesis of [AuAg(C6F5)(DAPTA)]NO3 (7). A similar procedure was
used in the synthesis of 7 with respect to 4 but using AgNO3 instead of
AgPF6. Yield: 30%.
1
31P{1H} NMR (acetone-d6, ppm): −18.3. H NMR (acetone-d6,
ppm): 2.09 (m, 6H, COMe), 3.82 (m, 1H, NCH2P), 4.18 (s, 2H,
NCH2P), 4.25 (d, J = 13.9 Hz, 1H, NCH2N), 4.45 (m, 1H, NCH2P),
4.85 (m, 1H, NCH2P), 4.99−5.12 (m, 2H, NCH2N), 5.59−5.68 (m,
1H, NCH2P), 5.75 (d, J = 14.1 Hz, 1H, NCH2N). 19F NMR (acetone-
d6, ppm): −164.0 (m, m-F), −160.3 (t, J = 21.6 Hz, p-F), −116.6 (m,
o-F). IR (KBr, cm−1): ν(CO) 1645; ν(Au-C6F5) 1507, 956, 790;
ν(CH2−P) 1458; ν(C−N) 1225. ESI-MS(+): m/z 594.07 ([M + H]+,
calcd m/z 594.06). Anal. Calcd: C, 30.37; N, 7.08; H, 2.72. Found: C,
30.57; N, 7.00; H, 2.85.
1
31P{1H} NMR (acetone-d6, ppm): −17.7. H NMR (acetone-d6,
ppm): 2.08 (m, 6H, COMe), 3.81 (t, J = 16 Hz, 1H, NCH2P), 4.28−
4.16 (m, 3H, NCH2P + NCH2N), 4.44 (m, 1H, NCH2P), 4.86 (d, J =
15.6 Hz, 1H, NCH2N), 4.97−5.12 (m, 2H, NCH2P + NCH2N), 5.58−
5.77 (m, 2H, NCH2P + NCH2N). 19F NMR (acetone-d6, ppm):
−163.9 (m, m-F), −160.1 (t, J = 20.4 Hz, p-F), −116.3 (m, o-F). IR
(KBr, cm−1): ν(CO) 1645; ν(Au-C6F5) 1503, 954, 800; ν(CH2−P)
−
1450; ν(NO3 ) 1384; ν(C−N) 1261. ESI-MS(+): m/z 699.961
([AuAg(C6F5)(DAPTA)]+, calcd m/z 699.961), 1461.911
([[Au2Ag2(C6F5)2(DAPTA)2]NO3]+, calcd m/z 1493.911). Anal.
Calcd for C15H16AgAuF5N4O5P·0.5CH3CN: C, 24.52; N, 8.04; H,
2.25. Found: C, 24.61; N, 8.06; H, 2.27.
Synthesis of [AuAg(C6F5)(PTA)]PF6 (3). Solid AgPF6 (72.8 mg,
0.288 mmol) was added to a solution of 1 (50 mg, 0.096 mmol) in
CH3CN (15 mL). The solution was stirred during 1 h and then
evaporated to dryness under vacuum to yield an orange solid.
−
31P{1H} NMR (acetone-d6, ppm): −42.5 (PTA), −144.3 (m, PF6 ).
Synthesis of [AuAg(C6F5)(DAPTA)]OTf (8). A similar procedure was
used in the synthesis of 8 with respect to 4 but using AgOTf instead of
AgPF6. Yield: 20%.
1H NMR (acetone-d6, ppm): 2.07 (s, CH3CN, overlapped with the
acetone-d6 signal), 4.60 (s, 6H, NCH2P), 4.74−4.90 (AB q, J = 13.1
Hz, 6H, NCH2N). 19F NMR (acetone-d6, ppm): −164.0 (m, m-F),
−160.5 (t, J = 20.4 Hz, p-F), −116.7 (m, o-F), −72.4 (d, J = 530.6 Hz,
1
31P{1H} NMR (acetone-d6, ppm): −17.8. H NMR (acetone-d6,
ppm): 2.05 (CH3CN, overlapped with the acetone-d6 signal), 2.08 (s,
3H, COMe), 2.09 (s, 3H, COMe), 3.80 (dt, J = 15.6 and 3.2 Hz, 1H,
NCH2P), 4.17 (s, 2H, NCH2P), 4.24 (d, J = 14 Hz, 1H, NCH2N),
−
PF6 ). IR (KBr, cm−1): ν(Au-C6F5) 1500, 978, 700; ν(CH2−P) 1455;
ν(C−N) 1241; ν(PF6−) 840, 551. ESI-MS(+): m/z 1276.88
H
DOI: 10.1021/acs.inorgchem.7b01901
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Article
4.44 (dt, J = 15.2 and 4 Hz, 1H, NCH2P), 4.84 (d, J = 14 Hz, 1H,
NCH2N), 4.99 (d, J = 10.4 Hz, 1H, NCH2P), 5.07 (d, J = 14 Hz, 1H,
NCH2N), 5.62 (dd, J = 16 and 8 Hz, 1H, NCH2P), 5.73 (d, J = 14 Hz,
1H, NCH2N). 19F NMR (acetone-d6, ppm): −163.9 (m, m-F), −160.2
(7) Schmidbaur, H.; Schier, A. Aurophilic interactions as a subject of
current research: an up-date. Chem. Soc. Rev. 2012, 41, 370.
́
(8) Lopez-de-Luzuriaga, J. M.; Monge, M.; Olmos, M. E.; Pascual, D.
Study of the Nature of Closed-Shell HgII···MI (M = Cu, Ag, Au)
Interactions. Organometallics 2015, 34, 3029.
−
(t, J = 20.8 Hz, p-F), −116.5 (m, o-F), −78.6 (s, CF3SO3 ). IR (KBr,
cm−1): ν(CO) 1646; ν(Au-C6F5) 1504, 952, 796; ν(CH2−P) 1450;
́
(9) Zhang, Q.-W.; Li, D.; Li, X.; White, P. B.; Mecinovic, J.; Ma, X.;
ν(CF3SO3−) 1259. ESI-MS(+): m/z 699.961 ([AuAg(C6F5)-
Ågren, H.; Nolte, R. J. M.; Tian, H. Multicolor Photoluminescence
Including White-Light Emission by a Single Host−Guest Complex. J.
Am. Chem. Soc. 2016, 138, 13541.
( D A P T A ) ] +
,
c a l c d m / z 6 9 9 . 9 6 1 ) , 1 5 4 8 . 8 7 5
([[Au2Ag2(C6F5)2(DAPTA)2]OTf]+, calcd m/z 1550.875. Anal.
Calcd for C16H16AgAuF8N4O5SP·0.5CH3CN·H2O: C, 22.98; N,
5.52; H, 2.21. Found: C, 23.12; N, 5.47; H, 2.23.
(10) Woodall, C. H.; Beavers, C. M.; Christensen, J.; Hatcher, L. E.;
Intissar, M.; Parlett, A.; Teat, S. J.; Reber, C.; Raithby, P. R. Hingeless
negative linear compression in the mechanochromic gold complex
[(C6F5Au)2(μ-1,4-diisocyanobenzene)]. Angew. Chem., Int. Ed. 2013,
52, 9691.
ASSOCIATED CONTENT
* Supporting Information
■
S
́
(11) Aguilo, E.; Gavara, R.; Baucells, C.; Guitart, M.; Lima, J. C.;
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.inorg-
chem.7b01901.
Llorca, J.; Rodríguez, L. Tuning supramolecular aurophilic structures:
the effect of counterion, positive charge and solvent. Dalton Trans.
2016, 45, 7328.
́
(12) Arcau, J.; Andermark, V.; Aguilo, E.; Gandioso, A.; Moro, A.;
Figures S1−S41 and Tables S1−S6 as described in the
Cetina, M.; Lima, J. C.; Rissanen, K.; Ott, I.; Rodríguez, L.
Luminescent alkynyl-gold(I) coumarin derivatives and their biological
activity. Dalton Trans. 2014, 43, 4426.
text PDF)
Accession Codes
(13) Gavara, R.; Llorca, J.; Lima, J. C.; Rodríguez, L. A luminescent
hydrogel based on a new Au(I) complex. Chem. Commun. 2013, 49,
72.
(14) Aguilo, E.; Gavara, R.; Lima, J. C.; Llorca, J.; Rodríguez, L. From
́
Au(I) organometallic hydrogels to well-defined Au(0) nanoparticles. J.
Mater. Chem. C 2013, 1, 5538.
CCDC 1563994−1563996 contain the supplementary crystal-
lographic data for this paper. These data can be obtained free of
charge via www.ccdc.cam.ac.uk/data_request/cif, or by email-
ing data_request@ccdc.cam.ac.uk, or by contacting The
Cambridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK; fax: +44 1223 336033.
́
(15) Moro, A. J.; Rome, B.; Aguilo, E.; Arcau, J.; Puttreddy, R.;
Rissanen, K.; Lima, J. C.; Rodríguez, L. A coumarin based gold(I)-
alkynyl complex: a new class of supramolecular hydrogelators. Org.
Biomol. Chem. 2015, 13, 2026.
AUTHOR INFORMATION
Corresponding Authors
*E-mail: m-elena.olmos@unirioja.es.
*E-mail: laura.rodriguez@qi.ub.es.
■
́
(16) Gavara, R.; Aguilo, E.; Fonseca-Guerra, C.; Rodríguez, L.; Lima,
J. C. Thermodynamic Aspects of Aurophilic Hydrogelators. Inorg.
Chem. 2015, 54, 5195.
ORCID
(17) Liang, J.; Chen, Z.; Yin, J.; Yu, G.-A.; Liu, S. H. Aggregation-
induced emission (AIE) behavior and thermochromic luminescence
properties of a new gold(I) complex. Chem. Commun. 2013, 49, 3567.
(18) Ito, H.; Saito, T.; Oshima, N.; Kitamura, N.; Ishizaka, S.;
Hinatsu, Y.; Wakeshima, M.; Kato, M.; Tsuge, K.; Sawamura, M.
Reversible Mechanochromic Luminescence of [(C6F5Au)2(μ-1,4-
Diisocyanobenzene)]. J. Am. Chem. Soc. 2008, 130, 10044.
(19) Ferrer, M.; Mounir, M.; Rodríguez, L.; Rossell, O.; Coco, S.;
Jose M Lopez de Luzuriaga: 0000-0001-5767-8734
́
́
Laura Rodríguez: 0000-0003-1289-1587
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
The authors are grateful to the Ministerio de Ciencia e
■
́
Gomez-Sal, P.; Martín, A. Effect of the organic fragment on the
mesogenic properties of a series of organogold(I) isocyanide
complexes. X-ray Crystal structure of [Au(CCC5H4N)(CNC6H4O-
(O)CC6H4OC10H21)]. J. Organomet. Chem. 2005, 690, 2200.
(20) Pinto, A.; Svahn, N.; Lima, J. C.; Rodríguez, L. Aggregation
Induced Emission of Gold(I) complexes in water or water mixtures.
Dalton Trans. 2017, 46, 11125.
Innovacion
́
of Spain (AEI/FEDER, UE Projects CTQ2016-
76120-P and CTQ2016-75816-C2-2-P). This research was
supported by a Marie Curie Intra European Fellowship within
the 7th European Community Framework Programme (to
R.G.). R.D. thanks CAR for a grant.
(21) Siele, V. I. Some reactions of 1,3,5-Triaza-7-phosphaadamantane
and its 7-Oxide. J. Heterocycl. Chem. 1977, 14, 337.
REFERENCES
■
(22) Mohr, F.; Cerrada, E.; Laguna, M. Organometallic Gold(I) and
Gold(III) Complexes Containing 1,3,5-Triaza-7-phosphaadamantane
(TPA): Examples of Water-Soluble Organometallic Gold Compounds.
Organometallics 2006, 25, 644.
(1) Gold−Metal Interactions and Applications; Laguna, A., Ed.; Wiley-
VCH: Weinheim, Germany, 2008.
(2) Pyykko, P. Relativity, Gold, Closed-Shell Interactions, and CsAu·
NH3. Angew. Chem., Int. Ed. 2002, 41, 3573.
̈
(23) Vergara, E.; Cerrada, E.; Casini, A.; Zava, O.; Laguna, M.;
Dyson, P. J. Antiproliferative Activity of Gold(I) Alkyne Complexes
Containing Water-Soluble Phosphane Ligands. Organometallics 2010,
29, 2596.
(3) Fernan
M.; Montiel, M.; Olmos, M. E.; Per
Pyridine gold complexes. an emerging class of luminescent materials.
Gold Bull. 2007, 40, 172.
́
dez, E. J.; Laguna, A.; Lop
́
ez-de-Luzuriaga, J. M.; Monge,
ez, J.; Rodríguez-Castillo, M.
́
(24) Assefa, Z.; Omary, M. A.; McBurnett, B. G.; Mohamed, A. A.;
Patterson, H. H.; Staples, R. J.; Fackler, J. P. Syntheses, Structure, and
Photoluminescence Properties of the 1-Dimensional Chain Com-
pounds [(TPA)2Au][Au(CN)2] and (TPA)AuCl (TPA = 1,3,5-Triaza-
7-phosphaadamantane). Inorg. Chem. 2002, 41, 6274.
(4) Calhorda, M. J.; Crespo, O.; Gimeno, M. C.; Jones, P. G.;
́ ́
Laguna, A.; Lopez-de-Luzuriaga, J. M.; Perez, J. L.; Ramon, M. A.;
Veiros, L. F. Synthesis, Structure, Luminescence, and Theoretical
Studies of Tetranuclear Gold Clusters with Phosphinocarborane
Ligands. Inorg. Chem. 2000, 39, 4280.
(25) Mohr, F.; Cerrada, E.; Laguna, M. Organometallic Gold(I) and
Gold(III) Complexes Containing 1,3,5-Triaza-7-phosphaadamantane
(TPA): Examples of Water-Soluble Organometallic Gold Compounds.
Organometallics 2006, 25, 644.
(5) Roundhill, D. M.; Fackler, J. P., Jr. Optoelectronic Properties of
Inorganic Compounds; Plenum: New York, 1999.
(6) Lima, J. C.; Rodríguez, L. Applications of gold(I) alkynyl systems:
a growing field to explore. Chem. Soc. Rev. 2011, 40, 5442.
I
DOI: 10.1021/acs.inorgchem.7b01901
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Article
(26) Forward, J. M.; Fackler, J. P., Jr.; Staples, R. J. Synthesis and
Structural Characterization of the Luminescent Gold(I) Complex
[(MeTPA)3AuI]I3. Use of NaBPh4 as a Phenyl-Transfer Reagent To
Form [(MeTPA)AuPh](BPh4) and (TPA)AuPh. Organometallics
1995, 14, 4194.
(27) Overton, A. T.; Lopez-de-Luzuriaga, J. M.; Olmos, M. E.;
́
Mohamed, A. A. Oxidative Rearrangement in Gold Organometallics.
Organometallics 2012, 31, 3460.
(42) Hsu, T. H. T.; Naidu, J. J.; Yang, B. J.; Jang, M. Y.; Lin, I. J. B.
Self-Assembly of Silver(I) and Gold(I) N-Heterocyclic Carbene
Complexes in Solid State, Mesophase, and Solution. Inorg. Chem.
2012, 51, 98.
́
(43) Uson, R.; Laguna, A.; Vicente, J. Preparation and properties of
stable salts containing mono- or bis-(pentafluorophenyl)aurate(I) and
mono-, tris-, or tetrakis-(pentafluorophenyl)aurate(III) ions. J. Chem.
Soc., Chem. Commun. 1976, 353.
́
(28) Bojan, V. R.; Lopez-de-Luzuriaga, J. M.; Manso, E.; Monge, M.;
Olmos, M. E. Metal-Induced Phosphorescence in
(Pentafluorophenyl)gold(III) Complexes. Organometallics 2011, 30,
4486.
́
(29) Echeverría, R.; Lopez-de-Luzuriaga, J. M.; Monge, M.; Moreno,
S.; Olmos, M. E. New Insights into the Au(I)···Pb(II) Closed-Shell
Interaction: Tuning of the Emissive Properties with the Intermetallic
Distance. Inorg. Chem. 2016, 55, 10523.
́
(30) Gimeno, M. C.; Lopez-de-Luzuriaga, J. M.; Manso, E.; Monge,
M.; Olmos, M. E.; Rodríguez-Castillo, M.; Tena, M. T.; Day, D. P.;
Lawrence, E. J.; Wildgoose, G. G. Synthesis, Photochemical, and
Redox Properties of Gold(I) and Gold(III) Pincer Complexes
Incorporating a 2,2′:6′,2″-Terpyridine Ligand Framework. Inorg.
Chem. 2015, 54, 10667.
́
(31) Bojan, R. V.; Czerwieniec, R.; Laguna, A.; Lasanta, T.; Lopez-de-
Luzuriaga, J. M.; Monge, M.; Olmos, M. E.; Yersin, H. Luminescent
gold−silver complexes derived from neutral bis(perfluoroaryl)-
diphosphine gold(I) precursors. Dalton Trans. 2013, 42, 4267.
(32) Fernan
M.; Olmos, M. E.; Per
Perfluorocarboxylates as Precursors of Supramolecular Au/Ag
́
dez, E. J.; Laguna, A.; Lop
́
ez-de-Luzuriaga, J. M.; Montiel,
́
ez, J.; Puelles, R. C. Mesitylgold(I) and Silver(I)
Systems. Organometallics 2006, 25, 4307.
(33) Fernandez, E. J.; Jones, P. G.; Laguna, A.; Lopez-de- Luzuriaga,
́ ́
J. M.; Monge, M.; Olmos, M. E.; Puelles, R. C. Perhalophenyl-
(tetrahydrothiophene)gold(I) Complexes as Lewis Bases in Acid−
Base Reactions with Silver Trifluoroacetate. Organometallics 2007, 26,
5931.
(34) Fernan
Lopez-de-Luzuriaga, J. M.; Monge, M.; Montiel, M.; Olmos, M. E.;
Puelles, R. C.; Sanchez-Forcada, E. Multiple Evidence for Gold(I)···
́
dez, E. J.; Hardacre, C.; Laguna, A.; Lagunas, M. C.;
́
́
Silver(I) Interactions in Solution. Chem. - Eur. J. 2009, 15, 6222.
(35) Rodríguez, L.; Ferrer, M.; Crehuet, R.; Anglada, J.; Lima, J. C.
Correlation between Photophysical Parameters and Gold−Gold
Distances in Gold(I) (4-Pyridyl)ethynyl Complexes. Inorg. Chem.
2012, 51, 7636.
(36) Ni, W.-X.; Qiu, Y.-M.; Li, M.; Zheng, J.; Sun, R. W.-Y.; Zhan, S.-
Z.; Ng, S. W.; Li, D. Metallophilicity-Driven Dynamic Aggregation of a
Phosphorescent Gold(I)−Silver(I) Cluster Prepared by Solution-
Based and Mechanochemical Approaches. J. Am. Chem. Soc. 2014, 136,
9532.
́
(37) Gavara, R.; Aguilo, E.; Schur, J.; Llorca, J.; Ott, I.; Rodríguez, L.
Study of the effect of the chromophore and nuclearity on the
aggregation and potential biological activity of gold(I) alkynyl
complexes. Inorg. Chim. Acta 2016, 446, 189.
(38) Gavara, R.; Lima, J. C.; Rodríguez, L. Effect of solvent polarity
on the spectroscopic properties of an alkynyl gold(I) gelator. The
particular case of water. Photochem. Photobiol. Sci. 2016, 15, 635.
(39) Burguete, M. I.; Galindo, F.; Gavara, R.; Izquierdo, M. A.; Lima,
J. C.; Luis, S. V.; Parola, A. J.; Pina, F. Use of Fluorescence
Spectroscopy To Study Polymeric Materials with Porous Structure
Based on Imprinting by Self-Assembled Fibrillar Networks. Langmuir
2008, 24, 9795.
(40) Rodríguez-Llansola, F.; Escuder, B.; Hamley, I. W.; Hayes, W.;
Miravet, J. F. Structural and morphological studies of the dipeptide
based L-Pro-L-Val organocatalytic gels and their rheological behaviour.
Soft Matter 2012, 8, 8865.
(41) Peng, C.; Guo, Y.; Turiv, T.; Jiang, M.; Wei, Q.-H.;
Lavrentovich, O. D. Patterning of Lyotropic Chromonic Liquid
Crystals by Photoalignment with Photonic Metamasks. Adv. Mater.
2017, 29, 1606112.
J
DOI: 10.1021/acs.inorgchem.7b01901
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