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The Phosphine-Stabilized GoldЦArsenic Clusters [Au19(AsnPr)8(dppe)6]Cl3 [Au10(AsnPr)4(dppe)4]Cl2 [Au17(AsnPr)6(As2nPr2)(dppm)6]Cl3 and [Au10(AsPh)4(dppe)4]Cl2 Synthesis Characterization and DFT Calculations.

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Communications
Cluster Compounds
DOI: 10.1002/anie.200504566
The Phosphine-Stabilized Gold–Arsenic Clusters
[Au19(AsnPr)8(dppe)6]Cl3, [Au10(AsnPr)4(dppe)4]Cl2, [Au17(AsnPr)6(As2nPr2)(dppm)6]Cl3,
and [Au10(AsPh)4(dppe)4]Cl2 : Synthesis,
Characterization, and DFT Calculations**
Paloma Sevillano, Olaf Fuhr, Marco Kattannek,
Paola Nava, Oliver Hampe, Sergej Lebedkin,
Reinhart Ahlrichs, Dieter Fenske,* and
Manfred M. Kappes
Dedicated to Professor Hans Georg von Schnering
on the occasion of his 75th birthday
A limited number of gold–arsenic complexes have been
described in the literature, including compounds containing
arsenic bridges (for example, [(Ph3PAu)4As]BF4,[1] [Au4(As4Ph4)2(PnPr3)4],[2]
and
[Au10(AsPh)4(PhAsSiMe3)2(PnPr3)6][2]) or terminal AsR3 ligands (for example,
[(Ph3As)xAu]BF4 (x = 2, 4),[3] [(Ph3AsAu)3O]BF4,[3] [Au(C6F5){(SPh2)2C(AuAsPh3)2}]ClO4,[4] and [Au4Cl2{Ph2PCH2As(Ph)CH2PPh2}2]X2 (X = PF6, NO3)[5]), as well as [Au16(AsPh3)8Cl6], which contains a centered icosahedron of 13
gold atoms.[6] In contrast, the rich chemistry of gold and gold–
chalcogen clusters has been extensively studied.[7–10] At first, it
seemed that gold clusters preferred icosahedral structures or
fragments thereof,[7a, b, 8d] but a variety of other structural
motifs have since been encountered: tetrahedra ([tBu3PAu]4(BF4)2[9c] and [(R3PAu)4O](BF4)2 (R = Ph, o-C6H4Me)[9k]),
square pyramids ([(Ph3PAu)5P](BF4)2,[9l]), trigonal bipyramids
([{(Ph3P)6Au5}P](BF4)3[9j]), edge-sharing bi-tetrahedra ([Au6(PPh3)6](NO3)2[8g]), noncentered and centered crowns (K[Au[*] Dr. P. Sevillano, Dr. O. Fuhr, Prof. Dr. D. Fenske
Institut f"r Anorganische Chemie
Universit)t Karlsruhe, 76128 Karlsruhe (Germany)
Fax: (+ 49) 721-608-8440
E-mail: dieter.fenske@aoc1.uni-karlsruhe.de
and
Institut f"r Nanotechnologie, Forschungszentrum Karlsruhe
Postfach 3640, 76021 Karlsruhe (Germany)
Dr. O. Hampe, Dr. S. Lebedkin, Prof. Dr. M. M. Kappes
Institut f"r Physikalische Chemie
Universit)t Karlsruhe, 76128 Karlsruhe (Germany)
and
Institut f"r Nanotechnologie, Forschungszentrum Karlsruhe
Postfach 3640, 76021 Karlsruhe (Germany)
M. Kattannek, Dr. P. Nava, Prof. Dr. R. Ahlrichs
Institut f"r Physikalische Chemie
Lehrstuhl f"r Theoretische Chemie
Universit)t Karlsruhe, 76128 Karlsruhe (Germany)
[**] This work was supported by the Deutsche Forschungsgemeinschaft
(Center for Functional Nanostructures), the Deutsch-Israelisches
Programm (DIP), and the Fonds der Chemischen Industrie.
dppe = 1,2-bis(diphenylphosphanyl)ethane, dppm = bis(diphenylphosphanyl)methane.
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(AuCl)(AuPPh3)8](PF6)2[9n] and [Au9{P(p-C6H4OMe)3}8](BF4)3[8c]), and octahedra ([Au6{P(p-C6H4Me)3}6](BF4)2[7c]
and [(Ph3PAu)6C](CH3OBF3)2[8i]).
Herein, we report the synthesis and properties of the new
compounds 1–4 obtained from reactions of gold(i) phosphine
complexes with As(R)(SiMe3)2 (R = nPr, Ph; Scheme 1).
Scheme 1. Synthesis of compounds 1–4. dppm = Ph2PCH2PPh2,
dppe = Ph2P(CH2)2PPh2.
The structures of 1–4 were determined by single-crystal
X-ray diffraction (Figures 1–3). However, the nature of the
central atom in 1 and the charge of the cluster could not be
unambiguously established on the basis of the diffraction
analysis. Therefore, electrospray ionization mass spectrometry (ESI-MS) experiments[11–13] (for 1–3) and density functional theory (DFT) calculations (for 1 and 3) were performed. Furthermore, photoluminescence measurements
were carried out to elucidate the origin of the unexpectedly
dark color of 1.
The positive-ion Fourier transform mass spectrum
obtained upon electrospraying a CH2Cl2 solution of 1 and 2
is shown in Figure 4. The main peak V can be unambiguously
assigned to the triply charged cluster ion [Au19(AsnPr)8(dppe)6]3+ in 1 on the basis of the m/z value (Table 1) and the
highly resolved isotope splitting (Figure 4, inset). Peak VI
Figure 2. Molecular structures of the cations in 2 (top; one of two
independent molecules) and 4 (bottom). For clarity atoms are only
numbered; Au gold, As blue, P violet; organic groups represented with
black sticks. Selected distances [pm] and angles [8]: 2: AuAu 298.0(2), AuAs 243.3(3)–245.8(3), AuP 230.1(8)–233.2(9); As-Au-As
169.85(1)–172.62(1), As-Au-P 166.4(2)–169.6(2), Au-As-Au 99.1(1)–
114.0(1). 4: AuAu 290.1(1), AuAs 242.9(2)–246.6(2), AuP
230.1(5)–233.1(4); As1-Au2-As2 176.51(6), As-Au-P 165.3(1)–175.1(1),
Au-As-Au 105.44(6)–111.99(7).
Figure 1. Molecular structures of the cations in 1 (left; molecule I) and 3 (right). For clarity atoms are only numbered; Au gold, As blue, P violet;
organic groups represented with black sticks. Selected distances [pm] and angles [8]: 1: Au10Au8 263.0(1), Au10Au5 286.4(1), Au10Au2
287.7(1), other AuAu 292.8(1), AuAs 239.6(3)–246.2(2), AuP 228.9(7)–232.2(5); Au8-Au10-Au8’ 175.82(9), Au2-Au10-Au5’ 173.63(4), Au2Au10-Au2’ 116.13(7), Au5-Au10-Au5’ 110.73(7), Au8-Au10-Au5 87.98(3), Au8-Au10-Au5’ 94.40(4), Au8-Au10-Au2 91.40(4), Au5-Au10-Au2 66.88(3),
As-Au-As 163.9(1)–173.9(1), As-Au-P 162.4(2)–170.2(1), Au-As-Au 100.60(9)–117.23(8). 3: As7As8 239.7(3), AuAu 290.7(2), AuAs 244.2(3)–
241.0(3), AuP 227.5(8)–232.0(7); As-Au-As 170.3(1)–173.7(1), As-Au-P 153.9(2)–173.7(2), Au-As-Au 96.53(9)–121.4(1), As-As-Au 108.9(1)–
110.7(1).
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mass spectrum of a solution of 3, we unequivocally identify
the ion [Au17(AsnPr)8(dppm)6]3+, as well as the ion pair
[Au17(AsnPr)8(dppm)6Cl]2+, which indicates the presence of
Cl as a counterion in 3 (Figure 5).
Figure 3. Polyhedral representations of the cations in 1–4 highlighting
the chains of Au3As (and Au2As2 in 3) tetrahedra (red and green).
Au gold, As blue, P violet; organic groups represented with black
sticks; propyl and phenyl groups omitted for clarity.
Figure 4. ESI mass spectrum (positive-ion mode) of 1 and 2 in CH2Cl2.
Inset: comparison of the calculated isotope splitting of the
[Au19(AsnPr)8(dppe)6]3+ ion and the observed isotope splitting of
peak V. For a complete peak assignment, see Table 1.
Table 1: Assignment of monoisotopic m/z peaks observed in the ESI
mass spectrum of 1 and 2 to cluster ions and comparison to the
calculated m/z values (see Figure 4).
m/z
Peak
I
II
III
IV
V
VI
Ion
exp.
calcd.
993.235
1306.075
2017.048
2227.006
2358.301
3554.962
993.236
1306.077
2017.053
2227.015
2358.326
3554.974
[Au(dppe)2]+
[Au6(AsnPr)2(dppe)3]2+
[Au10(AsnPr)4(dppe)4]2+
[Au17(AsnPr)8(dppe)6]3+
[Au19(AsnPr)8(dppe)6]3+
[Au19(AsnPr)8(dppe)6Cl]2+
also stems from 1: it results from the association of one Cl
counterion to the trication (such ion-pair formation is
common in ESI-MS). We assign peak III to the cluster
cation of 2, and peak IV to a cluster of composition [Au17(AsnPr)8(dppe)6]3+ with an unknown structure. In the ESI
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Figure 5. ESI mass spectrum (positive-ion mode) of 3 in CH2Cl2. Inset:
comparison of the experimental and calculated isotope splitting of the
[Au17(AsnPr)8(dppm)6]3+ ion peak.
Compounds 1–4 each contain two chains of corner-sharing
Au3As tetrahedra, which are compressed along their C3 axes
(Figure 3). The Au3 faces of opposing tetrahedra in different
chains form elongated trigonal antiprisms. The gold atoms
within each chain are nearly linearly coordinated (153.9–
176.58) by either two arsenic atoms, or by one arsenic atom
and one phosphorus atom. In most cases, the arsenic atoms
are bonded to three gold atoms and an organic group, in a
distorted tetrahedral arrangement. The bidentate phosphine
ligands interconnect the chains of Au3As tetrahedra. All
AuAs and AuP distances are within the expected ranges.
A new structural feature is found in 1: a centered
octahedron of seven gold atoms (Figure 1). Compound 1
crystallizes in the tetragonal space group P42/nbc with twelve
formula units per unit cell.[14] The asymmetric unit comprises
one half and one quarter of two molecules (I and II), which
occupy two different crystallographic positions (with site
symmetries C2 and D2). The two molecules have identical
compositions and slightly different structural parameters
(Table 2). The trications of 1 consist of two helically arranged
U-shaped Au9As4 chains, which are each built up from four
corner-sharing Au3As tetrahedra (Figures 1 and 3). The six
gold atoms at the shared corners in the two chains form a
distorted octahedron, which contains Au10 at its center.
Interactions between the central atom and the vertex atoms
lead to two very short distances (Au10Au8) and four longer
ones (Au10Au5 and Au10Au2; Table 2, entries 1–3). The
angles between the gold atoms in the octahedron range from
66.88(3)–116.13(7)8 (cis) and from 173.67(4)–175.82(9)8
(trans). The resulting AuAu edge distances, which are
larger than 316.3 pm, indicate weak aureophilic interactions.[15]
Compound 2 crystallizes in the orthorhombic space group
C2221 with eight formula units per unit cell.[14] The asymmetric unit contains two half molecules, whose structural
parameters are nearly identical within standard deviations.
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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Table 2: Comparison of selected experimental and calculated
interatomic distances [pm] in molecules I and II of 1 and in the model
compounds 1 a, 1 b, and 1 c.[a]
Entry
Bond
Exp. I
X = Au10
q=+3
Exp. II
X = Au10
q=+3
1a
X = Au
q=+3
1b
X = As
q = 1
1c
X = As
q=+1
1
2
3
4
5
6
7
8
9
10
11
12
13
14
XAu2
XAu5
XAu8
As1Au2
As2Au8
As3Au5
As3’Au7
As3Au9
As4Au2
As4’Au8
As4Au3
Au7P
Au3P
Au9P
287.7(1)
286.4(1)
263.0(1)
243.4(2)
240.2(3)
242.8(2)
243.8(2)
244.0(2)
242.7(2)
239.6(3)
242.8(3)
229.8(5)
229.7(8)
231.9(7)
281.8(1)
281.8(1)
265.9(1)
243.6(2)
240.0(2)
243.6(2)
244.5(2)
246.2(2)
243.4(2)
240.0(2)
241.2(2)
230.5(6)
228.9(7)
231.5(6)
291.4
291.4
272.1
247.8
245.8
247.8
246.9
246.3
246.5
245.8
245.6
233.1
232.7
233.2
284.8
284.8
269.6
249.0
248.1
249.0
246.5
246.4
249.8
248.1
244.4
231.5
233.8
231.9
277.6
277.6
275.5
246.8
247.6
246.8
246.8
246.0
250.2
247.6
244.6
232.4
233.0
232.7
[a] The atomic numbering refers to Figure 1. Columns Exp. I and Exp. II
contain the experimental data for molecules I (C2 symmetry) and II (D2
symmetry) of 1, respectively. X specifies the central atom (Au10 in 1;
Figure 1) and q the charge (+ 3 in 1) of the model compounds
[XAu18(AsnPr)8{Me2P(CH2)2PMe2}6]q.
The cations consist of two opposing Au5As2 units that are
composed of two corner-sharing Au3As tetrahedra each
(Figures 2 and 3). Analogous structures have been observed
for gold selenide clusters, for example, [Au10Se4(dppm)4]2+,
[Au10Se4(dpppe)4]2+
(dpppe = Ph2P(CH2)5PPh2),
and
[Au10Se4(depe)4]2+ (depe = Et2P(CH2)2PEt2).[10b, c]
Compound 3 crystallizes in the triclinic space group P1̄
with two formula units per unit cell.[14] The molecular
structure of the trication can be described as two opposing
zigzag chains of gold–arsenic tetrahedra with the compositions Au9As4 and Au8As4 (Figures 1 and 3). The Au9As4 chain
consists of four corner-sharing Au3As tetrahedra, as observed
in the chains 1 and 2. The Au8As4 chain is built from two
Au3As tetrahedra and two interpenetrating Au2As2 tetrahedra, which share a common As1As2 edge from an As2nPr2
group. The appearance of ligands containing AsAs bonds,
formed by redox side-reactions, has also been observed for
arsenide clusters of other coinage metals.[2]
Compound 4 crystallizes in the orthorhombic space group
Pbcn with four formula units per unit cell.[14] The dication in 4
has a structure very similar to that of 2 (Figures 2 and 3),
containing two opposing Au5As2 units that are each composed
of two Au3As tetrahedra.
To clarify both the composition and the charge of the
[Au19(AsnPr)8(dppe)6]3+ ion in 1, DFT calculations were
undertaken, prior to the ESI-MS characterization. The
structure of the cation in 3 was also investigated to ascertain
the performance of the computational method.
The calculated and experimental interatomic distances of
the cation of 3 are compared in Figure 6. All of the calculated
AsX (X = Au, As, P) and more than 90 % of the calculated
AuX bond lengths are within 6 pm of the experimental
lengths, the calculated values always being larger than the
experimental ones. The largest deviations in the AuAu
Angew. Chem. Int. Ed. 2006, 45, 3702 –3708
Figure 6. Histogram of deviations between experimental and
calculated interatomic distances in the cation of 3. Two types of
distances are considered: AsX and AuX (X = Au, As, P) up to
300 pm. The number of cases of each type is given in brackets.
distances occur for the nonbonded atom pairs Au3Au4
(12 pm) and Au12Au13 (17 pm; Figure 1). The proximity of
these pairs of atoms is imposed by the bidentate phosphine
ligands, which predictably leads to larger errors in the
calculated distances. Thus, the accuracy of the calculated
structure of 3 is similar to that attained for other cluster
compounds;[11, 16] with the exception of particularly long or
weak bonds, the calculated and measured bond distances
differ by less than 6 pm.
For the cluster of 1, three model compounds 1 a–c of
formula [XAu18(AsnPr)8{Me2P(CH2)2PMe2}6]q, where X is the
atom in position Au10 (Figure 1), and q is the ion charge, were
considered and structurally optimized.
½AuAu18 ðAsnPrÞ8 fMe2 PðCH2 Þ2 PMe2 g6 3þ ðX ¼ Au, q ¼ þ3Þ 1 a
½AsAu18 ðAsnPrÞ8 fMe2 PðCH2 Þ2 PMe2 g6 ðX ¼ As, q ¼ 1Þ 1 b
½AsAu18 ðAsnPrÞ8 fMe2 PðCH2 Þ2 PMe2 g6 þ ðX ¼ As, q ¼ þ1Þ 1 c
On the basis of the structural analysis, 1 a seemed to be the
most likely variant. Model compounds 1 b and 1 c were
chosen, because in these variants the gold atom at the center
of the unusual Au7 moiety in the cation of 1 is replaced by an
anion. The q = 1 charge of 1 b corresponds to the most
common oxidation states (Au+, As3); the q = + 1 charge of
1 c allows the accommodation of a chloride counterion.
Structure optimizations were performed in D2 symmetry,
the point symmetry of molecule II of 1 (see above). In Table 2,
the calculated and experimentally determined AsAu,
AuAu, and AuP distances are compared.
The results are surprising, as the bond lengths for all three
compounds match comparatively well with the experimental
bond lengths, considering that structural differences also
occur between the two crystallographically independent
molecules I and II of 1 (Table 2, entries 1 and 2). A more
detailed analysis is necessary to discriminate between the
alternatives. If the shorter bonds are considered (Table 2,
entries 4–14), it is apparent that the lengths calculated for 1 a
are slightly greater than the experimental lengths, the
deviations being in the usual range (less than 6 pm). The
same holds for 1 b and 1 c, with the exception that the values in
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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entries 5, 9, and 10 of Table 2 have deviations of up to 8 pm.
As the calculated XAu2 and XAu5 distances for 1 c are too
short and the calculated XAu8 distance is clearly too long
(Table 2, entries 1–3), this model can be discarded. On the
basis of the calculated bond lengths, we prefer model 1 a, but
cannot definitely exclude 1 b. Whether X = As or Au is
present as the central atom in the cation of 1 can only be
decided by ESI-MS.
Further support for the assignment of X = Au in the cation
of 1 is provided by the comparison of the calculated electronic
energies of 1 a with photoluminescence data for 1. The
photoluminescence excitation (PLE) and emission (PL)
spectra of crystals of 1 and 3 dispersed in nujol are shown in
Figure 7. Both clusters display weak near-infrared lumines-
and 1 c, supporting the assignment of X = Au in the cation of
1.
The emission of 1 a (vertical dipole-forbidden transition
from the minimum of the lowest excited state 3A to the
ground state) is calculated at an energy of 1.18 eV (1048 nm),
in reasonable agreement with the relatively weak PL peak
observed at l = 810 nm at T = 25 K. A possible reason for the
difference between these values could be the replacement of
the phenyl groups by methyl groups in the model compounds
used for the calculations. We therefore replaced the eight
methyl groups of the two bidentate phosphine ligands that
connect Au4 to Au7 and Au4’ to Au7’ (Figure 1) in 1 a by
phenyl groups. However, this model led to only slight changes
in the calculated transition energies for absorption: 1.40 (886)
[3A], 2.58 (480) [3B1], 2.58 (480) [3B2], 2.46 eV (504 nm) [3B3];
and for luminescence: 1.21 eV (1025 nm) [3A]. The difference
between the observed and predicted PL energies may be due
to a structural change in the excited state; that is, the
luminescence may occur from an excited-state structure that
is different from the one located.
At low temperatures, an unusual emission consisting of
two components at l 725 and 910 nm is observed for 3
(Figure 7, curves c and e). The PLE spectrum corresponding
to the first component (acquired at the emission wavelength
of 700 nm) is dominated by a sharp peak at l 525 nm. Such a
spectral shape cannot be explained by the presence of another
isomer of 3 or another gold complex. Therefore, we suppose
that the dual emission may be the result of different, weakly
coupled radiative relaxation channels in 3. This interesting
issue is the subject of further investigation.
Experimental Section
Figure 7. Normalized PLE and PL spectra of nujol mulls of crystals of
1 (top) and 3 (bottom). The emission and excitation wavelengths for
the PLE and PL spectra, respectively, of 1 are indicated by short vertical
lines. The emission wavelengths for the PLE spectra of 3 are a) 950 nm
and b) 700 nm, and the excitation wavelengths for the PL spectra of 3
are c) 400 nm, d) 500 nm, and e) 550 nm. Insets: temperature
dependence of the integrated PL intensities of 1 (excitation at 450 nm)
and 3 (excitation at 400 nm).
cence, the intensity of which strongly increases upon cooling
below 50 K (Figure 7, insets). Similar, but very weak and
broad PL peaks with maxima at l 840 and 890 nm were
observed in CH2Cl2 solutions of 1 and 3 at ambient temperature (not shown).
The PLE spectrum of 1 consists of a poorly structured
absorption band between l = 400 and 700 nm, which is
consistent with the black color of the crystals. The calculated
vertical excitations of 1 a (point group D2, excitation from the
HOMO a to the LUMOs a, b1, b2, b3) are: 1.38 (894) [3A,
dipole forbidden], 2.66 (465) [3B1], 2.62 (472) [3B2], and
2.59 eV (479 nm) [3B3].[17] These values are in good agreement
with the PLE spectrum of 1. Much smaller excitation energies,
well under 1 eV, are calculated for the model compounds 1 b
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All experiments were carried out under a purified nitrogen atmosphere. CH2Cl2 was dried over P2O5, THF over sodium/benzophenone,
and n-pentane over LiAlH4. As(nPr)(SiMe3)2 was synthesized from
LiAs(SiMe3)2 and nPrCl using a modified literature method.[18]
As(Ph)(SiMe3)2,[19] [(AuCl)2dppe],[10d] and [(AuCl)2dppm][10d] were
prepared according to standard procedures.
1, 2: As(nPr)(SiMe3)2 (0.03 mL, 0.116 mmol) was added to a
suspension of [(AuCl)2dppe] (0.1 g, 0.116 mmol) in CH2Cl2 (10 mL).
The resulting deep yellow solution was layered with n-pentane, and
black crystals of 1 and yellow crystals of 2 formed after a few days.
The crystals were separated by hand for the spectroscopic measurements.
3: As(nPr)(SiMe3)2 (0.033 mL, 0.124 mmol) was added to a
solution of [(AuCl)2dppm] (0.105 g, 0.124 mmol) in CH2Cl2 (10 mL).
The resulting brown solution was layered with THF, and orange
crystals of 3 formed after a few weeks.
4: As(Ph)(SiMe3)2 (0.04 mL, 0.116 mmol) was added to a
suspension of [(AuCl)2dppe] (0.1 g, 0.116 mmol) in CH2Cl2 (10 mL).
By layering the resulting yellow solution with n-pentane, yellow
crystals of 4 were obtained.
X-ray structure determination: Data were collected on a STOE
IPDS II diffractometer using MoKa radiation (l = 0.71073 I). Structure solution and refinement against F 2 were carried out using the
SHELXS and SHELXL programs.[20] CCDC-297861 (1), CCDC297862 (2), CCDC-297863 (3), and CCDC-297864 (4) contain the
supplementary crystallographic data for this paper. These data can be
obtained free of charge from The Cambridge Crystallographic Data
Centre via www.ccdc.cam.ac.uk/data_request/cif.
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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Mass spectra were recorded on a Fourier transform ion cyclotron
resonance (FT-ICR) mass spectrometer (Bruker Daltonics, APEX II)
equipped with a 7T magnet and an electrospray ionization source
(Analytica of Branford), as well as a noncommercial radio-frequency
ion optics for improved sensitivity. Solutions of hand-picked crystals
of 1 and 2, and of 3 in CH2Cl2 were sprayed using nitrogen as
nebulizing gas at a flow rate of 300 mL h1. The desolvation capillary
was typically heated to 353 K.
For the collection of the PL and PLE spectra, crystals of 1 and 3
were dispersed in nujol, layered between two quartz plates, and
placed in a closed-cycle optical cryostat (Leybold) operating at 20–
293 K. The spectra of solutions of 1 and 3 in CH2Cl2 were measured in
standard cuvettes at ambient temperature. Emission spectra were
corrected for the wavelength-dependent response of the spectrometer.[10b]
DFT calculations were carried out with the TURBOMOLE
program package.[21] The phenyl groups in the cations of 1 and 3 were
replaced by methyl groups to reduce computational cost. The TPSS
functional was chosen, because it describes the interactions of gold
atoms particularly well and gives better structural parameters than
other functionals (for example, BP86).[22] We used the newly
developed triple zeta valence with polarization (TZVP) basis set
(including an f set for P, As, and Au) with the corresponding auxiliary
bases; for hydrogen atoms, the smaller split-valence (SV) basis was
adopted.[23] A relativistic effective core potential (RECP) was used
for gold.[24] All calculations were carried out using the multipole
accelerated resolution of identity (MARI-J) technique.[25]
[9]
[10]
Received: December 22, 2005
Revised: March 3, 2006
Published online: May 8, 2006
.
Keywords: arsenic · cluster compounds · density functional
calculations · gold · mass spectrometry
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Crystallographic data: 1·7 CH2Cl2 : C187H214As8Au19Cl17P12, tetragonal, space group P42/nbc, Z = 12, a = 4280.3(6), c =
3883.0(8) pm, V = 71 140(20) U 106 pm3, T = 180(2) K, 1calcd =
2.179 g cm3, 68 271 data measured, 26 514 unique data (Rint =
0.0531), 1555 parameters, wR2 = 0.2026 (all data), R1 = 0.0678
(I > 2 s(I)), max./min. electron density 2.946/6.005 e A3 (the
remaining electron density is located near the lattice-bound
solvent molecules, suggesting additional disorder). 2:
C116H124As4Au10Cl2P8, orthorhombic, space group C2221, Z = 8,
a = 2237.6(5), b = 2339.5(5), c = 4667.6(9) pm, V = 24 434(8) U
106 pm3, T = 200(2) K, 1calcd = 2.232 g cm3, 67 071 data measured, 23 763 unique data (Rint = 0.0879), 911 parameters,
wR2 = 0.2259 (all data), R1 = 0.0775 (I > 2 s(I)), max./min. electron density 4.676/2.531 e A3, Flack parameter 0.05(2), e21 =
0.779. 3·2 CH2Cl2 : C176H192As8Au17Cl7P12, triclinic, space group
P1̄, Z = 2, a = 1776.4(4), b = 2151.2(4), c = 3221.4(6) pm, a =
88.04(3), b = 77.25(3), g = 73.93(3)8, V = 11 534(4) U 106 pm3,
T = 200(2) K, 1calcd = 1.980 g cm3, 108 569 data measured,
39 671 unique data (Rint = 0.1429), 1114 parameters, wR2 =
0.2368 (all data), R1 = 0.0824 (I > 2 s(I)), max./min. electron
density 3.233/1.484 e A3. 4·2 CH2Cl2 : C130H120As4Au10Cl6P8,
orthorhombic, space group Pbcn, Z = 4, a = 1938.7(4), b =
2865.0(6), c = 2810.9(6) pm, V = 15 613(5) U 106 pm3, T =
200(2) K, 1calcd = 1.877 g cm3, 64 894 data measured, 15 143
unique data (Rint = 0.1054), 634 parameters, wR2 = 0.2184 (all
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
3707
Communications
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The states 3A, 3B1, 3B2, and 3B3 can be calculated by standard
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www.angewandte.org
2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2006, 45, 3702 –3708
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stabilizer, calculations, cl3, asph, cl2, phosphine, dft, synthesis, clusters, dppm, dppe, characterization, as2npr2, asnpr, au19, au10, goldцarsenic, au17
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