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org/JACS Communication

Photoluminescence of Doped Superatoms M@Au12 (M = Ru, Rh, Ir)

Homoleptically Capped by (Ph2)PCH2P(Ph2): Efficient Room-
Temperature Phosphorescence from Ru@Au12
Shinjiro Takano, Haru Hirai, Takuya Nakashima, Takeshi Iwasa, Tetsuya Taketsugu,
and Tatsuya Tsukuda*
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sı Supporting Information

ABSTRACT: A series of doped gold superatoms M@Au12 (M = Ru, Rh, Ir) was synthesized by capping with the bidentate ligand
(Ph2)PCH2P(Ph2). A single-crystal X-ray diffraction analysis showed that all the M@Au12 superatoms had icosahedral motifs with a
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significantly higher symmetry than that of the pure Au13 counterpart due to different coordination geometries. The Ru@Au12
superatom exhibited a room-temperature phosphorescence with the highest quantum yield of 0.37 in deaerated dichloromethane.
Density functional theory calculations suggested that the efficient phosphorescence is ascribed to a rapid intersystem crossing due to
the similarity between the singlet and triplet excited states in terms of structure and energy.

L igand-protected gold clusters exhibit novel photoinduced

phenomena arising from the nonmetallic, discrete energy
levels. Photoluminescence (PL)1−11 is a typical example of
to the formation of 1O2. A density functional theory (DFT)
calculation on a model, [Ru@Au12(dmpm)6]2+ (dmpm =
(Me2)PCH2P(Me2)), showed that the rapid intersystem
such phenomena. The PL quantum yields (QYs) reach as high crossing (ISC) at room temperature is ascribed to the
as ∼10−1 as reported for [Au13(dppe)5Cl2]3+ (dppe = energetic and structural similarity between the T1 and S1 states.
(Ph2)PCH2CH2P(Ph2)),12 [Au13(NHC)9Cl3]2+ (NHC = N- Clusters 1−3 in a pure form (Figures S1−S6) were
heterocyclic carbene),13 and [Au13(di-NHC)5Br2]3+.14 Another synthesized according to the methods described in the
interesting photoinduced phenomenon is the singlet oxygen Supporting Information.24 Cluster 1 was crystallized as a salt
(1O2) photosensitization via the energy transfer from the of B5O10H4− (B5),25 probably formed via the hydrolysis of
triplet state.15,16 The relaxation dynamics of the photoexcited NaBH4. The crystal structure of 1·(B5)2 (Figure 1a)
state have been extensively studied by means of time-resolved demonstrates that 1 had nearly a perfect icosahedral Ru@
spectroscopy and theoretical calculations.17−20 A key to
Au12 core with a pseudo Th symmetry, as indicated by the small
enhancing the PLQYs of the protected Au clusters is to retard
value (0.062) of the continuous symmetry measure (CSM).26
the nonradiative decay of a photoexcited state by decoupling
with vibrationally excited states in the electronic ground state. Crystal structures of PF6− salts of 1−3 were solved by SCXRD
This can be achieved by reducing the density of vibrationally as summarized in Table 1. Clusters 1−3 had icosahedral M@
excited states by a rigidification of the Au core21 and expanding
the energy gap between the highest occupied molecular orbital
(HOMO) and the lowest unoccupied molecular orbital
(LUMO).22
To test the hypothesis, we developed here prototypical
systems composed of icosahedral M@Au12 superatomic cores
homoleptically protected by short diphosphines. For the
dopant M, we chose Ru, Rh, and Ir, which have a lower
valency than Au,23 since the HOMO−LUMO gap may be
Figure 1. (a) X-ray structure of 1·(B5)2 and coordination geometries
enlarged according to an empirical rule.11 For the diphosphine of dppm (red sticks) in (b) 1·(B5)2 and (c) [Au13(dppm)6]5+.27 Color
ligand, we chose (Ph2)PCH2P(Ph2) (dppm) having less code: yellow = Au; green = Ru; blue = P; gray sticks = C.
structural flexibility than dppe to restrict the internal motion
of the core. We herein synthesized [RuAu12(dppm)6]2+ (1),
[RhAu12(dppm)6]3+ (2), and [IrAu12(dppm)6]3+ (3) and Received: May 14, 2021
revealed their icosahedral structures by single-crystal X-ray Published: July 7, 2021
diffraction (SCXRD) analyses. Cluster 1 in deaerated
dichloromethane (DCM) at room temperature exhibited a
red (∼720 nm) phosphorescence with the highest QY of
∼0.37, which was almost completely quenched by O2, leading
© 2021 The Authors. Published by
American Chemical Society https://doi.org/10.1021/jacs.1c05019
10560 J. Am. Chem. Soc. 2021, 143, 10560−10564
Journal of the American Chemical Society pubs.acs.org/JACS Communication

Table 1. Structural Data of 1−3 Obtained by an SCXRD indicates that the counteranion does not affect the PL
Analysis properties. Clusters 2 and 3 in deaerated DCM exhibited PL
at 910 and 735 nm (Figure 2b,c) with QYs of 0.0126 and
average bond length (Å)
0.135 (Figure S10), respectively.
cluster M−Au Au−Au Au−P CSMa The PL intensity of 1 was drastically quenched to 3.4% and
1·(B5)2 2.727 ± 0.007 2.868 ± 0.059 2.301 ± 0.011 0.062 ∼0.5% under air and pure O2, respectively (Figure 2a). In
1·(PF6−)2 2.730 ± 0.003 2.872 ± 0.061 2.305 ± 0.016 0.061 contrast, the PL intensities of 2 and 3 were suppressed to 89%
2·(PF6−)3 2.737 ± 0.016 2.879 ± 0.066 2.308 ± 0.014 0.079 and 62% under pure O2, respectively (Figure 2b,c). In the
3·(PF6−)3 2.741 ± 0.014 2.883 ± 0.072 2.301 ± 0.013 0.091 following, we will focus on the PL properties of 1.
a
Continuous symmetry measure. Phosphorescence of 1O2 was observed at 1274 nm from the
aerated DCM solution of 1 (Figure 2d), indicating that 1 acted
Au12 cores (M = Ru, Rh, Ir) with a pseudo Th symmetry: the as a triplet photosensitizer. The PL of 1 is assigned mainly to
CSM values were 0.061, 0.079, and 0.091, respectively. Table 1 phosphorescence from the triplet excited state (T1), because
also indicates that the dopant and counteranion did not affect the PL intensity was almost completely suppressed by the
the structures of the M@Au12 cores of 1−3. The highly presence of O2. The phosphorescence lifetime (τ) in the
symmetrical cores of 1−3 are in sharp contrast to the distorted absence of O2 was determined to be 5.7 μs, while that in air-
Au13 core (D3 symmetry) of [Au13(dppm)6]5+ with CSM = equilibrated DCM containing 2.2 mM O2 (ref 28) was reduced
0.568.11,27 This significant difference in the core symmetry to 0.22 μs (Figure 2e). By using the values of τ and the PLQY
between 1−3 and [Au13(dppm)6]5+ arises from the difference (Φ) at [O2] = 0 and 2.2 mM (Figures 2a,e), the rate constants
in the coordination geometry of the dppm ligands (Figure of the phosphorescence (kr), nonradiative decay (knr), and
1b,c). quenching (kq) were estimated to be 6.4 × 104 s−1, 1.1 × 105
The black and red traces in Figure 2 show the absorption s−1, and 2.0 × 109 s−1 M−1, respectively.24 The kq value of 1 is
and PL spectra of 1−3 in deaerated DCM, respectively. The comparable to that of a representative triplet photosensitizer
[Ru(bpy)3]2+ (2.75 × 109 s−1 M−1).29 Recently, an efficient
phosphorescence was also observed from an Au@Cu14 cluster
even in an aerated solution.30,31 The efficient room-temper-
ature phosphorescence will find interesting applications in the
photon upconversion based on a triplet−triplet annihilation as
recently demonstrated using [PtAg24(SR)18]2−.32
A question arises as to why fluorescence from the S1 state
was not observed from 1. To address this question, a
temperature-dependent optical measurement was conducted
on 1 in a deaerated EtOH−MeOH (1:1 v/v) mixture. Figure
3a shows that four absorption bands are monotonically blue-
shifted and sharpened with a decrease in the temperature. This
behavior can be explained by the suppression of the hot band
transition at a reduced temperature.33,34 A reduction in the
temperature resulted in a sudden blue shift of the PL emission
wavelength from ∼700 to ∼660 nm at a narrow temperature
range of 120−140 K (Figure 3b): a similar phenomenon was
Figure 2. Absorption (solid black) and PL spectra (red) of (a) 1· also observed in frozen DCM (Figure S11). By deconvoluting
(B5)2, (b) 2·(PF6−)3, and (c) 3·(PF6−)3 in deaerated DCM. Dashed the PL spectra in Figure 3b, we found that another state
black lines represent the excitation spectra of PL at (a) 720, (b) 910, besides T1 is responsible for the 660 nm emission at a low
and (c) 735 nm. Green and blue traces correspond to the PL under temperature (<120 K) (Figure S12). The other state is
air and O2 atmosphere, respectively. (inset, a) Magnified view of the assigned to the S1 state, since the PL was observed even in the
PL spectra. (d) NIR emission spectra of 1·(PF6−)2 under Ar (black) presence of O2 (Figure S13). Namely, the PL at less than 120
and air (red) excited at 440 nm. (inset) Photographs of 1 in DCM
under Ar (left) and air (right) excited at 340 nm, respectively. (e) The
K is mainly assigned to fluorescence. The PL lifetimes
PL (720 nm) decay curves of 1·(B5)2 in DCM under Ar (red) and air estimated by fitting the decay curves with a single exponential
(blue) excited at 371 nm. Black and green traces represent the fitted component (Figures 3c and S14) are plotted as a function of
results using a single exponential function. the temperature in Figure 3c and summarized in Table S1. The
lifetime gradually increased with a reduction in the temper-
ature from 7.3 μs at 300 K to 14.2 μs at 140 K and jumped up
quantized electronic structure of 1 was confirmed by a well- to more than 20 μs at 120−80 K. The PL decay curve at 130 K
structured spectral profile and voltammogram (Figure S7). (Figure 3d) is composed of a fast (13.6 μs) decay component
The spectral onsets of 1, 2, and 3 were 635, 840, and 730 nm centered at ∼660 nm, followed by a slower rise and decay (7.0
(1.95, 1.47, and 1.69 eV), respectively. Cluster 1 had the and 14.5 μs) component centered at ∼700 nm. The
largest HOMO−LUMO gap among 1−3 as expected from the temperature-dependent PL of 1 is summarized in Scheme 1.
empirical rule: the HOMO−LUMO gap increases when At room temperature, the S1 state formed by the internal
doping a smaller group element at the center of Au13.11 conversion of the photoexcited Sn states quickly undergoes ISC
Cluster 1 in deaerated DCM exhibited an intense PL peak at to the T1 state (Scheme 1a). The T1 state thus populated emits
720 nm (Figure 2a). The PLQYs for 1·(B5)2 and 1·(PF6−)2 a red phosphorescence (720 nm; 1.72 eV) with a QY of 0.37,
estimated by the absolute method under Ar (Figures S8 and which was efficiently quenched by O2 to generate 1O2. When
S9) were as high as 0.365 and 0.379, respectively. This result the temperature was reduced to less than 130 K, the ISC was
10561 https://doi.org/10.1021/jacs.1c05019
J. Am. Chem. Soc. 2021, 143, 10560−10564
Journal of the American Chemical Society
Figure 3. Temperature-dependent optical properties of 1·(B5)2 in deaerated EtOH−MeOH mixture. (a) UV−Vis absorption spectra. (inset) Peak
energy of band C plotted as a function of the temperature. (b) PL emission spectra excited at 500 nm. (inset) Plot of the peak position as a function
of the temperature. (c) PL decay profiles. (inset) Plot of the decay time constant as a function of the temperature. (d) PL decay profile at 130 K.
Green dots correspond to the PL intensities integrated over 635−730 nm, while blue and red dots show the PL intensities integrated over 640−680
and 680−720 nm, respectively. Blue and red emission spectra in the inset were recorded at less than 20 μs and more than 20 μs after the pump laser
(400 nm).
Scheme 1. PL Processes from 1 at (a) More than 140 K and
(b) Less than 130 K
suppressed almost completely, and the PL switched to
fluorescence from the S1 state (660 nm; 1.88 eV) (Scheme
1b).
We hypothesized that the efficient ISC in 1 at a temperature
of more than 140 K is associated with a subthermal barrier
between the S1 and T1 states. This situation is realized when
the S1 and T1 states are energetically and structurally similar
given that the barrier is generated by the avoided crossing of
the potential surfaces of the S1 and T1 states. To test the
hypothesis, we conducted DFT calculations on a model
system, [RuAu12(dmpm)6]2+ (1Me) (dmpm = (Me2)PCH2P-
(Me2)). The optimized structure of 1Me in the S0 state is shown
in Figure 4a. A natural bond orbital analysis of 1Me (Table S2)
revealed that Ru has a formal valency of −2 and withdraws two
Figure 4. (a) Optimized structures and (b) bond length distributions
of 1Me in the S0, S1, and T1 states. (c) Schematic potential energy
curves relevant to PL.
10562
pubs.acs.org/JACS Communication
valence electrons of Au. According to the superatom complex
model,35 the number of valence electrons in 1 is calculated to
be 8 (=12 − 2 − 2), suggesting that the Ru@Au12 core
corresponds to an electronically closed superatom. A Kohn−
Sham orbitals analysis of 1Me (Figure S15) supports the closed
superatomic electron configuration (1S)2(1P)6, whereas a
recent DFT study proposed the electron configuration of
(1S)2(1P)2(1D)10(1P)4 for [RuAu12(dppe)5Cl2].36 The opti-
mized structures of 1Me in the S1 and T1 states are presented in
Figure 4a. A detailed analysis (Figure 4b and Table S3) reveals
the structural similarity between the S0, S1, and T1 states. The
phosphorescence energy was calculated to be 1.23 eV from the
energy difference between the T1 and S0 states at the T1-
optimized structure, while the fluorescence energy was
determined to be 1.49 eV from the energy difference between
the S1 and S0 states at the S1-optimized structure. Figure 4c
indicates that the T1 and S1 states are comparable in energy
(ΔE = 0.03 eV). On the basis of these theoretical results, we
conclude that a low energy barrier is responsible for the rapid
ISC. However, further studies are necessary, including the
doping effects on spin−orbit coupling, to elucidate the
mechanism.
In summary, icosahedral superatoms M@Au12 (M = Ru, Rh,
Ir) homoleptically protected by rigid diphosphines, dppm,
were synthesized and characterized by SCXRD analyses and
DFT calculations. The M@Au12 superatoms had a higher
symmetry and larger HOMO−LUMO gaps compared to the
pure Au13 counterpart.27 The Ru@Au12 superatom exhibited
an O2-sensitive phosphorescence at 720 nm with a QY of 0.37
at room temperature, while it emitted fluorescence at 660 nm
at a low temperature of less than 130 K. The temperature-
induced switching between phosphorescence and fluorescence
was explained by a small energy barrier for ISC from the S1 to
T1 state.
■ ASSOCIATED CONTENT
* Supporting Information
sı
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/jacs.1c05019.
Synthesis details and other characterization data (PDF)
Accession Codes
CCDC 2076176−2076179 contain the supplementary crys-
tallographic data for this paper. These data can be obtained
https://doi.org/10.1021/jacs.1c05019
J. Am. Chem. Soc. 2021, 143, 10560−10564
Journal of the American Chemical Society
free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by
emailing 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.
■
AUTHOR INFORMATION
Corresponding Author
Tatsuya Tsukuda − Department of Chemistry, Graduate
School of Science, The University of Tokyo, Tokyo 113-0033,
Japan; Elements Strategy Initiative for Catalysts and
Batteries, Kyoto University, Kyoto 615-8520, Japan;
orcid.org/0000-0002-0190-6379; Email: tsukuda@
chem.s.u-tokyo.ac.jp
Authors
Shinjiro Takano − Department of Chemistry, Graduate
School of Science, The University of Tokyo, Tokyo 113-0033,
Japan; orcid.org/0000-0001-9262-5283
Haru Hirai − Department of Chemistry, Graduate School of
Science, The University of Tokyo, Tokyo 113-0033, Japan
Takuya Nakashima − Division of Materials Science, Nara
Institute of Science and Technology, Nara 630-0192, Japan;
orcid.org/0000-0002-5311-4146
Takeshi Iwasa − Department of Chemistry, Faculty of Science,
Hokkaido University, Sapporo 060-0810 Hokkaido, Japan;
Elements Strategy Initiative for Catalysts and Batteries, Kyoto
University, Kyoto 615-8520, Japan; orcid.org/0000-
0002-1611-7380
Tetsuya Taketsugu − Department of Chemistry, Faculty of
Science, Hokkaido University, Sapporo 060-0810 Hokkaido,
Japan; Elements Strategy Initiative for Catalysts and
Batteries, Kyoto University, Kyoto 615-8520, Japan;
orcid.org/0000-0002-1337-6694
Complete contact information is available at:
https://pubs.acs.org/10.1021/jacs.1c05019
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This research was financially supported by JST, CREST (Grant
No. JPMJCR20B2), the Elements Strategy Initiative for
Catalysts & Batteries (ESICB) (Grant No.
JPMXP0112101003) of MEXT, and by JSPS KAKENHI
(Grant Nos. JP19K15499, JP20H00370, and JP20H04652).
The SCXRD experiment was supported by the Nano-
technology Platform (Advanced Characterization Nanotech-
nology Platform, Project No. JPMXP09A20UT0024) of
MEXT, Japan. Mr. Y. Okajima (NAIST) is acknowledged for
his technical assistance in the temperature-dependent lifetime
measurement.
■
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