Optical properties of silver(I) hexauoroantimonate(V):

luminescence from a metal-to-metal charge transfer state

involving a transition and a main group metal
Horst Kunkely, Arnd Vogler
*
Institut fur Anorganische Chemie, Universitat Regensburg, D-93040 Regensburg, Germany
Received 21 October 2003; accepted 12 December 2003
Published online: 14 January 2004
Abstract
The salt Ag

SbF

6
shows a greenish-yellow luminescence (k
max
528 nm) which originates from a Ag
I
!Sb
V
metal-to-metal
charge transfer triplet.
2004 Elsevier B.V. All rights reserved.
Keywords: Electronic spectra; Photoluminescence; Charge transfer; Silver; Antimony
The chemistry of the main group metals is dominated
by the electron conguration s
2
(e.g., Tl
I
, Sn
II
, Pb
II
,
Sb
III
, Bi
III
) and s
0
(e.g., Tl
III
, Sn
IV
, Pb
IV
, Sb
V
). The
photochemistry and photophysics of coordination
compounds of these metals has been studied in some
detail [14]. The s
2
complexes are characterized by low-
energy metal-centered (MC) sp excited states which are
frequently emissive [13], and occasionally reactive
[1,2,4]. In analogy to d
0
complexes of transition metals,
s
0
complexes with simple ligands such as halides have
available only ligand-to-metal charge transfer (LMCT)
states which are not emissive, but reactive. We have
recently observed that the d
10
/d
0
combination as it oc-
curs in AgReO
4
shows a luminescence which originates
from a Ag
I
!Re
VII
metal-to-metal charge transfer
(MMCT) excited state [5]. Accordingly, it is conceivable
that a suitable d
10
/s
0
combination is also emissive. We
explored this possibility and selected the compound
Ag
I
Sb
V
F
6
for the present study. This choice was not
only based on the analogy to AgReO
4
. The silver cation
shows a MC 4d !5s transition at very high energies
[6,7]. LMCT transitions of SbF

6
are certainly also lo-
cated at exceedingly high energies owing to the fact that
uoride is hardly reducing. For comparison, SbCl

6
shows its longest-wavelength LMCT absorption at
k
max
272 nm [8]. Moreover, Sb(V) has been shown to
act as a CT acceptor for Sb(III). Mixtures of Sb(III) and
Sb(V) in HCl display low-energy MMCT absorptions
[9]. From these considerations it follows that AgSbF
6
is
a promising candidate for the observation of a lumi-
nescent Ag
I
!Sb
V
MMCT excited state which is not
obscured by excited states of the separate components
Ag

and SbF

6
at comparable energies.
The compounds AgSbF
6
and NaSbF
6
are commer-
cially available from Alfa Aesar and used without fur-
ther purication. Emission and excitation spectra were
recorded on a Hitachi 850 spectrouorometer equipped
with a Hamamatsu R928 photomultiplier for measure-
ments upto 900 nm. The luminescence spectra were
corrected for monochromator and photomultiplier e-
ciency variations. Emission quantum yields were
obtained according to a literature procedure which has
been applied to powdered samples [10]. Emission
lifetimes were measured on a luminescence analysis
system (model LS-100-07) from Photon Technology
International.
*
Corresponding author. Tel.: +49-941-9434485; fax: +49-941-
9434488.
E-mail address: arnd.vogler@chemie.uni-regensburg.de (A. Vo-
gler).
1387-7003/$ - see front matter 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.inoche.2003.12.027
www.elsevier.com/locate/inoche
Inorganic Chemistry Communications 7 (2004) 400401
Under ambient conditions solid AgSbF
6
shows a
greenish-yellow luminescence (k
max
540 nm) with a
quantum yield of / 10
4
at k
exc
300 nm. At 77 K
this emission (Fig. 1) shifts to k
max
528 nm and be-
comes more intense (/ 10
3
). It decays with s 3:4
ls. The excitation spectrum (Fig. 1) displays two bands
at k
max
234 and 290 nm. The salt NaSbF
6
is not lu-
minescent. In acetonitrile NaSbF
6
starts to absorb at
250 nm. Any absorption maximum of SbF

6
must be
located below 200 nm.
According to the structural features AgSbF
6
is rather
ionic [11]. It contains isolated SbF

6
octahedra as they
occur also in other SbF

6
salts. The silver ions are at-
tached to SbF

6
via uoride bridges. Ag

is thus coor-
dinated by six uoride ions forming a distorted
octahedron. There are no close Ag

/Ag

contacts.
The Ag

ion is characterized by a metal-centered

(MC) 4d !5s transition at 255 nm [6,7]. The absorption
spectra of simple Ag

species exhibit their longest-

wavelength ds bands below 250 nm [6,12,13]. The
corresponding absorption of the Ag
I
F
5
6
moiety does
certainly also occur in this spectral region. The anion
SbCl

6
shows a long-wavelength LMCT absorption at
k
max
272 nm [8]. Since F

is less reducing than Cl

the
LMCT absorption of SbF

6
displays its longest-wave-
length maximum below 200 nm. Accordingly, the exci-
tation band of AgSbF
6
at k
max
234 nm is attributed to
the Ag

(or Ag
I
F
5
6
) ion while the longer-wavelength
excitation at 290 nm must result from the interaction
between Ag
I
and Sb
V
. It is then logically assigned to a
Ag
I
!Sb
V
MMCT transition taking into account the
reducing character of Ag
I
and the oxidizing nature of
Sb
V
.
The emission of AgSbF
6
certainly originates from
this MMCT state. In agreement with the general be-
havior of heavy elements such as silver and antimony
the emissive state is suggested to be a triplet. This
assumption is supported by the relatively slow decay
of this emission.
In this context it should be noted that the MC
emission of isolated Ag

centers occurs at very high

energies (250 nm) [1416]. However, long-wavelength
emissions from silver(I) compounds are also known
[1720], but in these cases a MC emission appears at
relatively low energies owing to direct silver-silver in-
teractions. In AgSbF
6
such silver clusters with short
silversilver distances are not present [11].
In summary, the salt AgSbF
6
is characterized by an
emission from a Ag
I
!Sb
V
MMCT triplet. It is a rare
case of a luminescent MMCT state. Moreover, it seems
to be the rst example of an emissive d
10
/s
0
system. It
also shows that a suitable combination of a transition
and main group metal generates new optical properties.
References
[1] A. Vogler, A. Paukner, H. Kunkely, Coord. Chem. Rev. 97 (1990)
285.
[2] A. Vogler, H. Nikol, Pure Appl. Chem. 64 (1992) 1311.
[3] A. Vogler, H. Nikol, Comments Inorg. Chem. 14 (1993) 245.
[4] O. Horvath, K.L. Stevenson, Charge Transfer Photochemistry of
Coordination Compounds, VCH, New York, 1993.
[5] H. Kunkely, A. Vogler, Inorg. Chim. Acta, in press.
[6] C.K. Jrgensen, Absorption Spectra and Chemical Bonding in
Complexes, Pergamon Press, Oxford, 1962.
[7] L.E. Orgel, J. Chem. Soc. (1958) 4186.
[8] A. Vogler, A. Paukner, Inorg. Chim. Acta 163 (1989) 207.
[9] G.C. Allen, N.S. Hush, Progr. Inorg. Chem. 8 (1967) 357.
[10] M.S. Wrighton, D.S. Ginley, D.L. Morse, J. Phys. Chem. 78
(1974) 2229.
[11] K. Matsumoto, R. Hagiwara, Y. Ito, O. Tamada, J. Fluorine
Chem. 110 (2001) 117.
[12] K. Fussgaenger, W. Martienssen, H. Bilz, Phys. Stat. Sol. 12
(1965) 383.
[13] W. Dreybrodt, K. Fussgaenger, Phys. Stat. Sol. 18 (1966) 133.
[14] C. Pedrini, B. Jacquier, Phys. Lett. A 69 (1979) 457.
[15] C. Pedrini, H. Chermette, F. Gaume-Mahn, J. Lumin. 24/25
(1981) 213.
[16] C. Pedrini, Solid State Commun. 69 (1979) 457.
[17] P.C. Ford, A. Vogler, Acc. Chem. Res. 26 (1993) 220.
[18] A. Vogler, H. Kunkely, Chem. Phys. Lett. 158 (1989) 74.
[19] F. Sabin, C.K. Ryu, P.C. Ford, A. Vogler, Inorg. Chem. 31 (1992)
1941.
[20] M. Henary, J.I. Zink, Inorg. Chem. 30 (1991) 3111.
Fig. 1. Electronic excitation (k
em
528 nm) and emission (k
exc
300
nm) spectrum of solid AgSbF
6
at 77 K, intensity in arbitrary units.
H. Kunkely, A. Vogler / Inorganic Chemistry Communications 7 (2004) 400401 401