Spatial extent of the singlet and triplet excitons in luminescent angular-shaped transition-metal diynes and polyynes comprising non-π-conjugated Group 16 main group elements

Article abstract of DOI:10.1002/chem.200501011

A novel approach based on conjugation interruption has been developed and is presented for a series of luminescent and thermally stable chalcogen-bridged platinum(II) polyyne polymers trans-[{-Pt(PBu₃)₂C≡C- (C₆H₄

Full text of DOI:10.1002/chem.200501011

DOI: 10.1002/chem.200501011
Spatial Extent of the Singlet and Triplet Excitons in Luminescent Angular-
Shaped Transition-Metal Diynes and Polyynes Comprising
Non-p-Conjugated Group 16 Main Group Elements
Suk-Yue Poon,[a] Wai-Yeung Wong,*[a] Kok-Wai Cheah,[b] and Jian-Xin Shi[a]
Abstract: A novel approach based on
conjugation interruption has been de-
veloped and is presented for a series of
luminescent and thermally stable chal-
cogen-bridged platinum(ii) polyyne
studied by NMR spectroscopy and
single-crystal X-ray structural analyses.
Upon photoexcitation, each one has an
intense purple-blue fluorescence emis-
sion near 400 nm in dilute fluid solu-
tions at room temperature. Harvesting
of the organic triplet emissions har-
nessed through the strong heavy-atom
effects of Group 10–12 transition
metals was studied in detail. These
metal- and chalcogen-based conjuga-
tion interrupters on the intersystem
crossing rate and on the spatial extent
of the lowest singlet and triplet exci-
tons was fully elucidated. We discuss
and compare the phosphorescence
spectra of these transition-metal diynes
and polyynes in terms of the nature of
the metal centre, conjugated chain
length and Group 16 spacer unit. Our
work here indicates that high-energy
triplet states in these materials intrinsi-
cally give rise to very efficient phos-
phorescence with fast radiative decays
and one could readily observe room-
temperature phosphorescence for the
platinum polyynes.
ꢀ
ꢁ
polymers
trans-[{ Pt(PBu3)2C C-
ꢁ ꢀ
(C6H4)E(C6H4)C C }n] (E=O, S, SO,
SO2). Particular attention was focused
on the photophysical properties of
these Group 10 polymetallaynes and
comparison was made to their binu-
clear model complexes trans-[Pt(Ph)-
metal-containing
aryleneethynylenes
spaced by chalcogen units were found
to have large optical gaps and high-
energy triplet states. The influence of
ꢁ
ꢁ
(PEt3)2C C(C6H4)E(C6H4)C CPt(Ph)-
(PEt3)2] and their closest Group 11
gold(i) and Group 12 mercury(ii) neigh-
ꢁ
ꢁ
bours, [MC C(C6H4)E(C6H4)C CM]
(M=Au(PPh3), HgMe; E=O, S, SO,
SO2). The regiochemical structures of
these angular-shaped molecules were
Keywords: alkynes · chalcogens ·
gold · mercury · phosphorescence ·
platinum
Introduction
within the realm of molecular electronics and materials sci-
ence. The use of platinium-containing polyynes both as sem-
iconductors and triplet emitters has been proposed.[7,8]
While considerable work has been devoted to investigations
of the nature of singlet excited states in conjugated poly-
mers,[9–11] much less is known about the nature of their trip-
let excited states. It was shown that the triplet states play an
increasing vital role in the ultimate efficiency of light-emit-
ting diodes (LEDs). For example, photoluminescence is af-
fected by the relative energies of the singlet and triplet
states, and the overall efficiency of LEDs is controlled by
the fraction of triplet states generated or harvested.[12–15] To
better understand the role of triplet states in optical and
electrical processes within conjugated materials and their
potential for a number of applications,[16–22] a comprehensive
investigation of their photophysics is essential. In the litera-
ture, work on the nonradiative decay of triplet states in con-
jugated polymers is still in its infancy. Yet radiationless tran-
sitions are more common than radiative transitions, so a
Over the past decade, conjugated ethynylated materials,
such as arylacetylenes,[1–4] polyarylenethynylenes[5,6] and
metal-containing acetylide complexes and polymers,[7,8] have
become the subject of numerous research endeavours, lead-
ing to a number of significant technological developments
[a] S.-Y. Poon, Dr. W.-Y. Wong, Dr. J.-X. Shi
Department of Chemistry and Centre for Advanced Luminescence
Materials
Hong Kong Baptist University
Waterloo Road, Kowloon Tong, Hong Kong (P. R. China)
Fax : (+852)3411-7348
E-mail: rwywong@hkbu.edu.hk
[b] Prof. K.-W. Cheah
Department of Physics and Centre for Advanced Luminescence
Materials
Hong Kong Baptist University
Waterloo Road, Kowloon Tong, Hong Kong (P. R. China)
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FULL PAPER
knowledge of triplet-state-decay mechanisms is necessary
for a full understanding of the photochemistry of conjugated
arylene–ethynylene systems.
We and others have circumvented the problem of the trip-
let state being nonemissive by using a model system consist-
ing of d8 Pt-containing ethynylenic conjugated complexes
Group 16 heteroatoms in the polymer chains. While the het-
eroatom can act as the conjugation-breaking unit to inter-
rupt the electronic p conjugation, these materials can also
offer an attractive combination of physical, optical and me-
chanical properties. In fact, sulfone-based poly(arylene
ether)s have gained considerable commercial and industrial
importance. Aromatic polymers that contain aryl ether or
aryl sulfone linkages generally have lower glass-transition
temperatures and greater chain flexibility than their corre-
sponding polymers without these groups in the chain.[31–33]
Also, it was well documented that aromatic sulfoxides are
photochemically active molecules and characterisation of
the triplet states of such simple organic molecules as PhEPh
(E=S, SO, SO2) has played a critical role in the develop-
ment of their photochemistry and photophysics.[34,35]
In the present work we report the first examples of
Group 10–12 metal–acetylide polymers and their dinuclear
congeners containing O, S, SO and SO2 functionalities.
These represent unprecedented model systems to evaluate
how the chalcogen-based conjugation interrupters would
limit the effective conjugation length of polymetallaynes.
The significance of the Group 16 residue in this class of ma-
terials in comparison to other conjugated linkers will be dis-
cussed.
ꢀ
ꢁ
and polymers of the general form trans-[{ Pt(PBu3)2C
ꢁ ꢀ
CRC C }n] for which phosphorescence can be observed
and the triplet energies can be estimated directly.[7,23,24] The
triplet energy level can be tuned over a wide range by vary-
ing the spacer group R. This has enabled a detailed study of
the relationship between triplet energy and the rate of non-
radiative decay for this class of conjugated materials. More
recently, similar research work has been extended to their
closest neighbours, such as d10 gold(i)[25] and mercury(ii)
complexes.[26] When a heavy atom is introduced into the
main chain, the intersystem crossing (ISC) rate is increased
due to the enhanced spin–orbit coupling. A number of liter-
ature reports have shown that the nonradiative decay of the
triplet states in a series of platinum-containing conjugated
polymers and their metal model complexes can be described
well by the energy-gap law[23a] and, therefore, work should
focus on materials with high-energy triplets to avoid compe-
tition with nonradiative decay. In contrast to the body of
work on luminescent metallaynes with the p-electron conju-
gated unit, there are no reports of similar systems possessing
Group 16 chalcogen units in the backbone. There are also
numerous reports on the syntheses and applications of
purely organic polymeric systems of arylene ether, sulfide,
sulfoxide and sulfone in the literature,[27–30] but little re-
search on rigid-rod chalcogen-derived metallaynes and their
corresponding polyynes has been carried out. To get a
deeper insight, it is important to develop synthetic strategies
leading to novel conjugated polymers with non-p-conjugated
Results and Discussion
Synthesis: The syntheses of bifunctional alkynylated precur-
sors bearing 4,4’-diphenyl ether, 4,4’-diphenyl sulfide, 4,4’-di-
phenyl sulfoxide and 4,4’-diphenyl sulfone (abbreviated as
H-T(O)T, H-T(S)T, H-T(SO)T, and H-T(SO2)T, respective-
ly) are outlined in Scheme 1. For H-T(O)T, 4,4’-bis[(trime-
thylsilyl)ethynyl]diphenyl ether was prepared by Pd/Cu-cat-
Scheme 1. Synthesis of the chalcogen-based diethynyl ligand precursors.
Chem. Eur. J. 2006, 12, 2550 – 2563
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2551

W.-Y. Wong et al.
ꢁ
alyzed coupling of Me3SiC CH to 4,4’-dibromodiphenyl
respectively. Model metal diynes and polyynes are differen-
tiated by use of the subscript 1 for the polyynes. The feed
mole ratios of the platinum chloride precursors and the di-
ethynyl ligands were 2:1 and 1:1 for the diyne and polyyne
syntheses, respectively. The diplatinum compounds were iso-
lated by preparative TLC on silica. Purification of the poly-
mers was accomplished by silica column chromatography
with CH2Cl2 as the eluent, and they were all obtained in
high purity. Likewise, the diethynyl precursors were used to
form dinuclear alkynyl complexes of AuI and HgII through
the reaction between the appropriate bis-alkynes and Au-
(PPh3)Cl or MeHgCl in the presence of a base.[36] The yields
of these transformations were high in each case. All the new
complexes and polymers are air-stable and can be stored
without any special precautions. They are found to be solu-
ble in chlorinated solvents such as CH2Cl2 but are generally
insoluble in hydrocarbons. They all gave satisfactory analyti-
cal data, and were characterised by fast-atom-bombardment
mass spectrometry (FAB-MS), and IR and NMR spectrosco-
py.
ether followed by removal of the TMS protecting group
using a catalytic quantity of KOH in MeOH to yield 4,4’-di-
ethynyldiphenyl ether. For H-T(S)T, diphenyl sulfide was
treated with acetyl chloride and aluminium chloride to
afford the corresponding diketone. Phosphoryl chloride was
then mixed with the diketone in DMF to give the dialde-
hyde that further reacted with NaOH in a dioxane/water
mixture to give 4,4’-diethynyldiphenyl sulfide. 4,4’-Diethy-
nyldiphenyl sulfide was used as the starting material for
making H-T(SO)T and H-T(SO2)T through two different
oxidation pathways. The ligand precursors with the sulfoxide
and sulfone groups were obtained by employing 30% hydro-
gen peroxide and m-chloroperoxybenzoic acid (mCPBA),
respectively, as the oxidizing agents. All attempts to produce
H-T(SO2)T from H-T(S)T by using an excess of or highly
concentrated H2O2 failed. The crude products from these re-
action mixtures were purified by passage through short col-
umns of silica gel and were recrystallised where necessary.
Scheme 2 shows the chemical structure and the synthetic
strategies for the metal complexes in the present study. The
as-prepared diethynyl synthons were used to form a series
of Group10–12 metallaynes and metallopolymers by adapta-
tion of the reported dehydrohalogenation procedures.[23,24]
The triple bonds are represented by T and the diphenyl
ether, sulfide, sulfoxide, and sulfone by O, S, SO and SO2,
Chemical characterisation: The spectroscopic data given in
the Experimental Section are in line with their assigned
structures. All the compounds possess a well-defined size
and structure. The IR spectra are each characterised by a
ꢁ
sharp n(C C) absorption band at aproximately 2090–
2138cm ꢀ1. The compounds with
the sulfoxide and sulfone
groups show sharp n(SO) and n-
(SO2) absorption bands at
about 1040–1049 and 1151–
1156 cmꢀ1, respectively. The for-
mulae of the binuclear com-
plexes were all successfully es-
tablished by using the intense
molecular-ion peaks in their re-
spective positive FAB mass
spectra. The NMR spectra were
indicative of the highly symmet-
rical structure of the binuclear
complexes and also revealed a
high degree of structural regu-
larity in the polymers. The
single 31P{1H} NMR signals
flanked by platinum satellites
for the platinum complexes and
polymers were consistent with a
trans geometry of the square-
1
planar Pt unit with the J(P,Pt)
values typical of those for relat-
ed trans-PtP2 systems.[23,24] In all
1
cases, H NMR resonances aris-
ing from the protons of the or-
ganic moieties were observed.
Notably, two distinct 13C NMR
signals for the a- and b-acety-
lenic carbon atoms were ob-
Scheme 2. Synthesis of the platinum(ii), gold(i) and mercury(ii) alkynyls. i) trans-[PtPh(Cl)(PEt3)2] (2 equiv),
CuI, iPr2NH, RT; ii) trans-[PtCl2(PBu3)2] (1 equiv), CuI, iPr2NH, RT; iii) [Au(PPh3)Cl] (2 equiv), NaOH/
MeOH, RT; iv) [MeHgCl] (2 equiv), NaOH/MeOH, RT.
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Chalcogen-Bridged Polymetallaynes
FULL PAPER
served, and the a-acetylide chemical shifts were shifted
downfield with respect to the free dialkyne, in agreement
ꢀ
with the formation of a metal C(sp) s bond.
The three-dimensional molecular structures of selected di-
nuclear complexes were confirmed by X-ray crystallography
(Figures 1–3). Pertinent bond lengths and angles are given
in Tables 1–3. All of these molecules were shown to adopt
angular geometry at the sp3-hybridised heteroatom. For the
platinum complexes, the coordination geometry at each Pt
centre is square-planar with the two PEt3 groups trans to
each other and the metal capping groups are connected by
Figure 2. X-ray crystal structure of [Au-T(O)T]. Thermal ellipsoids were
drawn at the 25% probability level.
ꢁ
the three diethynyl ligands. The C C bond lengths are char-
acteristic of metal–alkynyl s bonding and the bond angles of
ꢀ ꢁ
the Pt C C units in the range of 173.0(8)–178.1(7)8 conform
to the rigid-rod nature of these molecules. In [Au-T(O)T],
ꢀ
the Au P bond lengths are typical at 2.2754(12) and
2.2702(15) Š,[36c] but appear longer than those of the chloro-
gold(i) phosphine complexes; a fact ascribed to the stronger
Figure 3. X-ray crystal structures of: a) [Hg-T(S)T], b) [Hg-T(SO)T] and
c) [Hg-T(SO2)T]. Thermal ellipsoids were drawn at the 25% probability
level.
trans influence of the alkynyl group as compared to that of
ꢀ
the chloro group. The Au C bond lengths span the narrow
range of 1.991(6)–2.025(4) Š. The geometry about the AuI
centre is essentially linear, and the P-Au-C angles are
174.23(13) and 177.12(17)8. As the bulky PPh3 ligands pre-
vent the close approach of adjacent molecules, no Au···Au
intermolecular contacts are apparent in this case. For the or-
Figure 1. X-ray crystal structures of: a) [Pt-T(S)T], b) [Pt-T(SO)T] and
c) [Pt-T(SO2)T]. Thermal ellipsoids were drawn at the 25% probability
level. All hydrogen atoms were omitted for clarity.
ꢀ ꢁ
ganomercurials, the Hg C C units are nearly linear with
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2553

W.-Y. Wong et al.
Table 1. Selected bond lengths [Š] and angles [8] for [Pt-T(S)T], [Pt-
T(SO)T] and [Pt-T(SO2)T].
the Hg-C-C angles being 172.0(11)–178.9(12)8. Examination
of the crystal packing diagram for each dimercury complex
shows the involvement of ligand-unsupported mercuriophi-
licity in its structure. The lattice is stabilized by various
weak intermolecular noncovalent Hg···Hg interactions
(4.130–4.147 for [Hg-T(S)T], 3.671–4.202 for [Hg-T(SO)T],
and 3.621–4.343 Š for [Hg-T(SO2)T]). Although each of
these mercuriophilic contacts is relatively weak, it is the
large number of them that play a supramolecular role and
generate a significant driving force for the solid-state aggre-
gation. We believe that such mercuriophilic forces are more
than just van der Waals interactions in these solid-state sys-
tems. The van der Waals radius of mercury has been debat-
ed and a value of up to 2.2 Š has been proposed recently,[37]
and is predicted to be a better estimate than the value
quoted by Bondi.[38] Here, the observed Hg···Hg separations
[Pt-T(S)T]
[Pt-T(SO)T]
[Pt-T(SO2)T]
ꢀ
Pt(1) P(1)
2.287(2)
2.289(2)
2.053(7)
2.017(8)
2.275(2)
2.286(2)
2.020(9)
2.057(8)
1.201(9)
1.225(10)
1.763(8)
1.769(8)
2.2971(16)
2.2869(17)
2.073(5)
2.2977(12)
2.2888(13)
2.075(4)
ꢀ
Pt(1) P(2)
ꢀ
Pt(1) C(6)
ꢀ
Pt(1) C(19)
2.011(5)
2.009(4)
ꢀ
Pt(2) P(3)
ꢀ
Pt(2) P(4)
ꢀ
Pt(2) C(34)
ꢀ
Pt(2) C(47)
ꢀ
C(19) C(20)
1.195(7)
1.793(6)
1.378(12)
1.201(6)
1.766(4)
1.432(4)
ꢀ
C(33) C(34)
ꢀ
S(1) C(24)
ꢀ
S(1) C(27)
ꢀ
S(1) O(1)
P(1)-Pt(1)-P(2)
174.16(8)
89.2(2)
88.8(2)
177.85(10)
90.0(2)
89.6(2)
178.1(7)
173.0(8)
175.5(9)
178.5(9)
102.7(4)
175.73(6)
91.63(16)
86.46(17)
174.81(5)
91.49(13)
86.49(13)
P(1)-Pt(1)-C(19)
P(2)-Pt(1)-C(19)
P(3)-Pt(2)-P(4)
ꢁ
are comparable to the values of 3.71–4.25 Š for [Hg(C
CR)2] (R=Ph, SiMe3),[39] and 4.077 and 4.449 Š computed
for molecular (HgH2)n clusters (n=2, 3),[40] and are towards
the upper limit of those accepted as representing metallo-
philic interactions.[41] None of these structures show p–p
stacking of the arene rings in the solid state.
P(3)-Pt(2)-C(34)
P(4)-Pt(2)-C(34)
Pt(1)-C(19)-C(20)
Pt(2)-C(34)-C(33)
C(19)-C(20)-C(21)
C(30)-C(33)-C(34)
C(sp2)-S(1)-C(sp2)
C(24)-S(1)-O(1)
O(1)-S(1)-O(1A)
175.8(6)
175.6(7)
176.5(5)
176.5(6)
100.0(4)
111.9(5)
106.2(3)
106.7(2)
121.1(4)
Structural and thermal properties of polymers: The thermal
properties of the polymers were examined by thermogravi-
metric analysis (TGA) and differential scanning calorimetry
(DSC) under nitrogen (Table 4). Analysis of the TGA trace
Table 2. Selected bond lengths [Š] and angles [8] for [Au-T(O)T].
Table 4. Structural and thermal properties of platinum polyynes.
ꢀ
ꢀ
Au(1) P(1)
2.2754(12)
2.2702(15)
1.167(6)
Au(1) C(19)
2.025(4)
1.991(6)
1.203(8)
1.413(6)
ꢀ
ꢀ
Au(2) P(2)
Au(2) C(34)
Polymer
Mn
Mw
Mw/Mn
Tdecomp(onset)[8C]
ꢀ
ꢀ
C(19) C(20)
C(33) C(34)
[Pt-T(O)T]1
[Pt-T(S)T]1
[Pt-T(SO)T]1
[Pt-T(SO2)T]1
12750
7020
6550
7930
37390
11430
11100
15480
2.93
1.63
1.69
1.95
363Æ5
361Æ5
354Æ5
335Æ5
ꢀ
ꢀ
C(24) O(1)
1.364(6)
C(27) O(1)
P(1)-Au(1)-C(19)
P(2)-Au(2)-C(34)
C(24)-O(1)-C(27)
174.23(13)
177.12(17)
119.5(4)
Au(1)-C(19)-C(20)
Au(2)-C(34)-C(33)
167.4(4)
171.7(5)
for the four PtII polymers shows that they all exhibit good
thermal stability. It has long been recognised that aromatic
polymers containing aryl ether or sulfone linkages have ex-
cellent thermal and mechanical properties.[28] These plati-
num polyynes, with different heteroatoms as the linkage
groups, retain greater than 95% of their mass under N2 up
to 335–3638C. The temperatures at which decomposition
Table 3. Selected bond lengths [Š] and angles [8] for [Hg-T(S)T], [Hg-
T(SO)T], and [Hg-T(SO2)T].
[Hg-T(S)T]
[Hg-T(SO)T]
[Hg-T(SO2)T]
ꢀ
Hg(1) C(1)
2.065(12)
2.011(14)
2.045(14)
2.044(15)
1.211(18)
1.191(17)
1.776(10)
1.766(13)
2.023(15)
2.031(13)
2.036(13)
2.106(16)
1.193(18)
1.200(19)
1.752(12)
1.819(12)
1.503(11)
2.065(11)
2.043(12)
2.052(12)
2.043(10)
1.199(15)
1.193(14)
1.768(9)
1.759(9)
1.447(7)
1.447(7)
ꢀ
Hg(1) C(2)
ꢀ
Hg(2) C(17)
begins appear higher than those in related polymers trans-
ꢀ
Hg(2) C(18)
[8b]
ꢀ
ꢁ
ꢁ ꢀ
[{ Pt(PBu3)2C C(p-C6H4)mC C }n] (m=1, 2, at ~3008C).
Thus, the introduction of heteroatoms can definitely in-
crease the thermal stability of this class of metal polyynes.
We observe a sharp weight loss of 28% for [Pt-T(O)T]1
whereas 40% of the weight was lost for [Pt-T(S)T]1, [Pt-
T(SO)T]1 and [Pt-T(SO2)T]1. The decomposition step is as-
cribed to the removal of one PBu3 group from [Pt-T(O)T]1
and the loss of six Bu groups from each of the latter three
polymers. These platinum polymers also reveal no discerni-
ble glass transitions in the DSC curves.
ꢀ
C(2) C(3)
ꢀ
C(16) C(17)
ꢀ
S(1) C(7)
ꢀ
S(1) C(10)
S(1) O(1)
S(1) O(2)
ꢀ
ꢀ
C(1)-Hg(1)-C(2)
C(17)-Hg(2)-C(18)
Hg(1)-C(2)-C(3)
Hg(2)-C(17)-C(16)
C(7)-S(1)-C(10)
C(7)-S(1)-O(1)
C(7)-S(1)-O(2)
O(1)-S(1)-O(2)
176.9(6)
177.2(6)
176.6(13)
172.0(11)
102.6(5)
177.8(6)
177.3(7)
178.9(12)
174.7(12)
99.7(6)
179.5(5)
176.8(5)
175.5(11)
175.6(12)
106.8(5)
107.5(5)
107.9(4)
119.3(4)
105.3(6)
The molecular weight data of our polymers, as determined
in THF by gel-permeation chromatography (GPC), are
shown in Table 4. The degree of polymerization calculated
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Chalcogen-Bridged Polymetallaynes
FULL PAPER
from Mw are 46, 14, 13 and 18for [Pt-T(O)T] 1, [Pt-
T(S)T]1, [Pt-T(SO)T]1 and [Pt-T(SO2)T]1, respectively. It
should be noted that GPC does not give absolute values of
molecular weights, but provides a measure of hydrodynamic
volume. Rodlike polymers in solution possess different hy-
drodynamic properties than flexible polymers. So, calibra-
tion of the GPC with polystyrene standards is likely to in-
flate the values of the molecular weights of the polyynes to
some extent. However, the lack of discernible resonances
that could be attributed to end groups in the NMR spectra
offers good support for the macromolecular nature of these
polyynes.
well-extended singlet excited state in the PtII polyynes. Gen-
erally speaking, the absorption energy of the oxygen-linked
metal compound is the largest for each metal type, whereas
the sulfone-containing counterpart shows the lowest absorp-
tion energy. In energy terms, the experimentally determined
HOMO–LUMO energy gaps (Eg) as measured from the
onset wavelength in the solid-film state are also shown in
Table 5. With reference to the similarly prepared bi(p-phen-
ꢁ
ꢁ
ylene)-linked compounds [MeHgC C(p-C6H4)2C CHgMe]
ꢁ
ꢁ
(309 nm), [(Ph3P)AuC C(p-C6H4)2C CAu(PPh3)] (326 nm),
ꢁ
ꢁ
trans-[Pt(Ph)(PEt3)2C C(p-C6H4)2C CPt(Ph)(PEt3)2]
ꢀ
ꢁ
ꢁ ꢀ
(349 nm),
and
trans-[{ Pt(PBu3)2C C(p-C6H4)2C C }n]
(372 nm), we find that the non-p-conjugated chalcogen unit
between the two phenyl rings hinders conjugation and
causes a blue-shift in the absorption wavelength (280–300,
303–318, 325—345 and 343–361 nm for our Hg, Au and Pt
dinuclear complexes, and Pt polymers, respectively). In
other words, the energy of the S1 singlet state (or the Eg
value) can be modified simply by varying the electronic
properties of the spacer group; this is vital for governing the
efficiency of triplet-state emission (vide infra).
Photophysical properties: The absorption and emission data
of the new metalated compounds are shown in Table 5. All
the metal alkynyls display similarly structured absorption
bands in the near UV region and the dependence of the ab-
sorption energies on the ligand type would suggest that the
1
absorption pattern is dominated by intraligand IL (p–p*)
transitions associated with the arylene–ethynylene moiety
from the S0 to S1 levels, possibly mixed with some admixture
of metal orbitals. Coordination of metal to the organic
system results in enhanced p!p* transitions. As compared
with the metal-free alkynes, we note that the position of the
lowest energy absorption band experiences a red-shift after
the inclusion of a metal fragment in all of these metal alkyn-
yls. This reveals that p conjugation is preserved through the
metal site by mixing of the frontier orbitals of the metal and
ligand. A simple glance tells us that the extent of p conjuga-
tion of our metalated compounds follows the order Pt>
Au >Hg according to the absorption data. Also, the transi-
tion energies of the platinum polymers are lowered with re-
spect to those of the diplatinum complexes, suggesting a
The thin-film photoluminescence (PL) spectra of the
metal alkynyls were probed at various temperatures
(Table 5, and Figures 4 and 5). Upon photoexcitation, we
1
observed an intense purple-blue (p–p*) fluorescence emis-
sion peak (S1!S0) near 400 nm in dilute fluid solutions at
290 K for each of them in agreement with the small Stokes
shift observed. We have shown that the organic triplet emis-
sions of our compounds with large optical gaps have been il-
luminated by the heavy-atom effect of Group 10–12 transi-
tion-metal elements. As the temperature was gradually de-
creased, we observed virtually no fluorescence band, but
only the prominent phosphorescence band emanating
Table 5. Photophysical data for the metal diynes and polyynes.
lmax [nm][a]
Eg [eV][b]
lem [nm][c]
Film (20 K)
[d]
CH2Cl2
Film
270
288
244*, 270
CH2Cl2 (290 K)
[H-T(O)T]
[H-T(S)T]
[H-T(SO)T]
[H-T(SO2)T]
[Pt-T(O)T]
[Pt-T(S)T]
[Pt-T(SO)T]
[Pt-T(SO2)T]
[Pt-T(O)T]1
[Pt-T(S)T]1
260 (1.6)
4.13
3.65
333, 344 (3.96, 1.64)
332, 346 (2.46, 1.94)
334, 341 (2.32, 1.61)
304 (9.10, 1.32)
-
244 (2.5), 278(2.7), 303* (1.5)
241* (2.5), 268(3.9)
249* (2.2), 270 (3.3)
269 (6.2), 292 (7.0), 325 (8.1)
297 (4.5), 334 (6.1)
249* (3.5), 304 (6.8), 333 (9.5)
305* (5.6), 345 (10.3)
267, 292, 343
-
4.12
3.62
3.63
3.39
3.43
3.24
3.40
3.26
3.28
3.18
3.67
3.41
3.62
-
-
259, 278, 290*
267, 291, 326
272*, 296, 334
271*, 304, 333
347
266, 291, 337
294, 344
266*, 299, 337
268*, 301*, 350
277*, 293, 311
278*, 319
368*, 375*, 421 (0.10, 1.57) 448, 468, 493
373*, 483, 509*, 521*, 536*
372*, 392 (0.33, 1.17), 407* 469, 495*
386 (0.25, 1.06)
370 (0.79, 1.43)
465, 489*, 499*, 513*
454, 475, 488
484, 510*, 522*, 537*
475, 501*, 527*
484, 509*, 536*
445, 474
477, 509, 530*
473, 493*, 523*
466, 500*, 515*
368(0.10, 1.72), 492*
382 (0.25, 0.78), 482*
382 (0.16, 0.98), 474*
389 (0.20, 1.35), 481
391 (0.59, 1.39), 430*
384 (0.88, 1.30)
269*, 296, 352
[Pt-T(SO)T]1 272*, 299, 349
[Pt-T(SO2)T]1 270*, 301*, 361
[Au-T(O)T]
[Au-T(S)T]
[Au-T(SO)T]
275* (8.1), 289 (10.9), 303 (11.4)
277* (4.9), 300 (6.0), 313 (6.3)
294 (12.0), 307 (12.8)
298, 313
365, 382 (1.17, 1.26)
388 (0.37, 0.93)
[Au-T(SO2)T] 269* (4.8), 286* (6.8), 308 (8.7), 318 (9.4) 271*, 295*, 311, 324 3.39
[Hg-T(O)T]
[Hg-T(S)T]
[Hg-T(SO)T]
280 (6.9)
264* (3.8), 290 (4.8)
279* (8.6), 289 (9.8)
294
3.82
3.48
3.69
3.46
392 (1.77, 1.14), 416*
395 (2.60, 1.12), 418*
363*, 384 (9.32, 1.22), 424* 375*, 394*, 452, 480, 495*, 544*
385 (2.72, 1.14) 375*, 385*, 448, 469*, 481*
372*, 396*, 440, 470, 504*
399*, 428*, 478, 495, 503*
275*, 310
285*, 302
290*, 310
[Hg-T(SO2)T] 266* (5.1), 291 (5.9), 300 (5.9)
[a] Extinction coefficients (104 mꢀ1 cmꢀ1) are shown in parentheses. [b] Estimated from the onset wavelength of the solid-state optical absorption. [c] As-
terisks indicate emission peaks appear as shoulders or weak bands. [d] Fluorescence quantum yields [%] and lifetimes [ns] shown in parentheses (fF, tF)
are measured in CH2Cl2 relative to anthracene.
Chem. Eur. J. 2006, 12, 2550 – 2563
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2555

W.-Y. Wong et al.
Figure 5. The photoluminescence (PL) and absorption spectra of Pt poly-
ynes. The absorption spectra are the dotted lines at higher energy mea-
sured at 290 K. PL spectra were taken at both 290 (a, in CH2Cl2) and
20 K (c, as thin films). For the polyyne [Pt-T(SO2)T]1, the 290 K PL
spectrum (d) measured as a thin film is also given.
Figure 4. The photoluminescence (c) and absorption (a) spectra of
thin films of binuclear complexes of Pt, Au and Hg taken at 20 and
290 K, respectively.
phorescence can be clearly identified for our platinum poly-
mers (see Figure 5) and is rarely found in the literature for
related systems containing heteroaromatic spacers. Presuma-
bly due to the internal heavy-atom effect of the sulfone
group, [Pt-T(SO2)T]1 shows the most intense phosphores-
cence band at 290 K among the four polymers and we can
even observe very strong solid-state triplet emission for [Pt-
T(SO2)T]1 in which the ratio of integrated intensities of
phosphorescence to fluorescence is greater than unity.
To examine the spatial extent of the singlet and triplet ex-
citons in our systems, we have constructed the energy level
scheme for the lower lying excitations (Figure 7) based on
the absorption and PL data. The energy values are absolute
values with respect to the S0 ground state. For the PtII sys-
tems, the lowest T1 state essentially remains strongly local-
ised, as can be inferred from the small energy difference be-
tween triplet emissions in the metal diynes and polyynes.
mainly from the central ligand chromophore. At 20 K, the
principal emissive peaks in the low-lying region that exhibit-
ed large Stokes shifts from the absorption spectra (Fig-
ures 4–6) possessed long emission lifetimes indicative of
their triplet parentage. The emission maxima are dependent
on the nature of the acetylide ligand and thus the lowest
emissive states in these compounds can tentatively be as-
3
signed as metal-perturbed IL (p–p*) transitions. The emis-
sion assignment can also be interpreted in terms of the ob-
served temperature dependence of the PL data. Representa-
tive examples of the temperature dependencies of the PL
spectra for the model compounds and polymers are dis-
played in Figure 6. In each case, when the temperature is
lowered, the triplet emission band increases in intensity; this
change is accompanied by a well-resolved vibronic structure
with most weight in the 0–0 vibrational peak, diagnostic of
the involvement of 3IL (p–p*) excited states. Such an in-
crease in intensity indicates a long-lived triplet excited state
that is more sensitive to thermally activated nonradiative
decay mechanisms.[7b] The phosphorescence lifetimes at the
peak maxima are found to be in the microsecond regime
(0.12–13.6 ms) at 20 K, typical of those observed in similar
polymetallaynes reported.[23,24] While we have a long-term
interest to observe triplet emission under ambient condi-
tions, this work is attractive in that room-temperature phos-
ꢀ
ꢁ
Previous calculations performed for trans-[{ Pt(PBu3)2C C-
ꢁ ꢀ
(p-C6H4)C C }n] (abbreviated as [Pt-T(P)T]1) also indicat-
ed the triplet to be confined to the phenylene ring.[42] Substi-
tution of the metal groups does not seem to alter this strong
confinement. All these efficient phosphorescent metal–or-
ganic systems containing the conjugation-interrupting
Group 16 elements exhibit T1–S0 gaps of 2.5 eV or above,
corresponding to S1(PL)–S0 gaps of around 3.13–3.57 eV.
The measured DE(S1–T1) values for our present systems are
constant at around 0.7Æ0.1 eV, corresponding closely to the
S1–T1 energy gaps estimated for some organic conjugated
2556
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Chem. Eur. J. 2006, 12, 2550 – 2563

Chalcogen-Bridged Polymetallaynes
FULL PAPER
Figure 6. Temperature dependence of the PL of: a) [Pt-T(S)T], b) [Pt-T(SO2)T]1, c) [Au-T(O)T] and d) [Hg-T(SO)T].
polymers.[43,44] We ascribe such a constant DE(S1–T1) value
to the exchange energy and possibly some additional con-
stant contribution due to the admixture of the metal orbi-
tals. All of the sulfides have triplet energies lower than the
corresponding sulfoxides, whereas those of the sulfones are
typically higher than those of the sulfoxides. These observa-
tions agree with some small-molecule, organic, aromatic
molecules ArEAr (Ar=aryl, E=S, SO, SO2). From experi-
ment, the T1–S0 gap generally changes with the E unit in the
order O>SO2 >SO>S for the metal diynes. However, the
T1 level for [Pt-T(SO2)T]1 appears to be slightly lower than
those of [Pt-T(S)T]1 and [Pt-T(SO)T]1, probably because
of its higher degree of polymerization (DP~18) than the
last two (~13–14). With the same ligand chromophore, the
T1 levels for the PtII and AuI compounds are in general
higher than those of the corresponding HgII congener. Hin-
dered conjugation by using different Group 16 element de-
rived units shifts the phosphorescence to the blue relative to
the conjugated biphenyl-spaced counterparts and the extent
of blue shift is the largest for the diphenyl ether derivatives
(approximately 0.44–0.48eV).
radiative (kr)P and nonradiative (knr)P decay rate constants
are calculated from the measured lifetime of triplet emission
(tP) and the phosphorescence quantum yield (fP) by the re-
lationships: (knr)P =(1ꢀfP)/tP and (kr)P =fP/tP. Table 6 shows
the relevant data for these photophysical parameters. Gen-
erally, we observe a rather strong dependence of fP with the
heavy-metal perturbation effect and the value of fP follows
the order PtII >AuI >HgII, and the Pt polyynes give more ef-
ficient phosphorescence than the Pt diynes; however, fP
does not vary much with the type of E group in the present
study. For phosphorescence in aromatic hydrocarbon mole-
cules, kr is typically found to be between 0.1 and 1 sꢀ1.[47] So,
the heavy-atom effect of Pt, Au and Hg increases the radia-
tive decay rate for the triplet emission by four orders of
magnitude. Comparing the (kr)P and (knr)P values for the in-
dividual metal polyynes and diynes with T1–S0 gaps of
2.5 eV or above it can be seen that the values for (knr)P are
comparable to those for (kr)P. For instance, insertion of the
Group 16 conjugation interrupters in the Pt polyyne systems
results in (kr)P values of (5.4–8.1)”104 sꢀ1 that are more effi-
cient relative to [Pt-T(P)T]1 ((kr)P =6”103 sꢀ1 at 20 K) by
about one order of magnitude.[23a] Our findings corroborate
the assertion that high-energy triplet states (and concurrent-
With the assumption that the ISC efficiency is close to
unity for third-row transition-metal chromophores,[45,46] the
Chem. Eur. J. 2006, 12, 2550 – 2563
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2557

W.-Y. Wong et al.
Figure 7. Electronic energy level diagram of metal diynes and polyynes containing Group16 main-group elements determined from absorption and PL
data. Dashed lines represent the levels for the metal diynes and polyyne containing the bi(p-phenylene) spacer. The S0 levels are arbitrarily shown to be
of equal energy.
Table 6. Some photophysical parameters for the phosphorescence emis-
sion at 20 K.
tion interrupters in such metal polyynes can limit the effec-
tive conjugation length and gives rise to efficient crossover
between S1 and T1 states.
E(T1–S0)
fp
tP (kr)P (”104) (knr)P (”104)
tr
[eV] [%] [ms]
[sꢀ1
4.1811.9
2.13
3.689.67
1.52
]
[sꢀ1
]
[ms][a]
We now compare the nonradiative decay of Pt diynes and
polyynes. Despite the fact that the same organic groups are
available for nonradiative decay in the metal polyynes and
diynes, it is possible to identify factors that may lead to dif-
ferent nonradiative behaviour. First of all, comparing the PL
spectra of platinum dimeric complexes and their corre-
sponding polymers, it can be seen that there is consistently
more weight in the vibronic side peaks of the triplet emis-
sion of the dimer than in the phosphorescence band of the
polymer. This suggests that there is less overlap between the
vibrational levels of the ground and excited states, and
therefore the triplet excited state in the dimer is more dis-
torted than that in the polymer. Calculations carried out for
[Pt-T(P)T]1 and its dimeric analogue have also shown this
to be the case. Secondly, since triplet excitons may diffuse
along a polymer chain, there could be bimolecular nonradia-
tive decay mechanisms such as triplet–triplet annihilation
occurring for the polymer that cannot occur in the short-
chain metal dimers. From Table 6, it is evident that, within
the limits of experimental error, the Pt polymers and dimers
[Pt-T(O)T]
[Pt-T(S)T]
2.77 25.9 6.21
2.57 24.811.6
2.64 27.6 7.49
2.66 20.813.6
2.73 45.86.38
2.56 48.6 6.02
2.61 51.3 7.27
2.56 46.3 8.57
2.7819.6 3.38
2.60 16.2 12.2
2.62 18.4 3.75
2.66 17.0 11.6
2.64 5.39 0.93
2.51 6.69 0.34
2.56 6.54 0.12
2.584.980.20
24.0
6.48 46.8
27.1
51.8 65.4
13.9
[Pt-T(SO)T]
[Pt-T(SO2)T]
[Pt-T(O)T]1
[Pt-T(S)T]1
[Pt-T(SO)T]1
[Pt-T(SO2)T]1
[Au-T(O)T]
[Au-T(S)T]
[Au-T(SO)T]
[Au-T(SO2)T]
[Hg-T(O)T]
[Hg-T(S)T]
7.18
.580
8.08
7.06
5.41
8.54
6.69
6.26
12.4
14.2
18.5
5.79
23.8 17.2
6.88
1.33
75.3
20.4
68.2
17.3
4.91
21.8
1.47
7.17
5.80
19.8274.4
54.5
101.7
5.08
778.8
[Hg-T(SO)T]
[Hg-T(SO2)T]
1.83
24.9
475.1
4.02
[a] The radiative lifetimes (tr) of the triplet excited state are deduced
from tr =tP/fP.
ly large optical gaps) intrinsically lead to the more efficient
phosphorescence in metal-containing arylene–ethynylenes.
Hence, the successful use of chalcogen-containing conjuga-
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Chem. Eur. J. 2006, 12, 2550 – 2563

Chalcogen-Bridged Polymetallaynes
FULL PAPER
appear to have similar (knr)P values. This is in agreement
with the fact that the site of emission and thus the vibrations
involved are the same. It also implies that any bimolecular
quenching processes in the polymers play a lesser role than
the vibrationally induced nonradiative decay.
vesting and the large triplet emission yield, and favoura-
ble radiative decay rate of triplet excitons is beneficial.
Experimental Section
Conclusion
General comments: All reactions were carried out under a nitrogen at-
mosphere with the use of standard Schlenk techniques, but no special
precautions were taken to exclude oxygen during workup. Solvents were
predried and distilled from appropriate drying agents. All chemicals,
unless otherwise stated, were obtained from commercial sources and
used as received. Preparative TLC was performed on 0.7 mm silica plates
(Merck Kieselgel 60 GF254) prepared in our laboratory. The compounds
A novel strategy is discussed that used a series of diethynyl-
based chalcogen-bridged biarylenes for the synthesis of tran-
sition-metal-containing macromolecules and related model
complexes. Their photoluminescent and electronic proper-
ties have been characterised in detail using optical methods.
The spatial extent of spectroscopic singlet and triplet ener-
gies as a function of the nature of the heavy metals and cen-
tral spacer groups is discussed in these metalated alkynyl
systems. The following observations and conclusions can be
made:
trans-[PtCl(Ph)(PEt3)2],[48] trans-[PtCl2(PBu3)2],[49] and trans-[{ Pt-
ꢀ
[23e]
ꢁ
ꢁ ꢀ
(PBu3)2C C(p-C6H4)C C }n]
were prepared by literature methods. In-
frared spectra were recorded as CH2Cl2 solutions or KBr pellets on a
Nicolet Magna550 Series II FTIR spectrometer. NMR spectra were mea-
sured in appropriate solvents on a JEOL EX270 or a Varian INOVA
400 MHz FT-NMR spectrometer, with 1H NMR chemical shifts quoted
relative to SiMe4 and 31P chemical shifts relative to an 85% H3PO4 exter-
nal standard. Fast atom bombardment (FAB) mass spectra were recorded
on a Finnigan MAT SSQ710 mass spectrometer. Electronic absorption
spectra were obtained with a Hewlett–Packard 8453 UV-visible spec-
trometer. For emission spectral measurement, the 325 nm line of a He/
Cd laser was used as an excitation source. The luminescence spectra were
analyzed by a 0.25 m focal-length double monochromator with a Peltier-
cooled photomultiplier tube and processed with a lock-in amplifier. For
low-temperature measurements, samples were mounted in a closed-cycle
cryostat (Oxford CC1104) in which the temperature could be adjusted
from 10 to 330 K. The solution emission spectra were measured on a PTI
Fluorescence Master Series QM1 spectrophotometer. The fluorescence
quantum yields were determined in CH2Cl2 solutions at 290 K against the
anthracene standard (fF =0.27). Phosphorescence quantum yields were
measured in solid thin films at 20 K relative to the prototype polymer
[Pt-T(P)T]1 (fP =0.30 at 20 K).[23a] The molecular weights of the poly-
mers were determined by GPC (HP1050 series HPLC with visible wave-
length and fluorescence detectors) using polystyrene standards and ther-
mal analyses were performed with the Perkin–Elmer TGA6 and Pyris
ꢀ
ꢁ
1) The phosphorescence of { MC C(C6H4)E(C6H4)-
ꢁ
ꢀ
C CM }-type materials containing the conjugation-inter-
rupting segment (M=Pt, Au, Hg; E=O, S, SO, SO2) is
very strong at low temperatures. All the three transition
metals (Pt, Au and Hg) can exert heavy-atom effects in
the enhancement of the ISC rate to harvest triplet state
light energy. The observed triplet yields are the highest
for PtII systems (0.21–0.28for diynes and 0.46–0.51 for
polyynes) among the three metal classes and the lowest
for the HgII counterparts.
2) We consider that the Group 16 heteroatom is a good
conjugation interrupter to limit the conjugation length.
All the materials show high-energy triplet states of
2.5 eV or above, leading to very efficient triplet emission,
in accord with the energy-gap law established for triplet
states in similar metalated systems. The use of chalcogen
Diamond DSC thermal analysers at a heating rate of 208Cminꢀ1
.
3
Caution: Organomercurials are extremely toxic and all experimentation
involving these reagents should be carried out in a well-ventilated hood.
atoms increases the accessibility of the (p–p*) excited
states and allows the spin-forbidden phosphorescence to
be easily observable even at room temperature for the
PtII polymers.
H-T(O)T: This compound was prepared as described previously[50] and it
was isolated in 88% yield. 1H NMR (270 MHz, CDCl3, 258C, TMS): d=
7.50 (d, 3J(H,H)=8.8 Hz, 4H; Ar), 6.98 (d, 3J(H,H)=8.8 Hz, 4H; Ar),
3.10 ppm (s, 2H; C CH); 13C NMR (67.8MHz, CDCl 3, 258C, TMS): d=
3) Generally, the order of triplet energies for the dinuclear
complexes is O>SO2 >SO>S within each metal class,
but the phosphorescence yield is relatively insensitive to
the nature of the E group.
4) Reduced conjugation upon incorporation of these
Group 16 elements markedly shifts the optical absorp-
tion and the phosphorescence band to the blue as com-
pared to other metal polyynes with carbocyclic and het-
erocyclic spacers. For the Pt and Au systems, we are able
to obtain comparable orders of magnitude for (knr)P and
(kr)P, which is rarely the case for polymetallaynes of this
kind in the literature.
5) The results are significant with regard to fundamental
understanding as well as providing design concepts for
triplet-state light-emitting systems for use in optoelec-
tronic research. This is desirable for the continual devel-
opment of LEDs that demand triplet-light-energy har-
ꢁ
ꢁ
156.85, 133.77, 118.77, 117.20 (Ar), 82.94, 76.92 ppm (C C); IR (CH2Cl2):
ꢀ1
+
ꢁ
ꢁ
n˜ =3295 ( CH), 2109 cm (C C); FAB-MS: m/z: 218[ M] .
H-T(S)T: The synthesis followed the reported procedures with an overall
3
yield of 41%.[51] 1H NMR (270 MHz, CDCl3, 258C, TMS): d=7.43 (d, J-
3
(H,H)=8.4 Hz, 4H; Ar), 7.28 (d, J(H,H)=8.4 Hz, 4H; Ar), 3.12 ppm (s,
2H; C CH); 13C NMR (67.8MHz, CDCl 3, 258C, TMS): d=136.31,
ꢁ
ꢁ
132.87, 130.71, 121.04 (Ar), 82.97, 78.22 ppm (C C); IR (CH2Cl2): n˜ =
ꢀ1
+
ꢁ
ꢁ
3296 ( CH), 2109 cm (C C); FAB-MS: m/z: 234 [M] .
H-T(SO)T: H2O2(aq) (19.8mmol, 30%) was added to a solution of bis-
(ethynylphenyl) sulfide (216 mg, 0.92 mmol) in CHCl3 (40 mL) under
reflux and the mixture was stirred overnight. After extraction with
CHCl3 and drying over MgSO4, the product (160 mg, 65%) was obtained
by purification using silica gel chromatography eluting with CH2Cl2.
1H NMR (270 MHz, CDCl3, 258C, TMS): d=7.61–7.27 (m, 8H; Ar),
3.18ppm (s, 2H; C CH); 13C NMR (67.8MHz, CDCl 3, 258C, TMS): d=
ꢁ
ꢁ
145.61, 133.05, 125.32, 124.60 (Ar), 82.24, 79.65 ppm (C C); IR (KBr):
ꢀ1
n˜ =3308( CH), 2112 (C C), 1049 cm (S=O); FAB-MS: m/z: 251 [M]+;
elemental analysis calcd (%) for C16H10OS: C 76.77, H 4.03; found: C
76.50, H 3.98.
ꢁ
ꢁ
Chem. Eur. J. 2006, 12, 2550 – 2563
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2559

W.-Y. Wong et al.
H-T(SO2)T: mCPBA (880 mg, 3.84 mmol) was added to a solution of bi-
s(ethynylphenyl) sulfide (180 mg, 0.77 mmol) in CH2Cl2 (20 mL) and the
mixture was stirred overnight. After extraction with CH2Cl2 and drying
over MgSO4, the product (120 mg, 57%) was isolated following silica gel
chromatography by elution with CH2Cl2. 1H NMR (270 MHz, CDCl3,
258C, TMS): d=7.88 (d, 3J(H,H)=8.6 Hz, 4H; Ar), 7.59 (d, 3J(H,H)=
the solution mixture was evaporated to dryness. The residue was redis-
solved in CH2Cl2, and filtered through a silica column using the same
eluent to remove ionic impurities and catalyst residues. After removal of
the solvent, the crude product was purified by precipitation in toluene
from MeOH. Subsequent washing with n-hexane and drying in vacuo
1
gave [Pt-T(O)T]1 as a yellow powder (69 mg, 71%). H NMR (400 MHz,
8.6 Hz, 4H; Ar), 3.25 ppm (s, 2H; C CH); 13C NMR (67.8MHz, CDCl 3,
CDCl3, 258C, TMS): d=7.26–7.19 (m, 4H; Ar), 6.84 (m, 4H; Ar), 2.15–
2.11 (m, 12H; PCH2), 1.60–1.57 (m, 12H; PCH2CH2), 1.47–1.41 (m, 12H;
CH2CH3), 0.92 ppm (t, 3J(H,H)=7.2 Hz, 18H; CH3); 13C NMR
(100.3 MHz, CDCl3, 258C, TMS): d=154.66, 131.93, 124.07, 118.39 (Ar),
ꢁ
ꢁ
258C, TMS): d=141.00, 132.92, 127.64 (Ar), 81.76, 81.22 ppm (C C); IR
ꢀ1
ꢁ
ꢁ
(KBr): n˜ =3274 ( CH), 2115 (C C), 1313, 1153 cm (SO2); FAB-MS: m/
z: 267 [M]+; elemental analysis calcd (%) for C16H10O2S: C 72.16, H
3.78; found: C 72.03, H 3.58.
107.99, 106.83 (C C), 26.32, 24.41, 23.83, 13.83 ppm (Bu); 31P NMR
ꢁ
(161.9 MHz, CDCl3, 258C, 85% H3PO4): d=3.96 ppm (1J(Pt,P)=
[Pt-T(O)T]: CuI (3 mg) was added to a stirred mixture of H-T(O)T
(12 mg, 0.06 mmol) and trans-[PtCl(Ph)(PEt3)2] (60 mg, 0.11 mmol) in
iPr2NH (10 mL) and CH2Cl2 (10 mL). The solution was stirred at room
temperature (RT) over a period of 15 h, after which all volatile compo-
nents were removed under vacuum. The crude product was taken up in
CH2Cl2 and purified on preparative silica TLC plates using n-hexane/
CH2Cl2 (3:2 v/v) as eluent. From the third pale yellow band (Rf =0.45)
2357 Hz); IR (CH2Cl2): n˜ =2102 cmꢀ1 (C C); elemental analysis calcd
ꢁ
(%) for (C40H62OP2Pt)n: C 58.88, H 7.66; found: C 58.58, H 7.43.
[Pt-T(S)T]1: This polymer was prepared by using a similar procedure to
that desribed above for [Pt-T(O)T]1 by using H-T(S)T (35 mg,
0.15 mmol) and trans-[PtCl2(PBu3)2] (100 mg, 0.15 mmol) to give [Pt-
T(S)T]1 as a yellow powder (50 mg, 40%). 1H NMR (400 MHz, CDCl3,
258C, TMS): d=7.24–7.13 (m, 8H; Ar), 2.12–2.08 (m, 12H; PCH 2), 1.57–
1.56 (m, 12H; PCH2CH2), 1.46–1.39 (m, 12H; CH2CH3), 0.92–0.88 ppm
(m, 18H; CH3); 13C NMR (100.3 MHz, CDCl3, 258C, TMS): d=131.85,
we obtained [Pt-T(O)T] as
a
yellow solid (33 mg, 48%). 1H NMR
(400 MHz, CDCl3, 258C, TMS): d=7.34–7.24 (m, 8H; Ar), 6.99–6.79 (m,
10H; Ar), 1.79–1.73 (m, 24H; CH2 of Et), 1.14–1.05 ppm (m, 36H; CH3
of Et); 13C NMR (100.3 MHz, CDCl3, 258C, TMS): d=156.44, 154.52,
ꢁ
131.35, 130.58, 127.75 (Ar), 109.75, 108.54 (C C), 26.30, 24.21, 23.67,
139.15, 132.01, 127.25, 124.32, 121.15, 118.37 (Ar), 111.64, 109.26 (C C),
13.77 ppm (Bu); 31P NMR (161.9 MHz, CDCl3, 258C, 85% H3PO4): d=
ꢁ
15.01, 8.01 ppm (Et); 31P NMR (161.9 MHz, CDCl3, 258C, 85 % H3PO4):
4.10 ppm (1J(Pt,P)=2350 Hz); IR (CH2Cl2): n˜ =2099 cmꢀ1 (C C); ele-
ꢁ
d=10.89 ppm (1J(Pt,P)=2641 Hz); IR (CH2Cl2): n˜ =2097 cmꢀ1 (C C);
mental analysis calcd (%) for (C40H62P2PtS)n: C 57.74, H 7.51; found: C
57.42, H 7.23.
ꢁ
FAB-MS: m/z: 1232 [M]+; elemental analysis calcd (%) for
C52H78OP4Pt2: C 50.64, H 6.37; found: C 50.32, H 6.08.
[Pt-T(SO)T]1: Following the same synthetic approach described for [Pt-
T(O)T]1, a yellow solid of [Pt-T(SO)T]1 (60 mg, 79%) was obtained
using H-T(SO)T (30 mg, 0.12 mmol) and trans-[PtCl2(PBu3)2] (80 mg,
0.12 mmol). 1H NMR (400 MHz, CDCl3, 258C, TMS): d=7.44 (d, 3J
(H,H)=8.4 Hz, 4H; Ar), 7.28 (d, 3J(H,H)=8.4 Hz, 4H; Ar), 2.08–2.05
(m, 12H; PCH2), 1.57–1.55 (m, 12H; PCH2CH2), 1.47–1.37 (m, 12H;
CH2CH3), 0.89 ppm (t, 3J(H,H)=7.2 Hz, 18H; CH3); 13C NMR
(100.3 MHz, CDCl3, 258C, TMS): d=140.95, 131.81, 131.27, 124.75 (Ar),
[Pt-T(S)T]: The procedure used to synthesise this compound was similar
to that used for [Pt-T(O)T] except that H-T(S)T (22 mg, 0.09 mmol) was
used instead of H-T(O)T. [Pt-T(S)T] was obtained as a yellow solid
(60 mg, 52%) after column chromatography eluting with n-hexane/
CH2Cl2 (3:1 v/v). 1H NMR (400 MHz, CDCl3, 258C, TMS): d=7.33–7.15
(m, 12H; Ar), 6.96 (m, 4H; Ar), 6.80 (m, 2H; Ar), 1.78–1.71 (m, 24H;
CH2 of Et), 1.13–1.05 ppm (m, 36H; CH3 of Et); 13C NMR (100.3 MHz,
CDCl3, 258C, TMS): d=156.20, 139.08, 131.53, 131.44, 130.62, 128.13,
112.78, 108.63 (C C), 26.25, 24.31, 23.81, 13.74 ppm (Bu); 31P NMR
ꢁ
127.26, 121.21 (Ar), 114.93, 109.67 (C C), 15.21, 8.10 ppm (Et); 31P NMR
(161.9 MHz, CDCl3, 258C, 85% H3PO4): d=4.85 ppm (1J(Pt,P)=
ꢁ
(161.9 MHz, CDCl3, 258C, 85% H3PO4): d=10.95 ppm (1J(Pt,P)=
2326 Hz); IR (KBr): n˜ =2098(C C), 1043 cm (S=O); elemental analy-
ꢀ1
ꢁ
2636 Hz); IR (CH2Cl2): n˜ =2094 cmꢀ1 (C C); FAB-MS: m/z: 1248[ M] ;
sis calcd (%) for (C40H62OP2PtS)n: C 56.65, H 7.37; found: C 56.44, H
7.05.
+
ꢁ
elemental analysis calcd (%) for C52H78P4Pt2S: C 49.99, H 6.29; found: C
49.78, H 6.02.
[Pt-T(SO2)T]1: A procedure similar to that described above for [Pt-
T(O)T]1 was used to obtain the [Pt-T(SO2)T]1 (83 mg, 81%) from H-T-
(SO2)T (32 mg, 0.12 mmol) and trans-[PtCl2(PBu3)2] (80 mg, 0.12 mmol).
1H NMR (400 MHz, CDCl3, 258C, TMS): d=7.74 (d, 3J(H,H)=8.4 Hz,
4H; Ar), 7.28(d, 3J(H,H)=8.4 Hz, 4H; Ar), 2.08–2.04 (m, 12H; PCH2),
1.56–1.53 (m, 12H; PCH2CH2), 1.45–1.36 (m, 12H; CH2CH3), 0.89 ppm
(m, 18H; CH3); 13C NMR (100.3 MHz, CDCl3, 258C, TMS): d=137.22,
[Pt-T(SO)T]: The procedure used to synthesise this compound was simi-
lar to that used for [Pt-T(O)T] except that H-T(SO)T (14 mg, 0.06 mmol)
was used and [Pt-T(SO)T] was obtained as a yellow solid (42 mg, 60%)
after column chromatography eluting with n-hexane/CH2Cl2 (4:1 v/v).
1H NMR (400 MHz, CDCl3, 258C, TMS): d=7.45–7.26 (m, 12H; Ar),
6.96 (m, 4H; Ar), 6.80 (m, 2H; Ar), 1.74–1.69 (m, 24H; CH2 of Et),
1.14–1.02 ppm (m, 36H; CH3 of Et); 13C NMR (100.3 MHz, CDCl3, 258C,
TMS): d=155.89, 140.65, 139.00, 131.41, 128.33, 127.33, 124.67, 121.32
ꢁ
133.81, 130.99, 127.22 (Ar), 115.66, 108.79 (C C), 26.24, 24.30, 23.81,
13.73 ppm (Bu); 31P NMR (161.9 MHz, CDCl3, 258C, 85% H3PO4): d=
(Ar), 109.72, 108.13 (C C), 15.01, 7.97 ppm (Et); 31P NMR (161.9 MHz,
4.45 ppm (1J(Pt,P)=2319 Hz); IR (KBr): n˜ =2097 (C C), 1317,
ꢁ
ꢁ
CDCl3, 258C, 85% H3PO4): d=11.01 ppm (1J(Pt,P)=2630 Hz); IR
1151 cmꢀ1 (SO2); elemental analysis calcd (%) for (C40H62O2P2PtS)n: C
55.61, H 7.23; found: C 55.39, H 7.33.
ꢀ1
(KBr): n˜ =2093 (C C), 1040 cm (S=O); FAB-MS: m/z: 1265 [M]+; ele-
ꢁ
mental analysis calcd (%) for C52H78OP4Pt2S: C 49.36, H 6.21; found: C
49.12, H 5.98.
[Au-T(O)T]: Au(PPh3)Cl (25 mg 0.05 mmol) in MeOH (15 mL) was
mixed with H-T(O)T (4.6 mg, 0.02 mmol) in CH2Cl2 (5 mL). NaOMe
(0.3 mL, 0.35 mmol) was added to this solution. Within a few minutes, a
light yellow solid precipitated from the homogeneous solution. The solid
was then collected by filtration after stirring for 2 h, was washed with
MeOH and was air-dried to give [Au-T(O)T] (16 mg, 67%). 1H NMR
(400 MHz, CDCl3, 258C, TMS): d=7.58–7.43 (m, 34H; Ar), 6.89 ppm
(m, 4H; Ar); 13C NMR (100.3 MHz, CDCl3, 258C, TMS): d=155.82,
134.37, 133.81, 131.53, 129.99, 129.44, 129.17, 118.49 (Ar), 103.77,
[Pt-T(SO2)T]: Similar to the preparation of [Pt-T(O)T], H-T(SO2)T
(15 mg, 0.06 mmol) was used to give [Pt-T(SO2)T] as a yellow solid
(40 mg, 57%) after column chromatography using n-hexane/CH2Cl2 (4:1
1
v/v) as eluent. H NMR (400 MHz, CDCl3, 258C, TMS): d=7.72 (m, 4H;
Ar), 7.32–7.28(m, 8H; Ar), 6.96 (m, 4H; Ar), 6.80 (m, 2H; Ar), 1.76–
1.66 (m, 24H; CH2 of Et), 1.14–1.02 ppm (m, 36H; CH3 of Et); 13C NMR
(100.3 MHz, CDCl3, 258C, TMS): d=138.93, 136.86, 134.36, 131.12,
130.93, 128.82, 127.39, 127.17 (Ar), 121.41, 109.88 (C C), 15.00, 7.97 ppm
103.50 ppm (C C); 31P NMR (161.9 MHz, CDCl3, 258C, 85 % H3PO4):
ꢁ
ꢁ
(Et); 31P NMR (161.9 MHz, CDCl3, 258C, 85% H3PO4): d=11.03 ppm
d=43.38ppm; IR (CH 2Cl2): n˜ =2112 cmꢀ1 (C C); FAB-MS: m/z: 1134
ꢁ
1
ꢀ1
( J(Pt,P)=2614 Hz); IR (KBr): n˜ =2090 (C C), 1371, 1155 cm (SO2);
FAB-MS: m/z: 1281 [M]+; elemental analysis calcd (%) for
C52H78O2P4Pt2S: C 48.74, H 6.14; found: C 48.55, H 6.00.
[M]+; elemental analysis calcd (%) for C52H38Au2OP2: C 55.04, H 3.38;
ꢁ
found: C 54.86, H 3.40.
[Au-T(S)T]: This complex was prepared by using the same conditions as
described above for [Au-T(O)T], but H-T(S)T (4.9 mg, 0.02 mmol) was
used instead to produce a light yellow solid in 54% yield (13 mg).
1H NMR (400 MHz, CDCl3, 258C, TMS): d=7.58–7.41 (m, 32H; Ar),
[Pt-T(O)T]1: Polymerization was carried out by mixing H-T(O)T
(26 mg, 0.12 mmol), trans-[PtCl2(PBu3)2] (80 mg, 0.12 mmol), and CuI
(3 mg) in iPr2NH/CH2Cl2 (20 mL, 1:1 v/v). After stirring at RT for 15 h,
2560
www.chemeurj.org
ꢀ 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2006, 12, 2550 – 2563

Chalcogen-Bridged Polymetallaynes
FULL PAPER
7.21–7.19 (m, 4H; Ar), 7.06 ppm (m, 2H; Ar); 13C NMR (100.3 MHz,
MS: m/z: 647 [M]+; elemental analysis calcd (%) for C18H14Hg2O: C
33.39, H 2.18; found: C 33.13, H 2.05.
CDCl3, 258C, TMS): d=134.36, 134.22, 133.01, 131.56, 130.46, 129.94,
129.18, 129.07 (Ar), 103.83, 103.51 ppm (C C); 31P NMR (161.9 MHz,
ꢁ
[Hg-T(S)T]: Similar to [Hg-T(O)T], [Hg-T(S)T] was prepared from H-
T(S)T (20 mg, 0.08mmol) and collected as a light yellow solid with a
yield of 71% (40 mg). 1H NMR (400 MHz, CDCl3, 258C, TMS): d=7.39
(d, 3J(H,H)=7.6 Hz, 4H; Ar), 7.35 (m, 4H; Ar), 0.70 ppm (t, 3J(H,H)=
146 Hz, 6H; HgMe); 13C NMR (100.3 MHz, CDCl3, 258C, TMS): d=
CDCl3, 258C, 85% H3PO4): d=43.30 ppm; IR (CH2Cl2): n˜ =2117 cmꢀ1
+
ꢁ
(C C); FAB-MS: m/z: 1150 [M] ; elemental analysis calcd (%) for
C52H38Au2P2S: C 54.27, H 3.33; found: C 54.02, H 3.10.
[Au-T(SO)T]: According to the same procedure described for the syn-
thesis of [Au-T(O)T], [Au-T(SO)T] was isolated from H-T(SO)T
(5.3 mg, 0.02 mmol) as a pale yellow solid in 61% yield (15 mg).
1H NMR (400 MHz, CDCl3, 258C, TMS): d=7.57–7.27 ppm (m, 38H;
Ar); 13C NMR (100.3 MHz, CDCl3, 258C, TMS): d=142.99, 134.19,
133.03, 131.58, 129.80, 129.09, 128.06, 124.78 (Ar), 103.01, 102.86 ppm
ꢁ
144.21, 135.40, 132.81, 130.70 (Ar), 122.05, 104.59 (C C), 7.11 ppm (Me);
IR (CH2Cl2): n˜ =2135 cmꢀ1 (C C); FAB-MS: m/z: 663 [M] ; elemental
+
ꢁ
analysis calcd (%) for C18H14Hg2S: C 32.58, H 2.13; found: C 32.33, H
2.05.
[Hg-T(SO)T]: A procedure similar to that employed for [Hg-T(O)T] was
used to give [Hg-T(SO)T] as a light yellow powder in 43% yield (24 mg)
from H-T(SO)T (20 mg, 0.08mmol). 1H NMR (400 MHz, CDCl3, 258C,
TMS): d=7.56–7.50 (m, 8H; Ar), 0.71 ppm (t, 3J(H,H)=142 Hz, 6H;
HgMe); 13C NMR (100.3 MHz, CDCl3, 258C, TMS): d=146.25, 144.57,
(C C); 31P NMR (161.9 MHz, CDCl3, 258C, 85% H3PO4): d=43.14 ppm;
ꢁ
ꢀ1
IR (KBr): n˜ =2116 (C C), 1043 cm (S=O); FAB-MS: m/z: 1166 [M]+;
ꢁ
elemental analysis calcd (%) for C52H38Au2OP2S: C 53.53, H 3.28; found:
C 53.45, H 3.06.
ꢁ
132.94, 124.71 (Ar), 126.50, 103.80 (C C), 7.09 ppm (Me); IR (KBr): n˜ =
[Au-T(SO2)T]: This compound was synthesised by a similar procedure to
that for [Au-T(O)T] from H-T(SO2)T (5.4 mg, 0.02 mmol), and it was iso-
lated as a pale yellow solid in 85% yield (20 mg). 1H NMR (400 MHz,
CDCl3, 258C, TMS): d=7.79 (m, 4H; Ar), 7.58–7.44 ppm (m, 34H; Ar);
13C NMR (100.3 MHz, CDCl3, 258C, TMS): d=138.92, 134.18, 132.82,
ꢀ1
2115 (C C), 1043 cm (S=O); FAB-MS: m/z: 68 0 M[ ]+; elemental anal-
ꢁ
ysis calcd (%) for C18H14Hg2OS: C 31.81, H 2.08; found: C 31.68, H 1.96.
[Hg-T(SO2)T]: By using H-T(SO2)T (20 mg, 0.07 mmol), an off-white
solid of [Hg-T(SO2)T] was collected (30 mg, 58%) after the usual
workup. 1H NMR (400 MHz, CDCl3, 258C, TMS): d=7.84 (d, 3J(H,H)=
7.6 Hz, 4H; Ar), 7.54 (d, 3J(H,H)=7.6 Hz, 4H; Ar), 0.73 ppm (t, 3J
(H,H)=148Hz, 6H; HgMe); 13C NMR (100.3 MHz, CDCl3, 258C, TMS):
ꢁ
131.65, 130.37, 129.71, 129.12, 127.33 (Ar), 102.44, 102.56 ppm (C C);
31P NMR (161.9 MHz, CDCl3, 258C, 85% H3PO4): d=42.99 ppm; IR
ꢀ1
(KBr): n˜ =2115 (C C), 1317, 1154 cm (SO2); FAB-MS: m/z: 1182 [M]+
ꢁ
ꢁ
d=148.36, 140.08, 132.78, 127.58 (Ar), 128.82, 103.31 (C C), 7.06 ppm
; elemental analysis calcd (%) for C52H38Au2O2P2S: C 52.80, H 3.24;
found: C 52.55, H 3.03.
ꢀ1
ꢁ
(Me); IR (KBr): n˜ =2137 (C C), 1320, 1156 cm (SO2); FAB-MS: m/z:
696 [M]+; elemental analysis calcd (%) for C18H14Hg2O2S: C 31.08, H
[Hg-T(O)T]: The organic diyne H-T(O)T (16 mg, 0.08mmol) in MeOH
(10 mL) was first combined with MeHgCl (50 mg, 0.20 mmol) in MeOH
(10 mL). We subsequently added 0.20m basic MeOH (13 mL) to give a
pale yellow suspension. The solvent was then decanted and the light
yellow solid of [Hg-T(O)T] was washed with MeOH (2”20 mL) and air-
dried (19 mg, 41%). 1H NMR (400 MHz, CDCl3, 258C, TMS): d=7.44
(d, 3J(H,H)=7.0 Hz, 4H; Ar), 6.93 (d, 3J(H,H)=7.0 Hz, 4H; Ar),
0.69 ppm (t, 3J(H,H)=140 Hz, 6H; HgMe); 13C NMR (100.3 MHz,
2.03; found: C 30.89, H 1.94.
Crystallography: Single crystals of seven compounds suitable for X-ray
crystallographic analyses were grown by slow evaporation of their respec-
tive solutions in CH2Cl2/n-hexane at RT. Crystal data, data collection pa-
rameters, and refinement results are listed in Table 7. The diffraction ex-
periments were carried out at 293 K on a Bruker Axs SMART1000 CCD
area-detector diffractometer using graphite-monochromated MoKa radia-
tion (l=0.71073 Š). The raw intensity data frames were integrated with
the SAINT+ program using a narrow-frame integration algorithm.[52]
Corrections for Lorentz and polarization effects were also applied by
CDCl3, 258C, TMS): d=156.42, 142.24, 133.67, 118.76 (Ar), 118.31,
ꢀ1
ꢁ
ꢁ
104.62 (C C), 7.26 ppm (Me); IR (CH2Cl2): n˜ =2138cm (C C); FAB-
Table 7. Summary of crystal structure data.
[Pt-T(S)T]
[Pt-T(SO)T]
[Pt-T(SO2)T]
C52H78O2P4Pt2S C58H52Au2OP2
1281.26 1220.87
[Au-T(O)T]
[Hg-T(S)T]
[Hg-T(SO)T]
[Hg-T(SO2)T]
formula
Mr
C52H78P4S
1249.26
C52H78OP4Pt2S
1265.26
C18H14Hg2S
663.53
C18H14Hg2OS
679.53
C18H14Hg2O2S
695.53
crystal size[mm3]
0.34”0.25”0.24 0.30”0.22”0.20 0.30”0.25”0.22 0.28”0.18”0.15 0.20”0.15”0.10 0.22”0.12”0.08 0.20”0.15” 0.09
crystal system
space group
a[Š]
b[Š]
c[Š]
triclinic
P1
monoclinic
C2/c
30.527(2)
9.0077(6)
20.4816(13)
90
92.5040(10)
90
5626.7(6)
4
monoclinic
C2/c
30.2194(14)
9.0729(4)
20.6748(10)
90
92.6350(10)
90
5662.6(5)
4
monoclinic
P21/n
10.8149(9)
12.9381(12)
37.132(3)
90
98.281(2)
90
5141.5(8)
4
monoclinic
C2/c
20.3521(15)
7.6683(6)
23.2552(17)
90
106.0430(10)
90
3488.0(5)
8
triclinic
P1
triclinic
P1
¯
¯
¯
9.7257(19)
14.376(3)
40.030(8)
89.89(3)
89.94(3)
84.45(3)
5570.7(19)
4
4.6555(5)
13.5283(15)
14.9441(16)
65.360(2)
89.928(2)
82.482(2)
846.66(16)
2
5.1002(8)
8.2840(13)
21.458(3)
100.238(3)
91.990(3)
101.242(3)
872.8(2)
2
a[8]
b[8]
g[8]
V[Š3]
Z
1calcd [gcmꢀ3
]
1.490
5.200
2488
1.494
5.151
2520
1.503
5.120
2552
1.577
5.800
2384
2.527
17.694
2384
2.666
18.232
612
2.647
17.693
628
m[mmꢀ1
F(000)
]
q range[8]
1.42–25.00
55186
19583
1.99–25.00
13465
4958
0.02980.03680.0573
3806
276
0.0338, 0.0805
0.0499, 0.0893
1.021
1.97–25.00
13678
4974
1.93–28.31
30444
11954
1.82–25.00
7844
3049
2.76–24.99
3433
2605
1.93–25.00
4276
2973
reflns collected
unique reflns
Rint
0.0560
0.0650
30.04480.038
2257
200
reflns obsvd [I>2.0s(I)] 11860
4102
276
0.0276, 0.0677
0.0380, 0.0737
1.018
6429
538191
0.0455, 0.0968
0.1119, 0.1210
0.949
2062
2318
parameters
1063
209
R1, wR2 [I>2.0s(I)][a]
R1, wR2 (all data)
GoF on F2[b]
0.0433, 0.0745
0.0887, 0.0841
0.876
0.0494, 0.1264
0.0681, 0.1453
0.913
0.0644, 0.1559
0.0735, 0.1621
0.989
0.0485, 0.1361
0.0625, 0.1555
0.947
[a] R1=ꢀjjFo jꢀjFc jj/ꢀjFo j. wR2={ꢀ[w(F2oꢀF2c)2]/ꢀ[w(Fo2)2]}1/2. [b] GoF=[(ꢀwjFo jꢀjFc j)2/(NobsꢀNparam)]1/2
.
Chem. Eur. J. 2006, 12, 2550 – 2563
ꢀ 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
2561

W.-Y. Wong et al.
SAINT. For each analysis, an empirical absorption correction based on
the multiple measurement of equivalent reflections was applied by using
the program SADABS.[53] The structures were solved by direct methods,
and expanded by difference Fourier syntheses using the software
SHELTXL.[54] Structure refinements were made on F2 by the full-matrix
least-squares technique. Unless stated otherwise, all the non-hydrogen
atoms were refined with anisotropic displacement parameters. The hydro-
gen atoms were placed in their ideal positions, but were not refined.
[21] Y. V. Romanovskii, A. Gerhard, B. Schweitzer, U. Scherf, R. I. Per-
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Acknowledgements
Financial support from a CERG Grant from the Research Grants Coun-
cil of the Hong Kong SAR, P.R. China (Project No. HKBU 2054/02P) is
gratefully acknowledged for this work. S.-Y.P. acknowledges the receipt
of a Li Po Chun Charitable Trust Fund Postgraduate Scholarship, admin-
istered by Hong Kong Baptist University. We also thank Dr. Z. Lin for
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Received: August 19, 2005
Published online: January 13, 2006
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