Synthesis, structures and spectroscopic properties of platinum(II), palladium(II) and copper(I) halide complexes with pyrimidine-phosphine ligand

Article abstract of DOI:10.1002/zaac.200700233

The reactions of pyrimidine-phosphine ligand N-[(diphenylphosphino)methyl]- 2-pyrimidinamine (L) with various metal salts of Pt^II, Pd ^II and Cu^I provide three new halide metal complexes, Pt₂Cl₄(μ-L)₂·2CH₂Cl ₂ (1), Pd₂Cl₄(μ-L)₂ (2), and [Cu₂(μ-I)₂L₂]_n (3). Single crystal X-ray diffraction studies show that complexes 1 and 2 display a similar bimetallic twelve-membered ring structure, while complex 3 consists of one-dimensional polymeric chains, which are further connected into a 2-D supramolecular framework through hydrogen bonds. In the binuclear complexes 1 and 2, the ligand L serves as a bridge with the N and P as coordination atoms, but in the polymeric complex 3, both bridging and chelating modes are adopted by the ligand. The spectroscopic properties of complexes 1-3 as well as L have been investigated, in which complex 3 exhibits intense photoluminescence originating from intraligand charge transfer (ILCT) π→π* and metal-to-ligand charge-transfer (MLCT) excited states both in acetonitrile solution and solid state, respectively.

Full text of DOI:10.1002/zaac.200700233

DOI: 10.1002/zaac.200700233
Synthesis, Structures and Spectroscopic Properties of Platinum(II), Palladium(II)
and Copper(I) Halide Complexes with Pyrimidine-phosphine Ligand
Jun-Feng Zhanga, Xin Gana, Quan-Qing Xub, Jian-Hua Chena, Mei Yuanb, and Wen-Fu Fua,b,
*
a Kunming / P.R. China, College of Chemistry and Chemical Engineering, Yunnan Normal University
b Peking / P.R. China, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences
Received April 6th, 2007.
Abstract. The reactions of pyrimidine-phosphine ligand N-[(di-
phenylphosphino)methyl]-2-pyrimidinamine (L) with various metal
salts of PtII, PdII and CuI provide three new halide metal comple-
xes, Pt2Cl4(µ-L)2·2CH2Cl2 (1), Pd2Cl4(µ-L)2 (2), and [Cu2(µ-I)2L2]n
(3). Single crystal X-ray diffraction studies show that complexes 1
and 2 display a similar bimetallic twelve-membered ring structure,
while complex 3 consists of one-dimensional polymeric chains,
which are further connected into a 2-D supramolecular framework
through hydrogen bonds. In the binuclear complexes 1 and 2, the
ligand L serves as a bridge with the N and P as coordination atoms,
but in the polymeric complex 3, both bridging and chelating modes
are adopted by the ligand. The spectroscopic properties of comple-
xes 1-3 as well as L have been investigated, in which complex 3
exhibits intense photoluminescence originating from intraligand
charge transfer (ILCT) πǞπ* and metal-to-ligand charge-transfer
(MLCT) excited states both in acetonitrile solution and solid
state, respectively.
Keywords: Platinum; Palladium; Copper; P-N ligand; Crystal
structure
Introduction
out. Herein, we report two interesting bimetallic twelve-
membered ring complexes Pt2Cl4(µ-L)2·2CH2Cl2 (1),
Pd2Cl4(µ-L)2 (2), and a polynuclear complex [Cu2(µ-I)2L2]n
(3). Both P,N-chelating and P,N-bridging coordination
modes are adopted by the new ligand to construct a one-
dimensional zigzag chain of 3, and the intermolecular inter-
action through extensive hydrogen bonds leads to a 2D
supramolecular framework. To the best of our knowledge,
there has been no example of such P-N ligand complex, in
which the ligand adopts two different coordination modes.
Furthermore, complex 3 exhibits intense photolumin-
escence both in the solid state and acetonitrile solution.
There has been considerable interest in using hemilabile li-
gands [1Ϫ4] for the construction of polyfunctional or-
ganometallic complexes [5Ϫ10], such as pyridylphosphine
ligands containing both hard (nitrogen) and soft (phos-
phorus) donor atoms [11Ϫ15]. These ligands can stabilize
various types of transition metals with different oxidation
states, such as AuI, AgI, CuI, PtII and PdII, according to
multiform coordination modes containing P-coordination,
N-coordination, P,N-chelating and P,N-bridging [16Ϫ23].
However, not all of the resulting coordination modes can be
exactly predicted owing to the influence of the coordination
sphere of metal ions, reaction temperature, solvent system
and so on [24, 25]. Recently, Song and co-workers reported
the synthesis of the nonrigid P-N ligand N-[(diphenylphos-
phino)methyl]-2-pyridinamine, as well as a series of tran-
sition metal complexes that display various coordination
modes [19]. However, few of this kind of complexes exhibit
photoluminescent properties. With the aim of further
understanding the coordination frameworks and properties
of such P-N ligand complexes, extending reactions of a new
P-N ligand N-[(diphenylphosphino)methyl]-2-pyrimidin-
amine (L) with various halide metal salts were carried
Experimental Section
Materials and reagents
All reactions were performed under
a nitrogen atmosphere.
K2PtCl4, Na2PdCl4, CuI, 2-aminopyrimidine and diphenylphos-
phine were purchased from Acros Chemicals Inc.. Pt(SMe2)2Cl2
was prepared by a literature method [26]. Other reagents were of
analytical grade and were used as received. All solvents were puri-
fied and distilled by standard procedures before use.
Synthesis of N-[(diphenylphosphino)methyl]-2-pyr-
imidinamine (L)
* Prof. Dr. Wen-Fu Fu
This ligand was prepared by the Mannich reaction of HPPh2.
HPPh2 (9.30 g, 50 mmol) was added with stirring to a solution of 2-
aminopyrimidine (4.75 g, 50 mmol) and paraformaldehyde (1.80 g,
60 mmol) in toluene (100 mL) at 65 °C. The mixture was stirred at
70-80 °C overnight and the solvent was removed under vacuum.
Technical Institute of Physics and Chemistry,
Chinese Academy of Sciences
Peking 100080, P.R. China
Fax: (ϩ8610) 6255 4670
E-mail: wf_fu@yahoo.com.cn
1718
 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2007, 633, 1718Ϫ1722

Platinum(II), Palladium(II) and Copper(I) Halide Complexes with Pyrimidine-phosphine Ligand
Table 1 Crystal data and structure refinement
Complexes
1
2
3
Formula
Fw
C36H36Cl8N6P2Pt2 C34H32Cl4N6P2Pd2 C34H32Cu2I2N6P2
1288.43
monoclinic
C2/c
941.20
monoclinic
P21/c
967.48
monoclinic
P21/n
Crystal system
Space group
Color
yellow
yellow
yellow
˚
a/A
18.413(3)
9.6175(17)
25.611(4)
102.576(2)
4426.6(13)
4
13.326(9)
8.893(6)
16.170(10)
109.546(7)
1806(2)
4
10.100(4)
33.869(12)
10.895(4)
107.104(6)
3562(2)
4
˚
b/A
˚
c/A
β/°
3
˚
V/A
Z
Dcalc /Mg/m3
θ range/°
Total refl.
Unique refl.(Rint
µ/mmϪ1
1.933
1.731
1.804
2.27-25.01
10893
3866 (0.0812)
6.904
2.62-25.01
8967
3173 (0.0429)
1.415
2.05-25.01
18326
6251(0.0882)
3.051
)
parameters
Goodness of fit
F(000)
244
1.017
2464
217
1.008
936
0.0353, 0.0681
0.0582, 0.0745
415
0.998
1888
0.0606, 0.1256
0.1269, 0.1526
R1, wR2[I>2σ(I)]a 0.0636, 0.1594
R1, wR2 (all data) 0.0780, 0.1703
Scheme 1 Reactions of ligand L. Reagents: (i) Pt(SMe2)2Cl2, (ii)
Na2PdCl4; (iii) CuI.
a R1 ϭ FoϪFc/Fo; wR2 ϭ {[w(Fo2ϪFc2)2]/ [w(Fo2)2]}1/2
Synthesis of [Cu2(µ-I)2L2]n (3)
The residue was recrystallized with CH2Cl2/CH3OH at Ϫ20 °C to
give 9.41 g (64 %) of L as white crystals. Anal. Calcd. (%) for
C17H16N3P: C, 69.60; H, 5.50; N, 14.33. Found (%): C, 69.53; H,
5.56; N, 14.38.
1H-NMR (CDCl3, 400 MHz, TMS): δ 4.24 (d, J ϭ 4.9 Hz, 2H, CH2), 5.21
(broad, 1H, NH), 6.51 (d, J ϭ 4.8 Hz, 1H), 7.34-7.35 (m, 6H), 7.44-7.50 (m,
4H), 8.25 (d, J ϭ 4.4 Hz, 2H). 13C-NMR (CDCl3): δ 40.1 (d, CH2), 110.5,
128.2, 128.3, 128.6, 132.5, 132.6, 157.6. 31P-NMR (CDCl3, 161.96 MHz,
85 % H3PO4): δ Ϫ17.09. Ms (m/z): 293 (Mϩ).
To a solution of L (0.15 g, 0.52 mmol) in 50 mL CH2Cl2, CuI
(0.10 g, 0.52 mmol) was added, and the mixture was stirred over-
night and filtered. The solvent of the filtrate was removed in
vacuum leaving a yellow solid. Light yellow crystals of 3 were ob-
tained by diffusion of diethyl ether into dichloromethane solution
in 52 % yield. Anal. Calcd (%) for C34H32N6P2I2Cu2: C 42.21, H
3.33, N 8.69. Found (%): C 42.34, H 3.28, N 8.63.
1H-NMR (CDCl3, 400 MHz, TMS): δ 4.46 (t, J ϭ 6.3 Hz, 4H, CH2), 5.30
(s, 2H, NH), 6.54 (t, J ϭ 4.8 Hz, 2H), 7.43-7.48 (m, 8H), 7.51-7.55 (m, 4H),
7.79-7.84 (m, 8H), 8.25 (d, J ϭ 4.8 Hz, 4H). 31P-NMR (CDCl3, 161.96 MHz,
85 % H3PO4): δ 29.16.
Synthesis of Pt2Cl4(µ-L)2·2CH2Cl2 (1)
X-ray crystallography
L (0.10 g, 0.34 mmol) and Pt(SMe2)2Cl2 (0.13 g, 0.34 mmol) were
mixed in 30 mL CH2Cl2 and the resulting solution was stirred for
3 h at room temperature. The solution was concentrated in vacuum
to ca. 5 mL and subsequent diethyl ether diffusion into the solution
afforded yellow crystals of 1 in 70 % yield. Anal. Calcd. (%) for
C34H32N6P2Cl4Pt2: C, 36.51; H, 2.88; N, 7.51. Found (%): C, 36.57;
H, 2.82; N, 7.46.
Crystals of 1-3 suitable for X-ray crystallography were obtained by
vapor diffusion of diethyl ether into CH2Cl2 solution. The details
of the crystallographic data and the selected bond lengths and
angles are listed in Tables 1 and 2, respectively. Diffraction data
were collected at room temperature with graphite-monochromated
˚
Mo Kα radiation (λ ϭ 0.71073 A) on a Rigaku R-AXIS RAPID
IP X-ray diffractometer. The diffraction data were corrected for
absorption correction using the ABSCOR program. The structures
were solved by direct methods using the program SHELXS 97 and
refined by full-matrix least squares on F2 using the SHELXL 97
program package [27]. The non-hydrogen atoms were refined aniso-
tropically. Crystallographic data(excluding structure factors) for the
structure 1-3 reported in this paper have been deposited with the
Cambridge Crystallographic Data Center, CCDC No. 641139 (1),
641140 (2), and 615648 (3). These data can be obtained free of
charge via http://www.ccdc.cam.ac.uk/conts/retrieving.html (or
from the CCDC, 12 Union Road, Cambridge CB2 1EZ, UK; fax:
ϩ44 1223 336033).
1H-NMR (CDCl3, 400 MHz, TMS): δ 4.76 (d, J ϭ 4.7 Hz, 4H, CH2), 5.30
(broad, 2H, NH), 6.46 (dd, J ϭ 4.7 Hz, 2H), 7.12 (t, J ϭ 7.3 Hz, 8H), 7.25
(t, J ϭ 7.3 Hz, 4H), 7.58 (dd, J ϭ 7.3 Hz, 8H), 7.87 (dd, J ϭ 4.7 Hz, 2H),
8.64 (t, J ϭ 6.6 Hz, 2H). 31P-NMR (CDCl3, 161.96 MHz, 85 % H3PO4):
δ 4.57.
Synthesis of Pd2Cl4(µ-L)2 (2)
L (0.10 g, 0.34 mmol) and Na2PdCl4 (0.10, 0.34 mmol) were mixed
in 30 mL CH2Cl2 and the resulting solution was stirred for 3 h at
room temperature. The undissolved material was filtered off and
the filtrate was concentrated in vacuum to ca. 3 mL. Diffusion of
diethyl ether into the solution afforded yellow crystals of 2 in 63 %
yield. Anal. Calcd (%) for C34H32N6P2Cl4Pd2: C, 43.39; H, 3.43;
N, 8.93. Found (%): C, 43.46; H, 3.47; N, 8.87.
Results and Discussion
Synthesis and Crystal Structures
1H-NMR (CDCl3, 400 MHz, TMS): δ 4.40 (s, 4H, CH2), 5.30 (broad, 2H,
NH), 7.44-7.59 (m, 16H), 7.64-7.69 (m, 6H), 7.76-7.86 (m, 4H). 31P-NMR
(CDCl3, 161.96 MHz, 85 % H3PO4): δ 29.13.
Scheme 1 shows the details of the synthetic strategy for
complexes 1-3. They were prepared by reactions of equimo-
Z. Anorg. Allg. Chem. 2007, 1718Ϫ1722
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J.-F. Zhang, X. Gan, Q.-Q. Xu, J.-H. Chen, M. Yuan, W.-F. Fu
˚
Table 2 Selected bond lengths/A and angles/° for complexes 1-3
1
Pt(1)-N(1)
Pt(1)-Cl(2)
N(1)-Pt(1)-P(1)
P(1)-Pt(1)-Cl(2)
P(1)-Pt(1)-Cl(1)
2.124(8)
2.288(3)
178.8(2)
92.8(1)
Pt(1)-P(1)
Pt(1)-Cl(1)
N(1)-Pt(1)-Cl(2)
N(1)-Pt(1)-Cl(1)
Cl(2)-Pt(1)-Cl(1)
2.236(3)
2.307(3)
88.4(2)
88.6(2)
175.6(1)
90.2(1)
2
3
Pd(1)-N(1)
Pd(1)-Cl(1)
N(1)-Pd(1)-P(1)
P(1)-Pd(1)-Cl(1)
P(1)-Pd(1)-Cl(2)
2.114(3)
2.280(3)
177.81(9)
89.58(6)
91.37(6)
Pd(1)-P(1)
Pd(1)-Cl(2)
N(1)-Pd(1)-Cl(1)
N(1)-Pd(1)-Cl(2)
Cl(1)-Pd(1)-Cl(2)
2.242(2)
2.293(2)
88.4(1)
90.7(1)
175.10(4)
Figure 1 The ORTEP drawing of the molecular plot of 1. The
hydrogen atoms are eliminated for clarity.
Cu(1)-P(1)
Cu(1)-I(1)
Cu(1)-Cu(2)
Cu(2)-P(2)
2.211(3)
2.641(2)
2.871(2)
2.236(3)
2.760(2)
93.1(2)
Cu(1)-N(1)
Cu(1)-I(2)
Cu(2)-N(4)#1
Cu(2)-I(1)
2.221(8)
2.589(2)
2.067(8)
2.679(2)
2.067(8)
124.20(9)
111.78(9)
115.98(5)
128.6(2)
57.97(4)
102.6(2)
100.64(8)
108.5(2)
126.14(9)
54.69(4)
Cu(2)-I(2)
N(4)-Cu(2)#2
P(1)-Cu(1)-N(1)
N(1)-Cu(1)-I(2)
N(1)-Cu(1)-I(1)
P(1)-Cu(1)-Cu(2)
I(2)-Cu(1)-Cu(2)
N(4)#1-Cu(2)-P(2)
P(2)-Cu(2)-I(1)
N(4)#1-Cu(2)-I(2)
I(1)-Cu(2)-I(2)
I(1)-Cu(2)-Cu(1)
P(1)-Cu(1)-I(2)
P(1)-Cu(1)-I(1)
I(2)-Cu(1)-I(1)
N(1)-Cu(1)-Cu(2)
I(1)-Cu(1)-Cu(2)
N(4)#1-Cu(2)-I(1)
P(2)-Cu(2)-I(2)
N(4)#1-Cu(2)-Cu(1)
P(2)-Cu(2)-Cu(1)
I(2)-Cu(2)-Cu(1)
107.0(2)
97.8(2)
136.65(9)
60.46(5)
125.3(2)
105.50(9)
112.9(2)
109.25(5)
56.71(4)
lar quantities of L and Pt(SMe2)2Cl2 for 1, Na2PdCl4 for
2, and CuI for 3, respectively, in dichloromethane at room
temperature. The single crystals of 1-3 are colored solids
(light-yellow for 1, deep-yellow for 2 and pale-yellow for 3)
and soluble in organic solvents such as dichloromethane,
chloroform and acetonitrile.
Figure 2 The ORTEP drawing of the molecular plot of 2. The
hydrogen atoms are eliminated for clarity.
The X-ray analysis shows that 1 consists of a bimetallic
twelve-membered ring located at an inversion center (Figure
1). The ligand L bridges two Pt(II) metal centers via its
P,N(pyrimidyl)-donor sites. Either of the Pt(II) centers is
coordinated to a P atom from one L ligand and a pyrimidyl
N atom from another one, and the pair of bidentate L
ligands are arranged in the head-to-tail configuration
which is similar to that found in [PdCl2(µ-P/N-
(Ph2PCH2NCH)C5H4N)]2·CHCl3 [28]. The other two coor-
dinating sites of Pt are occupied by two chloride ligands in
a trans mode. The distances of Pt(1)-N(1), Pt(1)-P(1), Pt(1)-
Cl(1) and Pt(1)-Cl(2) are 2.124(8), 2.236(3), 2.288(3) and
L ligand and a pyrimidyl N atom from another one. Two L
ligands and two PdII atoms form a twelve-membered ring,
in which the two L ligands are arranged in a head-to-tail
configuration. The distance of Pd(1)-N(1), Pd(1)-P(1),
Pd(1)-Cl(1) and Pd(1)-Cl(2) are 2.114(3), 2.2418(16),
˚
2.2804(15) and 2.2925(15) A, respectively. The N(1)-Pd(1)-
P(1) (177.81(9)°) and Cl(1)-Pd(1)-Cl(2) (175.10(4)°) angles
are close to 180°. The least-squares plane through the
atoms Pd(1), N(1), Cl(1), P(1), and Cl(2) has a mean devi-
˚
ation of 0.05 A. The dihedral angle between the plane
˚
2.307(3) A, respectively. The N(1)-Pt(1)-P(1) and Cl(2)-
Pd(1)-N(1)-Cl(1)-P(1)-Cl(2) and the pyrimidine ring is
Pt(1)-Cl(1) angles are 178.8(2) and 175.59(12)°, respectively.
65.9°, which is much less than that in 1. The non-bonded
˚
The least-squares plane through the atoms Pt(1), N(1),
Pd···Pd separation in this complex is 4.921 A, which is
˚
Cl(1), P(1) and Cl(2) has a mean deviation of 0.03 A. The
slightly longer than that in twelve-membered ring dipal-
˚
dihedral angle between the planes Pt(1)-N(1)-Cl(1)-P(1)-
ladium complexes linked by a pyridine-P ligand (4.594 A)
Cl(2) and the pyrimidine ring is 76.0°. The non-bonded
[19].
˚
Pt···Pt separation in this complex is 4.595 A.
Comparison with the binuclear structures of 1 and 2, Fig-
ure 3 shows that complex 3 is composed of neutral one-
dimensional copper(I) iodide chains built on binuclear
[Cu2(µ-I)2L2] subunits. As shown in Figure 3a, the asym-
metric unit of the structure of 3 has two L ligands and two
The perspective view of 2 is shown in Figure 2. The coor-
dination environment of the PdII metal atom in 2 is similar
to that of the PtII atom found in 1. Either of the PdII atoms
is coordinated to two chloride ligands, a P atom from one
1720
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Platinum(II), Palladium(II) and Copper(I) Halide Complexes with Pyrimidine-phosphine Ligand
Figure 4 UV-vis absorption spectra of complexes 1-3 and ligand
L in acetonitrile solution. dashed dot line: 1, 1.5ϫ10Ϫ5 molLϪ1
dot line: 2, 1.2ϫ10Ϫ5 molLϪ1; solid line: 3, 1.0ϫ10Ϫ5 molLϪ1
dashed line: L, 1.0ϫ10Ϫ5 molLϪ1
;
;
.
Figure 3 (a) The ORTEP diagram of 3. (b) View of the infinite
chain architecture of 3. (c) View of the 2-D framework of 3 through
hydrogen bonds. The phenyl rings are eliminated for clarity.
Figure 5 Emission spectra for 3 and the free ligand L upon excita-
tion at 320 nm at room temperature. Solid line: 3 in acetonitrile
solution; dashed line: 3 in solid state upon excitation at 350 nm;
dot line: L in acetonitrile solution.
Cu atoms bridged by iodine atoms. It should be pointed
that there are two kinds of coordination modes for the li-
gand L: one is P;fgN-chelating, and the other is P;fgN-bridg-
ing. Two bridging iodine atoms, as well as a pyrimidine N
atom and a chelating P atom from the same ligand or bridg-
ing P and N atoms from different ligands complete the dis-
torted tetrahedral coordination geometry of Cu(1) and
Spectroscopic properties
UV-vis absorption spectra of 1-3 and the ligand L measured
in CH3CN are shown in Figure 4. The spectra are
characterized by absorptions bands at 315-325 nm
(λmax/nm (ε/104 molϪ1dm3cmϪ1) for 1: 321 (1.20), 2:
320(1.16), 3: 317 (1.22), L: 317 (1.21)). Compared with ab-
sorption spectrum the ligand L (λmax ϭ 317 nm), the spec-
tral shapes of the complexes in CH3CN are similar to that
of the free ligand. Therefore, they are attributed to π;Ǟπ;*
absorption of heterocyclic P-N ligand.
1 and 2 are not luminescent both in the solid state and
in solution. Upon excitation at 320 nm, complex 3 and free
ligand L exhibit room-temperature emission at 385 and
369 nm in degassed acetonitrile solution, respectively (Fig-
ure 5). We tentatively assign the emission bands to originate
from the intraligand charge transfer π;Ǟπ;* excited state.
While the solid-state emission of 3 at 480 nm is ascribed to
come from d(Cu)Ǟπ;*(L) metal-to-ligand charge-transfer
excited state.
˚
Cu(2), respectively. The Cu-P (2.211(3) and 2.236(3) A),
˚
Cu-N (2.221(8) and 2.067(8) A) and Cu-I (2.6409(17),
˚
2.5885(17), 2.6409(17) and 2.6785(16) A) bond lengths fall
within the normal range for copper-iodide, phosphine and
nitrogen complexes. The bond angles around copper atom
vary from 93.1(2) to 125.3(2)°. The Cu···Cu distance in 3 is
˚
2.871(2) A, which is a little longer than twice of van der
˚
Waals radius of Cu (2.8 A).
As shown in Figure 3b, the iodine-bridged binuclear cop-
per units are connected by P;fgN-bridging ligand to Cu(2)
atoms into a zigzag polymeric chain, supporting terminal
[LCu(1)(I)2] fragments. In the crystal packing of 3 (Figure
3c), hydrogen-bonding interactions are observed between
the uncoordinated N(2) and N(3) atoms from two different
chelating L ligands in two neighboring chains. Thus, the
pair of chelating L ligands are linked into a pseudo eight-
membered ring through intermolecular N-H···N hydrogen
Conclusion
˚
bonds (N(2)···N(3) 3.086 A; N(3)-H(3)-N(2) 158.04°), and
the zigzag polymeric chains further linked into a 2D frame-
work.
Two binuclear complexes Pt2Cl4(µ-L)2 (1), Pd2Cl4(µ-L)2 (2)
and a polynuclear complex [Cu2(µ-I)2L2]n (3) with N-[(di-
Z. Anorg. Allg. Chem. 2007, 1718Ϫ1722
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1721

J.-F. Zhang, X. Gan, Q.-Q. Xu, J.-H. Chen, M. Yuan, W.-F. Fu
[9] W. H. Chan, K. K. Cheung, T. C. W. Mak, C. M. Che, J.
Chem. Soc., Dalton Trans. 1998, 873.
[10] T. Tanase, T. Igoshi, K. Kobayashi, Y. Yamamoto, J. Chem.
phenylphosphino)methyl]-2-pyrimidinamine (L) have been
prepared and characterized so as to reveal the coordinate
modes of P;fgN-chelating and P;fgN-bridging for the new
ligand L. Indeed, an X-ray crystallographic study shows
that complexes 1 and 2 both adopting P;fgN-bridging coor-
dination mode display a bimetallic twelve-membered ring
structure, while complex 3 consists of one-dimensional
polymeric chains, which are further connected into a 2-D
supramolecular framework through hydrogen bonds. Inter-
estingly, two different coordination modes of ligand L,
P;fgN-chelating and P;fgN-bridging, were found in 3. Fur-
thermore, 3 exhibits intense photoluminescence originating
from π;Ǟπ;* and MLCT excited states both in acetonitrile
solution and solid state, respectively.
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Acknowledgments. The work was supported by the National Natu-
ral Science Foundation of China (20671094, 20471066). We are
grateful to the State Key Project (2005CCA06800) for the financial
support. We thank foundation (50418010) for NSFC/RGC Joint
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