Template construction of a series of supramolecular coordination polymers via 6,7-dihydro-5H-[1,4]diazepino[1,2,3,4-lmn][1,10]phenanthroline-4,8-diium cation

Article abstract of DOI:10.1080/00958972.2011.579117

Five cation-induced complexes, (phen-dzp) [ZnBr₃N₃] (1), (phen-dzp) [ZnCl₂Br₂] (2), (phen-dzp) (H ₃O)₂ [Fe(CN)₆] (3), (phen-dzp)₂ [Cu₂I₆] (4), and [(phen-dzp)(Ag₂Br ₄)]_n (5) [phen-dzp = (C₁₅H₁₄N ₂)²⁺, 6,7-dihydro-5H-[1,4]diazepino[1,2,3,4-lmn][1,10] phenanthroline-4,8-diium], have been synthesized via self-assembly in solution. The crystal structures of 1-3 show that they all crystallize in monoclinic systems with mononuclear structures. Compound 4 is a binuclear coordination polymer. Complex 5 possesses a 2-D supramolecular layer with the organic cation phen-dzp trapped in it; interestingly, each inorganic polymeric planar layer is composed of large, decagon rings formed by sharing four Br^- and four [Ag₂Br₄] quadrilateral units with six adjacent decagon rings. The results provide insights into template effects of synthetic approaches on the construction of supramolecular compounds. The structures of 1-5 have been characterized by elemental analysis, infrared spectra, and single-crystal X-ray crystallography. Solid-state photoluminescence properties of 1-5 have been determined.

Full text of DOI:10.1080/00958972.2011.579117

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Template construction of a series
of supramolecular coordination
polymers via 6,7-dihydro-5H-
[1,4]diazepino[1,2,3,4-lmn]
[1,10]phenanthroline-4,8-diium cation
Zhenhua Zhang a , Yunyin Niu a , Seikweng Ng b , Benlai Wu a &
HongWei Hou a
a Department of Chemistry, Zhengzhou University, Zhengzhou
450052, P.R. China
b Department of Chemistry, University of Malaya, Kuala Lumpur
50603, Malaysia
Published online: 10 May 2011.
To cite this article: Zhenhua Zhang , Yunyin Niu , Seikweng Ng , Benlai Wu & HongWei Hou (2011):
Template construction of a series of supramolecular coordination polymers via 6,7-dihydro-5H-
[1,4]diazepino[1,2,3,4-lmn][1,10]phenanthroline-4,8-diium cation, Journal of Coordination
Chemistry, 64:10, 1683-1694
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Journal of Coordination Chemistry
Vol. 64, No. 10, 20 May 2011, 1683–1694
Template construction of a series of supramolecular
coordination polymers via 6,7-dihydro-5H-[1,4]diazepino
[1,2,3,4-lmn][1,10]phenanthroline-4,8-diium cation
ZHENHUA ZHANGy, YUNYIN NIU*y, SEIKWENG NGz,
BENLAI WUy and HONGWEI HOUy
yDepartment of Chemistry, Zhengzhou University, Zhengzhou 450052, P.R. China
zDepartment of Chemistry, University of Malaya, Kuala Lumpur 50603, Malaysia
(Received 22 December 2010; in final form 18 March 2011)
Five cation-induced complexes, (phen-dzp) [ZnBr3N3] (1), (phen-dzp) [ZnCl2Br2] (2),
(phen-dzp) (H3O)2 [Fe(CN)6] (3), (phen-dzp)2 [Cu2I6] (4), and [(phen-dzp)(Ag2Br4)]n (5)
[phen-dzp ¼ (C15H14N2)2þ
,
6,7-dihydro-5H-[1,4]diazepino[1,2,3,4-lmn][1,10]phenanthroline-
4,8-diium], have been synthesized via self-assembly in solution. The crystal structures of 1–3
show that they all crystallize in monoclinic systems with mononuclear structures. Compound 4
is a binuclear coordination polymer. Complex 5 possesses a 2-D supramolecular layer with the
organic cation phen-dzp trapped in it; interestingly, each inorganic polymeric planar layer is
composed of large, decagon rings formed by sharing four Brꢀ and four [Ag2Br4] quadrilateral
units with six adjacent decagon rings. The results provide insights into template effects of
synthetic approaches on the construction of supramolecular compounds. The structures of 1–5
have been characterized by elemental analysis, infrared spectra, and single-crystal X-ray
crystallography. Solid-state photoluminescence properties of 1–5 have been determined.
Keywords: Template effect; Photoluminescence property; X-ray crystal structure
1. Introduction
Although the term template effect was first used and defined at the beginning of the
1960s [1], surprising discoveries and new applications in the field of supramolecular
chemistry in the 1990s provoked a boom in the subject. More and more examples cover
the relevance of the template effect under the heading of rational synthesis. Metal ions
can act as templates with neutral molecules, hydrogen bonds, and electrostatic
interactions and also supporting formation of supramolecular compounds. A template
is described as temporary or external if it is eliminated at the end of a synthesis and not
incorporated into the end product [2]. If molecular compounds originally present are
also found in the end product, it is defined as a permanent template [3]. Supramolecular
compounds, especially coordination polymers directed by organic cations [4–9], have
become one of the most active areas of chemical engineering and molecular science.
*Corresponding author. Email: niuyy@zzu.edu.cn
Journal of Coordination Chemistry
ISSN 0095-8972 print/ISSN 1029-0389 online ß 2011 Taylor & Francis
DOI: 10.1080/00958972.2011.579117

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Z. Zhang et al.
N
N
H C
CH
2
2
CH
2
Scheme 1. Organic cation phen-dzp.
Our recent studies reported a cuprous thiocyanate polymer directed by the azotic
heterocyclic organic template 1,5-bis(pyridinium) pentane cation [10].
In order to explore self-assembly and mechanism in M–X supramolecular coordi-
nation polymers, we select Cu(þ), Ag(þ), Zn(2þ), and Fe(2þ) as metal cations and
phen-dzp as organic cation-template in this article. Five supramolecular compounds
were obtained and structurally characterized. In all the structures, the organic cation is
a permanent template which serves to counterbalance the charge on the inorganic anion
and induce formation of the whole supramolecular structure.
2. Experimental
2.1. General
Commercial reagents were used without purification and all experiments were carried
out in open atmosphere. 1,10-Phenanthroline monohydrate and 1,3-dibromoalkane
were used as received. Other chemicals were obtained from commercial sources and
used as received. Elemental analyses of all crystals were performed on a VARIO EL
(Heraeus) CHNS analyzer. Infrared (IR) spectra were recorded using a Bruker Tensor
27 spectrophotometer from 4000 to 400 cmꢀ1 using KBr pellets. The fluorescence
spectra of 1–5 were recorded using a HITACHI F-4500 (fluorescence spectro-
photometer) in a 1-cm quartz cell. The excitation and emission bandwidths were set
at 5 nm.
2.2. Synthesis
2.2.1. Synthesis of 6,7-dihydro-5H-[1,4]diazepino[1,2,3,4-lmn][1,10]phenanthroline 4,8-
diium (phen-dzp). The phen-dzp (scheme 1) [11, 12] was synthesized from 1,10-
phenanthroline monohydrate (5 mmol, 1 g) and 1,3-dibromoalkane (10 mmol, 2.02 g)
was heated to 70–80ꢁC, and refluxed for 6 h giving yellow precipitate. The reaction
mixture was cooled to room temperature, the precipitate was collected, recrystallized
with methanol and ether, and dried in vacuum; 2.3 g yellow powder was obtained
(80% yield).

Template effects for supramolecules
1685

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Z. Zhang et al.
ꢁ
˚
Table 2. Selected bond lengths (A) and angles ( ) within the coordination spheres in 1–5.
1
Br(1)–Zn(1)
N(3)–Zn(1)
Br(1)–Zn(1)–Br(3)
Br(3)–Zn(1)–Br(2)
2.309(4)
2.025(16)
108.32(13)
110.95(11)
Br(2)–Zn(1)
N(3)–N(4)
N(3)–Zn(1)–Br(2)
N(3)–Zn(1)–Br(1)
2.357(3)
1.16(3)
107.9(6)
114.9(6)
Br(3)–Zn(1)
N(4)–N(5)
Br(1)–Zn(1)–Br(2)
N(3)–Zn(1)–Br(3)
2.319(3)
1.09(2)
108.97(14)
105.8(6)
2
Cl(1)–Zn(1)
Br(2)–Zn(1)
N(1–C(15)
2.35(2)
2.434(8)
1.485(8)
1.489(7)
121.1(5)
111.0(3)
120.4(5)
Cl(2)–Zn(1)
N(1)–C(1)
N(2)–C(10)
Br(1)–Zn(1)–C(l2)
C(1)–N(1)–C(15)
C(l1)–Zn(1)–Br(2)
C(10)–N(2)–C(13)
2.31(2)
1.342(8)
1.330(8)
108.7(7)
117.7(5)
108.7(7)
119.1(5)
Br(1)–Zn(1)
N(1)–C1(2)
N(2)–C(11)
Br(1)–Zn(1)–C(l2)
C(12)–N(1)–C(15)
Br(1)–Zn(1)–C(l2)
C(11)–N(2)–C(13)
2.307(10)
1.374(8)
1.382(7)
106.9(6)
120.2(5)
106.9(6)
119.4(5)
N(2)–C(13)
C(1)–N(1)–C(12)
Br(1)–Zn(1)–Br(2)
C(10)–N(2)–C(11)
3
Fe(1)–C(18)
Fe(1)–C(20)
N(3)–C(16)
N(6)–C(19)
C(18)–Fe(1)–C(19)
C(19)–Fe(1)–C(20)
C(19)–Fe(1)–C(21)
C(16)–Fe(1)–C(17)
1.8699(16)
1.9179(16)
1.157(2)
1.162(2)
88.36(7)
90.41(7)
88.01(7)
90.19(6)
Fe(1)–C(19)
Fe(1)–C(21)
N(4)–C(17)
N(7)–C(20)
C(19)–Fe(1)–C(16)
C(16)–Fe(1)–C(20)
C(16)–Fe(1)–C(21)
C(20)–Fe(1)–C(17)
1.8856(16)
1.9209(16)
1.162(2)
1.160(2)
91.89(7)
85.78(6)
90.52(6)
91.56(7)
Fe(1)–C(16)
Fe(1)–C(17)
N(5)–C(18)
N(8)–C(21)
C(18)–Fe(1)–C(20)
C(18)–Fe(1)–C(21)
C(18)–Fe(1)–C(17)
C(21)–Fe(1)–C(17)
1.9124(15)
1.9218(16)
1.153(2)
1.162(2)
92.79(7)
90.92(7)
89.61(7)
90.15(6)
4
I(1)–Cu(1)
I(3)–Cu(1)
N(1)–C(13)
N(2)–C(10)
I(2)–Cu(1)–I(3)
C(1)–N(1)–C(5)
C(6)–N(2)–C(11)
2.632(2)
2.736(3)
I(2)–Cu(1)
N(1)–C(1)
N(2)–C(6)
I(1)–Cu(1)–I(2)
I(1)–Cu(1)–I(3)
C(1)–N(1)–C(13)
C(10)–N(2)–C(6)
2.635(2)
1.340(17)
1.364(18)
110.61(9)
113.83(9)
117.4(12)
120.6(13)
I(3)–Cu(1)
N(1)–C(5)
N(2)–C(11)
I(1)–Cu(1)–I(3)
I(3)–Cu(1)–I(3)
C(5)–N(1)–C(13)
C(10)–N(2)–C(11)
2.701(2)
1.378(18)
1.488(18)
109.31(8)
101.13(8)
119.7(11)
118.1(13)
1.500(17)
1.337(18)
115.60(9)
121.8(12)
120.1(11)
5
Br(1)–Ag(1)
Br(4)–Ag(1)
Br(3)–Ag(2)
N(1)–C(1)
N(2)–C(6)
Br(1)–Ag(1)–Ag(2)
Br(1)–Ag(1)–Br(4)
Br(3)–Ag(2)–Ag(1)
Br(2)–Ag(2)–Br(4)
Br(4)–Ag(2)–Br(3)
C(10)–N(2)–C(6)
C(1)–N(1)–C(5)
2.8111(18)
2.9169(16)
2.8966(16)
1.262(18)
1.421(17)
56.88(4)
110.15(5)
122.65(6)
113.47(6)
102.18(5)
122.3(13)
124.0(13)
Br(2)–Ag(1)
Br(1)–Ag(2)
Br(4)–Ag(2)
N(1)–C(5)
N(2)–C(10)
Br(2)–Ag(1)–Ag(2)
Br(2)–Ag(1)–Br(4)
Br(1)–Ag(2)–Br(2)
Br(1)–Ag(2)–Br(3)
Br(4)–Ag(2)–Ag(1)
C(10)–N(2)–C(11)
C(1)–N(1)–C(13)
2.8513(16)
2.8264(18)
2.8665(16)
1.389(17)
1.313(19)
56.76(4)
105.06(5)
113.60(5)
104.10(6)
135.01(6)
117.9(11)
117.2(11)
Br(3)–Ag(1)
Br(2)–Ag(2)
Ag(2)–Ag(1)
N(1)–C(13)
N(2)–C(11)
Br(3)–Ag(1)–Br(4)
Br(4)–Ag(2)–Ag(1)
Br(1)–Ag(2)–Br(4)
Br(2)–Ag(2)–Br(3)
Br(3)–Ag(2)–Ag(1)
C(6)–N(2)–C(11)
C(5)–N(1)–C(13)
2.8322(17)
2.8372(16)
3.100(2)
1.548(16)
1.467(16)
100.88(5)
135.01(6)
112.55(5)
109.84(5)
122.65(6)
118.6(12)
117.4(11)
2.2.2. Synthesis of 1. An ethanol solution of phen-dzp ꢃ 2Br (0.388 g, 1 mmol)
was added to a stirring colorless solution of ZnCl2 (0.134 g, 1.0 mmol) dissolved
in 10 mL of DMF/H2O (volume ratio of 4 : 1) in the presence of excess NaN3 (0.325 g,
5.0 mmol). The solution was then filtered and slowly evaporated in a vial at room
temperature. White crystals of 1 suitable for X-ray analysis were obtained after 3 days
in 56% yield. Anal. Calcd for C15H14Br3N5Zn (%): C, 31.61; H, 2.46; N, 12.29.
Found (%): C, 31.65; H, 2.43; N, 12.30. IR (KBr, cmꢀ1): 712 ꢆ(C–C); 1461 ꢆ(C¼N);
697 ꢆ(pyridine).

Template effects for supramolecules
1687
Figure 1. (a) The basic structural unit of 1. (b) Packing structure of 1.
2.2.3. Synthesis of 2. A methanol solution of phen-dzp ꢃ 2Br (0.388 g, 1 mmol) was
added to a stirring colorless solution of ZnCl2 (0.134 g, 1.0 mmol) dissolved in 10 mL of
DMF/H2O (volume ratio of 4 : 1). The solution was then filtered and slowly evaporated
in a vial at room temperature. White crystals of 2 suitable for X-ray analysis were
obtained after 7 days in 41% yield. Anal. Calcd for C15H14Br2Cl2N2Zn (%): C, 34.72;
H, 2.70; N, 5.40. Found (%): C, 34.73; H, 2.68; N, 5.52. IR (KBr, cmꢀ1): 712 ꢆ(C–C);
1461 ꢆ(C¼N); 697 ꢆ(pyridine); 2020 ꢆ(NꢄN¼N).
2.2.4. Synthesis of 3. A methanol solution of phen-dzp ꢃ 2Br (0.388 g, 1 mmol) was
added to a stirring colorless solution of K4Fe(CN)6 (0.33 g, 1.0 mmol) dissolved in
10 mL of DMF/H2O (volume ratio of 4 : 1). The solution was then filtered and slowly
evaporated in a vial at room temperature. Black crystals of 3 suitable for X-ray analysis
were obtained after 7 days in 63% yield. Anal. Calcd for C21H20FeN8O2 (%): C, 53.39;
H, 4.23; N, 23.58. Found (%): C, 53.35; H, 4.25; N, 23.56. IR (KBr, cmꢀ1): 712 ꢆ(C–C);
1461 ꢆ(C¼N); 697 ꢆ(pyridine); 2040 ꢆ(CꢄN).
2.2.5. Synthesis of 4. An ethanol solution of phen-dzp ꢃ 2Br (0.388 g, 1 mmol) was
added to a stirring pale yellow solution of CuI (0.190 g, 1.0 mmol) dissolved in 10 mL of

1688
Z. Zhang et al.
Figure 2. (a) The basic structural unit of 2. (b) Packing structure of 2.
DMF/H2O (volume ratio of 3 : 1) in the presence of excess KI (1.83 g, 5.0 mmol). The
solution was then filtered and slowly evaporated in a vial at room temperature. Yellow
crystals of 4 suitable for X-ray analysis were obtained after several weeks in 32% yield.
Anal. Calcd for C15H14CuI3N2 (%): C, 27.00; H, 2.10; N, 4.20. Found (%): C, 26.98;
H, 2.08; N, 4.23. IR (KBr, cmꢀ1): 710 ꢆ(C–C); 1469 ꢆ(C¼N); 695 ꢆ(pyridine).
2.2.6. Synthesis of 5. A methanol solution of phen-dzp ꢃ 2Br (0.388 g, 1 mmol) was
added to a stirring pale yellow solution of AgBr (0.188 g, 1.0 mmol) dissolved in 10 mL
of DMF/H2O (volume ratio of 3 : 1) in the presence of excess KBr (0.36 g, 5.0 mmol).
The reaction vessel was left to stand 3 days at room temperature. Large dark-yellow
crystals of 5 suitable for X-ray analysis were obtained in 73% yield. Anal. Calcd for
C15H14Ag2Br4N2 (%): C, 23.76; H, 1.85; N, 3.69. Found (%): C, 23.74; H, 1.86; N, 3.67.
IR (KBr, cmꢀ1): 711 ꢆ(C–C); 1465 ꢆ(C¼N); 690 ꢆ(pyridine).
2.3. X-ray crystallography
Data were collected for five crystals on a Bruker APEX CCD area-detector
˚
diffractometer using graphite-monochromated Mo-Kꢀ radiation (ꢇ ¼ 0.7103 A).

Template effects for supramolecules
1689
Figure 3. (a) The basic structural unit of 3. (b) 3-D architecture of 3.
The X-ray intensities were corrected for absorption using a semi-empirical procedure
[13]. The crystal structure was solved by direct methods and refined by full-matrix least
squares based on F2 [14]. Crystal data and structure refinement parameters for 1–5 are
given in table 1, and selected bond lengths and angles in table 2.
3. Results and discussion
3.1. IR spectra
Typical absorption bands at 3750–3000 cmꢀ1 (m, broad) and around 1650–1400 cmꢀ1
are assignable to the presence of water and the skeleton vibration of 1,10-phenanthro-
line monohydrate. The spectrum of phen-dzp has characteristic bands due to ꢆ(C–C),
ꢆ(C¼N), and pyridine at 713, 1466, and 699 cmꢀ1. Relative to the terminal CꢄN
stretch at 2040 cmꢀ1 in the IR spectrum of 3, the terminal NꢄN¼N stretch is
at 2020 cmꢀ1 in 1.

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Z. Zhang et al.
Figure 4. (a) A drawing of the copper(I) coordination environment in 4. (b) The supramolecular architecture
of 4 in the ac plane.
3.2. The crystal structures of 1–5
3.2.1. Crystal structure of (phen-dzp) [ZnBr3N3] (1). Single-crystal structure analysis
reveals that 1 crystallized in monoclinic system with space grꢀoup P2(1). The structural
unit of 1, shown in figure 1(a), consists of one Zn2þ, three Br , one N3ꢀ, and one phen-
dzp. The Zn is four-coordinate with three Brꢀ and one N to form tetrahedral geometry;
˚
˚
the bond lengths range from 2.025(16) A toꢀ2.357(3) A and bond angles vary from
105.8(6)ꢁ to 114.9(6)ꢁ. Within each unit, Br connects with phen-dzp2þ through a
hydrogen bond, forming a 2-D architecture through weak hydrogen-bond interactions
(shown in figure 1b). The organic cation plays a role of permanent template in the
structure.
3.2.2. Crystal structure of (phen-dzp) [ZnCl2Br2] (2). The structure of 2 is similar to 1,
crystallized in monoclinic system with space group P2(1)/n. The structural unit of 2,
shown in figure 2(a), consists of one Zn2þ, two Brꢀ, two Clꢀ, and one phen-dzp. The
Zn is four-coordinate with two Brꢀ and two Clꢀ in a tetrahedron. The bond lengths of

Template effects for supramolecules
1691
Figure 5. (a) A drawing of the silver(I) coordination environment in 5. (b) The decagon ring of 5.
(c) Packing structure of 5 in the ac plane.
˚
˚
Zn–Br and Zn–Cl range from 2.282(15) A to 2.434(8) A and bond angles vary from
104.3(8)ꢁ to 108.7(7)ꢁ. With each unit, two Brꢀ connect with three phen-dzp2þ through
hydrogen bonds. In both 1 and 2, there exist hydrogen-bond interactions [15] forming a
3-D architecture (shown in figure 2b). In the solid state, the phen-dzp2þ array around
the anion spreads infinitely along the b-axis.
3.2.3. Crystal structure of (phen-dzp)(H3O)2 [Fe(CN)6] (3). Single-crystal structure
analysis revealed that 3 crystallized in monoclinic system with space group P2(1)/n. The
structural unit of 3 is shown in figure 3(a), which consists of one [Fe(CN)6]4ꢀ and two
phen-dzp cations and two H3Oþ. The Fe is six-coordinate by six CNꢀ groups with
ꢁ
˚
˚
Fe–C bond lengths from 1.8699(16) A to 1.9218(16) A and bond angles from 85.78(6)
to 92.79(7)ꢁ. The organic cation is a permanent template counterbalancing the charge
on [Fe(CN)6]4ꢀ (figure 3b).
3.2.4. Crystal structure of (phen-dzp)2 [Cu2I6] (4). Single-crystal structure analysis
reveals that 4 consists of [C15H14N2]2þ as a structure-directing agent and [Cu2I6]4ꢀ
.
Compound 4 is a binuclear polymer. In the polyanionic framework [Cu2I6]4ꢀ, as shown

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Z. Zhang et al.
Figure 6. (a) Solid-state fluorescence spectrum of 2 and phen-dzp ꢃ 2Br at room temperature. (b) Solid-state
fluorescence spectrum of 3. (c) Solid-state fluorescence spectra of 4 and phen-dzp ꢃ 2Br at room temperature.
(d) Fluorescence spectra of 5 and phen-dzp ꢃ 2Br at room temperature.
in figure 4(a), the coordination environments of coppers are identical. Each is four-
coordinate in a distorted tetrahedral geometry by two ꢈ2-Iꢀ and two terminal Iꢀ. The
˚
˚
bond distances around Cu are 2.632(2) A to 2.701(2) A and the bondꢀangles range from
109.31(8)ꢁ to 115.60(9)ꢁ. The two Cu ions are bridged by two ꢈ2-I with a Cu ꢃ ꢃ ꢃ Cu
distance of 3.4538 A. From the b-axis, phen-dzp2þ array around the polyanionic chains
˚
(figure 4b). We have synthesized {[Cu2(SCN)4(phen-dzp)]}n [16], to compare with zinc
chloride and potassium ferrocyanide, the halogen/pseudohalogenoocuprates (I) and the
organic cation-template form complexes easily.
3.2.5. Crystal structure of [(phen-dzp)(Ag2Br4)]n (5). The X-ray single-crystal structure
analysis reveals that 5 crystallizes in the monoclinic system with space group P2(1)/c.
Complex 5 is a 2-D polymeric architecture with phen-dzp2þ trapped in the infinite 2-D
inorganic [Ag2Br4]n network. In the polymeric structure, the basic unit is [Ag2Br4].
The unit structure is shown in figure 5(a). In [Ag2Br4], two Ag ions are connected by
two m2-Brꢀ forming quadrilateral rings. If we ignore the interaction of Ag–Ag
˚
[3.100(2) A], Ag forms tetrahedral geometry. Bond distances around Ag(1) are

Template effects for supramolecules
1693
˚
˚
˚
˚
2.8111(18) A to 2.9169(16) A and around Ag(2) from 2.8264(18) A to 2.8966(16) A;
bond angles around Ag(1) range from 105.06(5)ꢁ to 117.77(5)ꢁ and around Ag(2) from
102.18(5)ꢁ to 113.60(5)ꢁ. Six Ag ions from four quadrilateral rings and four m2-Brꢀ
formed a decagon (figure 5b). So each inorganic polymeric planar net is composed of
large decagons formed by sharing four Brꢀ and four [Ag2Br4] quadrilateral units
with six adjacent decagons. Topologically, in 5 the network can be identified as a
regular 2-D (6,3) net (Supplementary material). In the whole structure, the phen-dzp,
acting as anti configuration, interlude irregularly in the 2-D network of the inorganic
polymer (figure 5c).
3.3. Solid-state photoluminescence properties of 1–5
Luminescent properties of MOFs are of interest owing to their higher thermal stability
than pure organic ligands and the ability to affect the emission wavelength and intensity
by metal coordination [17]. The solid spectra of 2–5 at room temperature are illustrated
in figure 6. The phen-dzp organic cation emits at 511 nm under excitation at 390 nm.
No photoluminescence was observed for 1. Excitation of the solid samples at 256 nm
(for 2), 460 nm (for 3), 410 nm (for 4), and 400 nm (for 5) produces emissions with
the peak maxima at 345 nm (for 2), 688 nm (for 3), 547 nm (for 4), and 533 nm
(for 5). Comparable with the organic cation, a blue shift of 166 nm in 2 and a red
shift in 3–5 have been observed. The emissions of 2 are tentatively ascribed to a ligand-
to-metal charge transfer while those of 3–5 are attributed to a ligand-to-ligand charge
transfer.
4. Conclusion
We have prepared and characterized five compounds. The structures of 1–3 show that
they are monoclinic systems with mononuclear structures. The crystal structure of 4 is
a binuclear polymer while 5 possesses a 2-D supramolecular network. The striking
structural difference among 1–5 is simply caused by one identical organic cation which
is mainly attributed to the template effects during the reactions. This presentation
summarizes the most important results on use of phen-dzp cation as an organic cation-
template for the synthesis of a range of metal halide/pseudohalide assemblies. The
phen-dzp in these compounds, acting as charge-compensating counterions, play an
important role in the crystal packing with the polymeric anionic layers or networks.
Further efforts are in progress to extend this method to other metal halides/
pseudohalides to evaluate the influences of cation structure modifications and different
anions on the resulting supramolecular structures as well to elucidate the mechanism of
inorganic polymeric framework formation.
Supplementary material
Supporting information: CCDC-800258, CCDC-800261, CCDC-800260, CCDC-
800259, and CCDC-723106 contain the supplementary crystallographic data for 1–5.

1694
Z. Zhang et al.
These data can be obtained free of charge via http://www.ccdc.cam.ac.uk/conts/
retrieving.html, or from the Cambridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK; Fax: þ44 1223 336 033 or Email: deposit@ccdc.cam.ac.uk.
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