Syntheses and structure characterization of inorganic/organic coordination polymers: Ag(dpa), Co(O3PH)(4,4′-bpy)(H2O), Zn(O3PH)(4,4′-bpy)0.5 and Mn[O2PH(C6H5)]2(4,4′ -bpy) (dpa = 2,2′-dipyridylamine; 4,4′-bpy = 4,4′-bipyridine)

Article abstract of DOI:10.1016/S0022-3697(01)00101-9

The synthesis and structure characterization of inorganic/organic coordination polymers was demonstrated. The hydrothermal synthesis of the polymers using microwave heating was used as a synthetic tool to reduce the reaction and crystallization time. X-ray crystallography was used to characterize the molecular structure of the polymers. The analysis of x-ray powder diffraction data suggested the structural influence of organic component and the geometrical preference of metal centers.

Full text of DOI:10.1016/S0022-3697(01)00101-9

Journal of Physics and Chemistry of Solids 62 ꢀ2001) 1629±1642
www.elsevier.com/locate/jpcs
Syntheses and structure characterization of inorganic/organic
0
coordination polymers: Agꢀdpa), CoꢀO PH)ꢀ4,4 -bpy)ꢀH O),
3
2
0
0
ZnꢀO PH)ꢀ4,4 -bpy) and Mn[O PHꢀC H )] ꢀ4,4 -bpy)
2
3
0.5
2
6
5
0
0
0
ꢀ
dpa ˆ 2,2 -dipyridylamine; 4,4 -bpy ˆ 4,4 -bipyridine)
Ju-Hsiou Liao , Pei-Ling Chen, Che-Chih Hsu
*
Department of Chemistry, National Chung Cheng University, 160 San-Hsing, Min-Hsiung, Chia-Yi 621, Taiwan
Received 27 December 2000; accepted 2 January 2001
Abstract
Four novel coordination polymers: Agꢀdpa) I, CoꢀO PH)ꢀ4,4 -bpy)ꢀH O) II, ZnꢀO PH)ꢀ4,4 -bpy)
0.5
0
0
III and
3
2
3
0
0
0
0
Mn[O
2
PHꢀC
6
H
5
)]
2
ꢀ4,4 -bpy) IV ꢀdpa ˆ 2,2 -dipyridylamine; 4,4 -bpy ˆ 4,4 -bipyridine), were synthesized by microwave
Ê
heating and characterized by X-ray crystallography. I crystallizes in monoclinic space group P21/n with a ˆ 11.576ꢀ2) A,
3
Ê
Ê
Ê
b ˆ 5.585ꢀ2) A, c ˆ 15.243ꢀ4) A, b ˆ 109.00ꢀ2)8, V ˆ 931.8ꢀ3) A . II crystallizes in monoclinic Cc space group with
3
Ê
Ê
Ê
Ê
a ˆ 22.477ꢀ7) A, b ˆ 5.280ꢀ1) A, c ˆ 10.404ꢀ4) A, b ˆ 96.08ꢀ3)8, V ˆ 1227.8ꢀ7) A . III crystallizes in monoclinic P21/c
3
Ê
Ê
Ê
Ê
space group with a ˆ 9.758ꢀ2) A, b ˆ 7.449ꢀ3) A, c ˆ 10.277ꢀ2) A, b ˆ 100.02ꢀ2)8, V ˆ 735.6ꢀ4) A . IV crystallizes in
3
Ê
Ê
Ê
Ê
monoclinic space group P2/c with a ˆ 10.174ꢀ1) A, b ˆ 11.817ꢀ3) A, c ˆ 18.784ꢀ4) A, b ˆ 102.14ꢀ1)8, V ˆ 2207.8ꢀ8) A . I
II
consists of linear metal±metal chains wrapped by dpa ligands. II and III consist of two-dimensional M ꢀO
3
0
PH) inorganic
0
sheets cross-linked by 4,4 -bpy ligands, while IV is formed by Mn[O
exhibits two-step thermal decomposition at ~200 and ~2508C, resulting in the reduction of Ag to Ag metal. II loses its
1
coordination water at ~1008C, leaving vacant coordination sites at Co ions, while the original framework remains intact. The
2 6 5 2
PHꢀC H )] sheets cross-linked by 4,4 -bpy ligands. I
1
2
0
removal of 4,4 -bpy in II±IV occurs at elevated temperatures above 250, 200 and 4008C respectively. q 2001 Elsevier Science
Ltd. All rights reserved.
1
. Introduction
[56±58] properties. The architecture of the hybrid inor-
ganic±organic networks involves the geometrical prefer-
ence of the metal ions as well as organic ligand building
blocks, which exhibit remarkable diversity in their molecu-
lar structures. However, the rational design of functional
materials is still at its exploratory stage and the construction
of extended solids remains unpredictable, due to many
subtle interactions of reaction variables such as temperature,
time, pH value, solvent and stoichiometry. The hydrother-
mal method has been widely used in the preparation and
crystallization of various metastable materials, including
zeolites, metal phosphate, phosphonates [59±65] as well
as numerous metal oxides [66±69]. Since its typical reaction
temperature range, 120±2208C, allows the incorporation of
organic species in the solid-state frameworks, this technique
has been used successfully in preparing coordination
Self-assembly of metal ions and multidentate organic
ligands attracts great attention because organic molecules
can alter inorganic microstructures, providing a promising
route for the design of novel materials [1]. To date, numer-
ous coordination polymers with multidimensional frame-
works, composed of channels or cavities of various sizes
and shapes, have been synthesized [2±18]. These inor-
ganic±organic coordination polymers are interesting
because of their potential applications in ion-exchange,
catalyst [19±24], molecule adsorption [25±29], electric
conductivities [30±38], magnetic [39±55] and optical
*
Corresponding author. Fax: 1886-52-721040.
E-mail address: chejhl@ccunix.ccu.edu.tw ꢀJ.-H. Liao).
0022-3697/01/$ - see front matter q 2001 Elsevier Science Ltd. All rights reserved.
PII: S0022-3697ꢀ01)00101-9

1630
J.-H. Liao et al. / Journal of Physics and Chemistry of Solids 62 ꢀ2001) 1629±1642
Table 1
Crystallographic data for I±IV
I
II
III
IV
Formula
Fw
AgN
3
C
10
278.06
H
8
CoPO
4
N
2
C
10
H
11
Zn
2
P
2
O
446.88
6
N
2
C
10
H
10
2 4 2 22 20
MnP O N C H
313.11
493.28
Ê
a ꢀA)
11.576ꢀ2)
5.585ꢀ2)
22.477ꢀ7)
5.280ꢀ1)
10.404ꢀ4)
96.08ꢀ3)
9.758ꢀ2)
7.449ꢀ3)
10.174ꢀ1)
11.817ꢀ3)
18.784ꢀ4)
102.14ꢀ1)
2207.8ꢀ8)
P2/c
Ê
b ꢀA)
Ê
c ꢀA)
15.243ꢀ4)
109.00ꢀ2)
931.8ꢀ4)
10.277ꢀ2)
100.02ꢀ2)
735.6ꢀ4)
b ꢀdeg)
3
Ê
V ꢀA )
1227.8ꢀ7)
Cc
Space group
P2
1
/n
1
P2 /c
Z value
442
1.982
21.20
25
4
3
r
calcd ꢀg/cm )
1.6942.018 84
1.4
2
1
m ꢀMoKa, cm
tempꢀ8C)
data observed [I . 2sꢀI)]
)
15.35
25
35.06
25
7.74
25
925
0.0438/0.0496
1021
0.0721/0.1463
1031
0.0422/0.0781
2944
a
b
R
1
/wR
2
0.0444/0.0688
a
R
1
ˆ S iF
o
u±uF
ꢀF) ˆ [SwꢀuF
c
i/S uF
u±uF
o
u.
2
c
b
2 1/2
wR
2
o
o
u) /SwF ] .
polymers [70±79]. Recently, although relatively few results
are unknown, microwave has been developed as a novel
heating technique for the hydrothermal ꢀsolventothermal)
synthesis of organic [80] or inorganic [81±83] solid-state
materials. As a consequence, the reaction and crystallization
time can be signi®cantly reduced from days to minutes, and
in some cases, new materials unreachable by conventional
hydrothermal techniques can be obtained. In an attempt to
search for stable microporous inorganic±organic networks,
we have utilized hydrothermal synthesis via microwave
heating as a synthetic tool. In this paper we demonstrate
the syntheses, structures and characterization of four inor-
ganic±organic coordination polymers.
pattern and the calculated pattern based on single crystal
X-ray data.
2
.2. Synthesis of Agꢀdpa) I
A mixture of 0.085 g ꢀ0.50 mmol) AgNO
0
3
, 0.344 g
2.00 mmol) 2,2 -dipyridylamine and 20 ml distilled water
ꢀ
in the mole ratio of 1:4:2222 was placed in a plastic auto-
clave lined with a 100 ml Telfon vessel. The mixture was
stirred until colorless gel was formed with a initial pH value
of 5.28. The autoclave was placed and heated in a micro-
wave oven at 30 psi ꢀcorresponding ~1208C in the phase
diagram of water) for 40 min. Final pH value was 6.18
after the reaction was completed. Tiny gray needles
2
. Experimental
Table 2
Non-hydrogen atomic coordinates and equivalent isotropic
2
2
.1. Materials and methods
temperature factors ꢀ AÊ ) for I
a
AgNO3 ꢀNext Chimica), CoꢀNO ) 6H O, MnꢀNO )
3 2
Atoms
x
y
z
U
eq
3
2
2
0
4
4
H
,4 -bipyridine ꢀAcros), ZnꢀNO
2
0
O, H
3
PO
3
, 2,2 -dipyridylamine ꢀRiedel-de Ha eÈ n),
ꢀShowa), and
Ag
0.9777ꢀ1)
1.1708ꢀ4)
0.8052ꢀ5)
0.8424ꢀ5)
0.7374ꢀ5)
0.6174ꢀ6)
0.5644ꢀ6)
0.6317ꢀ6)
0.7522ꢀ6)
0.7817ꢀ5)
0.6785ꢀ6)
0.6414ꢀ7)
0.7026ꢀ6)
0.8024ꢀ6)
0.2510ꢀ2)
2 0.0021ꢀ1) 0.045ꢀ1)
0.0220ꢀ3) 0.031ꢀ1)
2 0.1088ꢀ4) 0.029ꢀ1)
0.0666ꢀ4) 0.034ꢀ1)
2 0.1754ꢀ4) 0.039ꢀ2)
2 0.2255ꢀ5) 0.044ꢀ2)
2 0.2061ꢀ5) 0.047ꢀ2)
2 0.1380ꢀ4) 0.040ꢀ2)
2 0.0884ꢀ4) 0.028ꢀ2)
0.0330ꢀ4) 0.030ꢀ2)
0.0584ꢀ4) 0.040ꢀ2)
0.1172ꢀ5) 0.048ꢀ2)
0.1485ꢀ5) 0.047ꢀ2)
0.1229ꢀ4) 0.041ꢀ2)
3
)
2
Nꢀ1)
Nꢀ2)
Nꢀ3)
Cꢀ1)
Cꢀ2)
Cꢀ3)
Cꢀ4)
Cꢀ5)
Cꢀ6)
Cꢀ7)
Cꢀ8)
Cꢀ9)
Cꢀ10)
0.2482ꢀ15)
0.0941ꢀ10)
0.4106ꢀ10)
0.2393ꢀ19)
0.2014ꢀ15)
ꢀ
C H )H PO ꢀStrem) were used as obtained, without
6 5 2 3
further puri®cation. Hydrothermal reactions were
performed using a CEM MDS-2000 microwave acceler-
ated reaction system. Infrared spectra ꢀIR) were
recorded from KBr pellets on a Perkin-Elmer 682 IR
spectrometer. Thermogravimetric analysis ꢀTGA) was
performed under air ¯ow at a heating rate of 58C/min
2 0.0065ꢀ15)
2 0.1558ꢀ13)
2 0.1044ꢀ13)
0.6133ꢀ13)
0.6778ꢀ13)
0.5328ꢀ16)
0.3214ꢀ13)
0.2748ꢀ18)
using
a Shimadzu TGA-50 system. X-ray powder
diffraction ꢀXRPD) data were recorded on a Shimadzu
XRD-6000 diffractometer. Simulated XRPD data were
calculated with the SHELXTL-XPOW program using
single-crystal data. The identity of bulk products is
con®rmed by the comparison of experimental XRPD
a
* *
i j
ij i j i j
S U a a a a .
U
eq ˆ ꢀ1/3)S

J.-H. Liao et al. / Journal of Physics and Chemistry of Solids 62 ꢀ2001) 1629±1642
1631
Table 3
Non-hydrogen atomic coordinates and equivalent isotropic
Table 5
Non-hydrogen atomic coordinates and equivalent isotropic
2
temperature factors ꢀA ) for II
2
temperature factors ꢀA ) for IV
Ê
Ê
a
a
Atom
x
y
z
U
eq
Atoms
x
y
z
U
eq
Co
0.0479ꢀ1)
0.0745ꢀ2)
0.0739ꢀ5)
0.0553ꢀ4)
0.0415ꢀ4)
0.0204ꢀ5)
0.1445ꢀ2)
0.1613ꢀ3)
0.2215ꢀ3)
0.2648ꢀ2)
0.2479ꢀ2)
0.1877ꢀ2)
0.1451ꢀ2)
0.1645ꢀ3)
0.2250ꢀ3)
0.2660ꢀ2)
0.2466ꢀ2)
0.1861ꢀ2)
0.1465ꢀ4)
0.6582ꢀ8)
0.8193ꢀ1)
1.0285ꢀ3)
0.012ꢀ1)
0.018ꢀ1)
0.022ꢀ2)
0.016ꢀ2)
0.019ꢀ2)
0.023ꢀ2)
0.021ꢀ3)
Mnꢀ1)
Mnꢀ2)
Pꢀ1)
0.0
0.2210ꢀ1)
0.3308ꢀ1)
0.2552ꢀ1)
0.2867ꢀ1)
0.2114ꢀ2)
0.3400ꢀ2)
0.3387ꢀ2)
0.2142ꢀ2)
0.2500
0.023ꢀ1)
0.021ꢀ1)
0.024ꢀ1)
0.027ꢀ1)
0.035ꢀ1)
0.032ꢀ1)
0.033ꢀ1)
0.034ꢀ1)
0.036ꢀ1)
0.032ꢀ1)
0.030ꢀ1)
0.025ꢀ1)
0.026ꢀ1)
0.039ꢀ1)
0.046ꢀ1)
0.054ꢀ1)
0.057ꢀ1)
0.038ꢀ1)
0.032ꢀ1)
0.057ꢀ1)
0.066ꢀ2)
0.080ꢀ2)
0.088ꢀ2)
0.067ꢀ2)
0.039ꢀ1)
0.036ꢀ1)
0.030ꢀ1)
0.028ꢀ1)
0.043ꢀ1)
0.046ꢀ1)
0.033ꢀ1)
0.034ꢀ1)
0.030ꢀ1)
0.031ꢀ1)
0.031ꢀ1)
0.031ꢀ1)
P
0.5000
0.2500
Oꢀ1)
Oꢀ2)
Oꢀ3)
Oꢀ4)
0.4206ꢀ19) 0.9482ꢀ9)
0.6113ꢀ17) 1.1613ꢀ9)
0.8854ꢀ19) 0.9651ꢀ8)
0.3157ꢀ1)
0.8093ꢀ1)
0.1873ꢀ2)
0.3969ꢀ2)
0.6889ꢀ2)
0.3718ꢀ1)
0.3737ꢀ1)
0.3263ꢀ1)
0.3397ꢀ1)
0.3257ꢀ1)
0.3406ꢀ1)
0.2500
Pꢀ2)
Oꢀ1)
2 0.1358ꢀ19) 0.6844ꢀ9)
0.0451ꢀ12) 0.8152ꢀ6)
Oꢀ2)
b
Nꢀ1)
Oꢀ3)
Oꢀ4)
Cꢀ1)
Cꢀ2)
Cꢀ3)
Cꢀ4)
Cꢀ5)
2 0.1960ꢀ14) 0.7796ꢀ11) 0.011ꢀ7)
2 0.2531ꢀ16) 0.7759ꢀ11) 0.024ꢀ8)
2 0.0995ꢀ2)
0.0
Nꢀ1)
2 0.5782ꢀ3)
0.0243ꢀ3)
2 0.0691ꢀ17) 0.8078ꢀ8)
0.1720ꢀ16) 0.8435ꢀ11) 0.020ꢀ7)
0.2291ꢀ14) 0.8472ꢀ10) 0.016ꢀ7)
0.022ꢀ3)
Nꢀ2)
0.0
0.2500
Nꢀ3)
Nꢀ4)
0.5000
0.5000
0.1275ꢀ3)
2 0.4737ꢀ3)
0.3114ꢀ3)
0.2500
0.2500
0
0
0
0
0
0
Nꢀ1 )
0.0380ꢀ12) 0.8137ꢀ6)
2 0.1113ꢀ20) 0.7163ꢀ8)
2 0.1669ꢀ21) 0.7168ꢀ9)
2 0.0730ꢀ17) 0.8146ꢀ8)
0.0763ꢀ21) 0.9119ꢀ9)
0.1319ꢀ20) 0.9115ꢀ7)
0.2545ꢀ14) 0.8242ꢀ6)
0.021ꢀ3)
0.024ꢀ7)
0.033ꢀ7)
0.022ꢀ3)
0.025ꢀ7)
0.023ꢀ6)
0.027ꢀ3)
Cꢀ1)
0.2790ꢀ3)
0.3636ꢀ4)
0.3369ꢀ4)
0.2257ꢀ5)
0.1408ꢀ4)
0.1684ꢀ4)
0.7561ꢀ4)
0.6877ꢀ4)
0.6360ꢀ5)
0.6537ꢀ5)
0.7217ꢀ6)
0.7745ꢀ5)
0.0583ꢀ4)
0.0615ꢀ4)
0.0
0.4553ꢀ2)
0.4965ꢀ2)
0.5618ꢀ2)
0.5851ꢀ2)
0.5439ꢀ2)
0.4793ꢀ2)
0.4449ꢀ2)
0.4911ꢀ2)
0.5427ꢀ2)
0.5475ꢀ3)
0.5027ꢀ3)
0.4518ꢀ2)
0.3079ꢀ2)
0.3109ꢀ2)
0.2500
Cꢀ1 )
Cꢀ2)
0.3897ꢀ3)
Cꢀ2 )
Cꢀ3 )
Cꢀ3)
Cꢀ4)
0.4300ꢀ3)
0.3915ꢀ4)
Cꢀ4 )
Cꢀ5)
0.3151ꢀ4)
Cꢀ5 )
Nꢀ2)
Cꢀ6)
Cꢀ7)
0.2742ꢀ3)
0.2063ꢀ3)
c
2 0.0466ꢀ2)
2 0.0879ꢀ2)
2 0.1485ꢀ2)
2 0.1678ꢀ2)
2 0.1264ꢀ3)
2 0.0659ꢀ3)
2 0.0465ꢀ2)
2 0.0813ꢀ3)
2 0.1418ꢀ3)
2 0.1675ꢀ2)
2 0.1327ꢀ3)
2 0.0722ꢀ3)
Cꢀ6)
Cꢀ7)
Cꢀ8)
Cꢀ9)
Cꢀ10)
0.0606ꢀ16) 0.8317ꢀ11) 0.041ꢀ9)
0.1166ꢀ18) 0.8284ꢀ12) 0.039ꢀ9)
Cꢀ8)
0.2586ꢀ4)
Cꢀ9)
0.1996ꢀ4)
0.3666ꢀ19) 0.8175ꢀ8)
0.032ꢀ4)
Cꢀ10)
Cꢀ11)
Cꢀ12)
Cꢀ13)
Cꢀ14)
Cꢀ15)
Cꢀ16)
Cꢀ17)
Cꢀ18)
Cꢀ19)
Cꢀ20)
Cꢀ21)
Cꢀ22)
Cꢀ23)
Cꢀ24)
0.0871ꢀ5)
0.0314ꢀ4)
0.5606ꢀ17) 0.8099ꢀ11) 0.021ꢀ7)
0.5045ꢀ14) 0.8133ꢀ11) 0.036ꢀ9)
0.0921ꢀ4)
0
0
0
0
Nꢀ2 )
0.2556ꢀ14) 0.8167ꢀ6)
0.2881ꢀ22) 0.6992ꢀ6)
0.3442ꢀ24) 0.6969ꢀ8)
0.3680ꢀ19) 0.8121ꢀ8)
0.3355ꢀ25) 0.9296ꢀ8)
0.2793ꢀ23) 0.9318ꢀ6)
0.027ꢀ3)
0.030ꢀ7)
0.033ꢀ7)
0.032ꢀ4)
0.051ꢀ9)
0.041ꢀ9)
2 0.5194ꢀ3)
2 0.4013ꢀ3)
2 0.3397ꢀ4)
2 0.2128ꢀ4)
2 0.1512ꢀ3)
2 0.0338ꢀ3)
0.0677ꢀ3)
Cꢀ6 )
Cꢀ7 )
Cꢀ8 )
0.0
0.2500
0
Cꢀ9 )
0.0396ꢀ4)
0.0366ꢀ4)
0.6140ꢀ4)
0.6188ꢀ4)
0.5000
0.3136ꢀ2)
0.3108ꢀ2)
0.2605ꢀ2)
0.2610ꢀ2)
0.2500
0
Cꢀ10 )
a
* *
eq ˆ ꢀ1/3)S S U a a a a .
U
i
j
ij
i
j
i
j
2 0.0487ꢀ3)
2 0.1094ꢀ4)
2 0.2372ꢀ4)
2 0.2980ꢀ3)
2 0.4152ꢀ3)
b
c
Site occupancy factor ˆ 0.43.
Site occupancy factor ˆ 0.50.
0.5000
0.2500
0.6025ꢀ3)
0.5983ꢀ3)
0.2295ꢀ2)
0.2305ꢀ2)
a
* *
eq ˆ ꢀ1/3)S S U a a a a .
U
i
j
ij
i
j
i j
Table 4
Non-hydrogen atomic coordinates and equivalent isotropic
2
temperature factors ꢀA ) for III
Ê
a
ꢀ0.123 g, yield ˆ 88.5%, based on Ag) were collected after
ltration and several washings with distilled water and acet-
Atoms
x
y
z
U
eq
®
Zn
0.3734ꢀ1)
0.3377ꢀ2)
0.2760ꢀ4)
0.5463ꢀ5)
0.3791ꢀ5)
0.2402ꢀ5)
0.1047ꢀ5)
0.0138ꢀ8)
0.0492ꢀ5)
0.1854ꢀ5)
0.2735ꢀ7)
0.0661ꢀ1)
0.3807ꢀ2)
0.2231ꢀ5)
0.6392ꢀ1)
0.8253ꢀ2)
0.7408ꢀ4)
0.7276ꢀ4)
0.4690ꢀ4)
0.5975ꢀ5)
0.6225ꢀ8)
0.5864ꢀ9)
0.5208ꢀ6)
0.4981ꢀ6)
0.5364ꢀ6)
0.023ꢀ1)
0.023ꢀ1)
0.028ꢀ1)
0.037ꢀ1)
0.033ꢀ1)
0.027ꢀ1)
0.047ꢀ2)
0.059ꢀ3)
0.026ꢀ1)
0.030ꢀ2)
0.032ꢀ2)
one. Larger crystals suitable for single-crystal crystallo-
graphic study were obtained, and the yield was raised to
0.138 g ꢀ99.3%) when the reaction proceeded for 5 h. IR
P
Oꢀ1)
Oꢀ2)
Oꢀ3)
Nꢀ1)
Cꢀ1)
Cꢀ2)
Cꢀ3)
Cꢀ4)
Cꢀ5)
2 0.0284ꢀ6)
0.1707ꢀ5)
ꢀ
KBr pellet): 3010 w, 1586 s, 1533 w, 1447 vs, 1420 s,
21
353 s, 982 w, 836 w, 763 s cm .
1
2 0.1461ꢀ7)
2 0.1408ꢀ9)
0.2735ꢀ9)
0
3 2
.3. Synthesis of CoꢀO PH)ꢀ4,4 -bpy)ꢀH O) II
2
2 0.4253ꢀ8)
2 0.4326ꢀ8)
2 0.2927ꢀ8)
The synthetic procedure is similar to that described
above. The 40-min reaction of 0.146 g ꢀ0.500 mmol)
CoꢀNO
3
)
2
z 6H
2
O, 0.041 g ꢀ0.50 mmol) H
0
3
PO
ꢀ3.00 mmol) 4,4 -bipyridine and 10 ml distilled water in
3
, 0.468 g
a
*
i
*
j
U
eq ˆ ꢀ1/3)S S U a a a a .
i
j
ij
i
j

1632
J.-H. Liao et al. / Journal of Physics and Chemistry of Solids 62 ꢀ2001) 1629±1642
Fig. 1. ORTEP diagram, labeling scheme for the one-dimensional structure of I.
Fig. 2. Packing diagram of I, viewed down the b-axis.

J.-H. Liao et al. / Journal of Physics and Chemistry of Solids 62 ꢀ2001) 1629±1642
1633
Table 6
Selected bond lengths ꢀA) and angles ꢀdeg) for I. Symmetry transformations used to generate equivalent atoms: #1 2 x 1 2, 2y 1 1, 2z;
2 2 x 1 2, 2y, 2z
Ê
#
Ag±Nꢀ1)
2.144ꢀ4)
2.298ꢀ5)
2.327ꢀ5)
Ag±Ag#1
Ag±Ag#2
2.826ꢀ2)
2.848ꢀ2)
Ag±Nꢀ2)
Ag±Nꢀ3)
Nꢀ1)±Agꢀ1)±Nꢀ2)
Nꢀ1)±Agꢀ1)±Nꢀ3)
137.3ꢀ2)
138.0ꢀ2)
Nꢀ2)±Agꢀ1)±Nꢀ3)
84.7ꢀ2)
Agꢀ1)#1±Agꢀ1)±Agꢀ1)#2
159.71ꢀ4)
the mole ratio of 1:1:6:1111 resulted in 0.083 g
ꢀ
applied to all the data. The structure was solved with direct
method ꢀSHELXS-86) [84], and was re®ned by a full-matrix
least-square technique available in the SHELXL-93 [85]
crystallographic software package. All the non-hydrogen
atoms were re®ned with anisotropic thermal parameters.
All the hydrogen atoms bonded to carbon atoms at
calculated idealized positions were included in structure
factor calculation but were not re®ned. The crystallographic
data and detailed information of structure solution and
re®nement are listed in Table 1. Atomic coordinates
and equivalent isotropic thermal parameters are given in
Tables 2±5.
yield ˆ 53.2%, based on Co) yellow chunky crystals of
II. Initial pH ˆ 3.05; ®nal pH ˆ 3.65. The yield was raised
to 0.124g, 79.5% with elongated reaction time for 5 h. IR
ꢀ
KBr pellet): 3135 s, 2300 s, 1646 m, 1592 s, 1553 w,
2
526 w, 1035 w, 1075 vs, 1008 s, 809 s cm .
1
1
0
2
.4. Synthesis of ZnꢀO PH)ꢀ4,4 -bpy) III
3 0.5
The synthetic procedure is similar to that described for the
preparation of I. The 40-min reaction of 0.149 g
ꢀ
0.500 mmol) ZnꢀNO ) , 0.041 g ꢀ0.50 mmol) H PO ,
3 2 3 3
0
0
.078 g ꢀ0.500 mmol) 4,4 -bipyridine and 10 ml distilled
water in the mole ratio of 1:1:1:1111 resulted in 0.059 g
yield ˆ 52.7%, based on Zn) white chucky crystals of III.
Initial pH ˆ 2.42; ®nal pH ˆ 2.28. The yield was raised to
.082 g, 72.2% with elongated reaction time for 5 h. IR
KBr pellet): 3010 w, 2350 m, 1606 s, 1533 w, 1487 w,
ꢀ
3. Results and discussion
3
.1. Crystal structures
0
ꢀ
2
1
The X-ray crystallographic analysis reveals that I forms a
one-dimensional structure as shown in Fig. 1. The backbone
1
420 w, 1155 w, 1088 vs, 1048 w, 816 s cm .
I
0
of the chain is constructed by Ag´´´Ag interaction. Each Ag
2
.5. Synthesis of Mn[O
2
PHꢀC
6
H
5
)]
2
ꢀ4,4 -bpy) IV
ion is coordinated by an amido N atoms and two pyridyl N
atoms from three different dpa ligands. These Agꢀdpa)
chains are running parallel to the b-axis as shown in Fig. 2.
Selected bond lengths and bond angles are listed in Table 6.
The synthetic procedure is similar to that described for
the preparation of I. The 40-min reaction of 0.099 g
ꢀ
0.50 mmol) MnꢀNO
3 2 2
) z 4H O, 0.079 g ꢀ0.5 mmol)
0
Ê
The Ag´´´Ag distances, 2.826ꢀ2) and 2.848ꢀ2) A, are
ꢀ
C H )H PO , 0.312 g ꢀ2.0 mmol) 4,4 -bipyridine and
3
6
5
2
1
in the range of d ±d close-shell attraction [86]. The
0
10
1
0 ml distilled water in the mole ratio of 1:1:4:1111 resulted
in 0.055 g ꢀyield ˆ 24.5%, based on Mn) yellow crystals of
Ag´´´Ag´´´Ag angle is deviated from linearity at
Ê
IV. IR ꢀKBr pellet): 3050 w, 2320 vs, 1586 s, 1536 w,
159.71ꢀ4)8. The Ag-Namine distance, 2.144ꢀ4) A, is shorter
Ê
1
7
480 w, 1440 w, 1194 vs, 1130 s, 1022 w, 982 s, 809 s,
2
than the Ag-Npyridine distances, 2.298ꢀ5) and 2.327ꢀ5) A. The
1
.
50 m, 730 w, 690 m cm
Ag and the three coordinated N atoms are in the same trian-
gular plane with Npyridine-Ag-Npyridine angle, 84.7ꢀ2)8, much
smaller than those of Namine-Ag-Npyridine angles, 137.3ꢀ2)8
and 138.0ꢀ2)8. The dihedral angle between the two pyridyl
rings in the dpa ligand is 53.3ꢀ2)8.
2
.6. X-ray crystallography
Single crystals of I±IV were mounted in air on the top of
a glass ®ber. The crystallographic work was performed at
58C on a Bruker P4automatic diffractometer with graphite
Fig. 3 shows that the three-dimensional structure of II is
0
2
built up by CoꢀO PH)ꢀH
ligands, resulting in rectangular grids with 5.4 £ 11.5 A
3
2
O) layers cross-linked by 4,4 -bpy
Ê
Ê
monochromated MoKa radiation ꢀl ˆ 0.71073 A). Initial
unit cells for I±IV were determined from 20 re¯ections
randomly located from hemisphere search. Unit cell
constants and an orientation matrix for data collection
were re®ned from 25 carefully centered re¯ections around
Co´´´Co separations. As shown in the asymmetric unit of
II
II, Fig. 4, the Co ion adopts an octahedral geometry. The
0
two N atoms, from two different 4,4 -bipyridines, are trans
to each other, occupying the axial positions. Three oxygen
2
2
2 u ˆ 258. Three standard re¯ections were measured peri-
odically every 97 re¯ections. No signi®cant decay was
atoms from each of the three different [HPO3] are located
at the equatorial positions, while a water molecule occupies
the remaining equatorial site. As illustrated in Fig. 3, arrays
observed. An empirical c-scan absorption correction was

1634
J.-H. Liao et al. / Journal of Physics and Chemistry of Solids 62 ꢀ2001) 1629±1642
Fig. 3. Packing diagram of II, viewed along a-axis.
0
Fig. 4. ORTEP diagram of II. Two possible orientations of disordered 4,4 -bipyridyl rings are illustrated in solid and dashed lines.

J.-H. Liao et al. / Journal of Physics and Chemistry of Solids 62 ꢀ2001) 1629±1642
1635
Table 7
Ê
Selected bond lengths ꢀA) and angles ꢀdeg) for II. Symmetry transformations used to generate equivalent atoms: #1 x, y 2 1, z; #2 x, 2y 1 1,
z 2 1/2
Co±Oꢀ1)
2.017ꢀ10)
2.066ꢀ9)
2.095ꢀ10)
2.103ꢀ9)
2.205ꢀ5)
2.196ꢀ5)
91.6ꢀ4)
179.5ꢀ4)
88.8ꢀ4)
92.4ꢀ4)
175.6ꢀ4)
87.2ꢀ4)
91.8ꢀ3)
92.4ꢀ3)
87.8ꢀ3)
89.2ꢀ3)
90.6ꢀ3)
90.7ꢀ3)
89.0ꢀ3)
91.0ꢀ3)
88.4ꢀ3)
Co±Nꢀ1)
0
2.240ꢀ5)
2.265ꢀ5)
1.506ꢀ10)
1.511ꢀ10)
1.524ꢀ10)
Co±Oꢀ3)#1
Co±Oꢀ4)
Co±Nꢀ1 )
P±Oꢀ1)
P±Oꢀ2)
P±Oꢀ3)
Co±Oꢀ2)#2
Co±Nꢀ2)
0
Co±Nꢀ2 )
Oꢀ1)±Co±Oꢀ3)#1
Oꢀ1)±Co±Oꢀ4)
Oꢀ3)#1±Co±Nꢀ1)
Oꢀ4)±Co±Nꢀ1)
89.9ꢀ3)
92.0ꢀ3)
88.5ꢀ3)
177.7ꢀ3)
178.8ꢀ3)
89.2ꢀ3)
89.6ꢀ3)
91.1ꢀ3)
88.7ꢀ3)
177.7ꢀ3)
179.6ꢀ3)
112.5ꢀ6)
116.1ꢀ5)
110.5ꢀ5)
Oꢀ3)#1±Co±Oꢀ4)
Oꢀ1)±Co±Oꢀ2)#2
Oꢀ3)#1±Co±Oꢀ2)#2
Oꢀ4)±Co±Oꢀ2)#2
Oꢀ2)#2±Co±Nꢀ1)
0
Nꢀ2 )±Co±Nꢀ1)
Nꢀ2)±Co±Nꢀ1)
0
Oꢀ1)±Co±Nꢀ1 )
0
0
Oꢀ1)±Co±Nꢀ2 )
Oꢀ3)#1±Co±Nꢀ1 )
0
0
Oꢀ3)#1±Co±Nꢀ2 )
0
Oꢀ4)±Co±Nꢀ1 )
Oꢀ2)#2±Co±Nꢀ1 )
0
Oꢀ4)±Co±Nꢀ2 )
0
0
0
Oꢀ2)#2±Co±Nꢀ2 )
Nꢀ2 )±Co±Nꢀ1 )
0
Oꢀ1)±Co±Nꢀ2)
Oꢀ3)#1±Co±Nꢀ2)
Oꢀ4)±Co±Nꢀ2)
Oꢀ2)#2±Co±Nꢀ2)
Oꢀ1)±Co±Nꢀ1)
Nꢀ2)±Co±Nꢀ1 )
Oꢀ1)±P±Oꢀ2)
Oꢀ1)±P±Oꢀ3)
Oꢀ2)±P±Oꢀ3)
of coordinated water molecules are pointed into the tunnels
0
those of normal tetrahedron due to the existence of apical
P±H bond.
As illustrated in Fig. 5, III is formed by wave-like
running parallel to b-axis. The two pyridyl rings in a 4,4 -
bpy are disordered in two possible orientations along the
axial axis. The framework of II crystallizes in a noncentro-
symmetric space group Cc, with all the P±H bonds of
0
ZnꢀO PH) layers cross-linked by 4,4 -bpy ligands, result-
3
3
ing in a three-dimensional structure. In the ZnꢀO PH)
2
2
[
HPO
3
]
units pointing in the same direction. Selected
bond lengths and bond angles are given in Table 7. The
layers, both Zn and P atoms are in tetrahedral coordina-
tion environment. As shown in Fig. 6, every Zn tetrahe-
22
Ê
Co±Owater distance, 2.095ꢀ10) A, are similar to the Co 2
dron corner-shares its three O atoms with three HPO
3
tetrahedra and the fourth site is bonded to a nitrogen
2
HPO3
2
Ê
distances, 2.017ꢀ10)~2.103ꢀ9) A. The Co±Nbpy
O
distances, 2.196ꢀ5)±2.265ꢀ5) A, are comparable to that
0
Ê
atom of 4,4 -bpy. The arrangement of these tetrahrdra
results in ꢀZn-O±P±O)2 eight-member rings and ꢀZn±
O±P±O)
0
Ê
found in CoꢀC O )ꢀ4,4 -bpy), 2.147 A [87]. The coordina-
2
4
II
tion environment of Co exhibits no signi®cant deviation
from an ideal octahedron. The three P±O distances
Ê
ꢀ1.506ꢀ10)±1.524ꢀ10) A) of the [HPO ] anion, fall in
the range of common phosphate P±O bond lengths, while
4
sixteen-member rings. Selected bond lengths
and bond angles of III are given in Table 8. The average
22
Ê
Zn±O distance, 1.92 A, and Zn±N distance, 2.044 A, are
Ê
3
0
slightly shorter than those in ZnꢀC
Ê
2
O
4
)ꢀ4,4 -bpy), 2.083
and 2.182 A [87]. Unlike II, the two pyridyl rings of
the O±P±O angles are larger ꢀ110.5ꢀ5)±116.1ꢀ5)8) than
0
each 4,4 -bpy ligand do not exhibit disordering along
the long axis of the molecule, due to the fact that the
adjacent pyridyl rings are better packed in III.
As illustrated in Fig. 7, the crystal structure of IV
Table 8
Ê
Selected bond lengths ꢀA) and angles ꢀdeg) for III. Symmetry trans-
formations used to generate equivalent atoms: #1 2x 1 1, 2y 1 1/
2, 2z 1 3/2; #2 x 2 , y 1 1/2, z 1 1/2
contains parallel {Mn[O
0
2
PHꢀC
6
H
5
)]}
n
chains, cross-
linked by 4 ,4-bpy ligands to form a two-dimensional
framework. As shown in the ORTEP drawing and label-
Zn±Oꢀ1)
Zn±Oꢀ2)
Zn±Oꢀ3)
Zn±Nꢀ1)
1.925ꢀ4) P±Oꢀ1)
1.907ꢀ4) P±Oꢀ2)#1
1.924ꢀ4) P±Oꢀ3)#2
2.044ꢀ5)
1.520ꢀ4)
1.501ꢀ4)
1.511ꢀ4)
II
ing scheme in Fig. 8, each Mn ion is surrounded by
2
2
four corner-sharing [ꢀC
6
H
5
)HPO
2
]
tetrahedra and two
0
4,4 -bpy ligands trans to each other. Selected bond
lengths and bond angles, given in Table 9, indicate
Mn and P are in normal octahedral and tetrahedral
environment respectively. The average Mn±O and
Oꢀ2)±Zn±Oꢀ3) 114.82ꢀ19) Oꢀ1)±Zn±Nꢀ1)
103.16ꢀ18)
Oꢀ2)±Zn±Oꢀ1) 116.41ꢀ18) Oꢀ2)#1±P±Oꢀ3)#2 112.2ꢀ3)
Oꢀ3)±Zn±Oꢀ1) 110.01ꢀ18) Oꢀ2)#1±P±Oꢀ1)
Oꢀ2)±Zn±Nꢀ1) 107.0ꢀ2)
Oꢀ3)±Zn±Nꢀ1) 103.9ꢀ2)
114.82ꢀ19)
116.41ꢀ18)
Oꢀ3)#2±P±Oꢀ1)
Ê
Mn±N distances are 2.15 and 2.35 A while the average
Ê
P±O and P±C distances are 1.50 and 1.81 A

1636
J.-H. Liao et al. / Journal of Physics and Chemistry of Solids 62 ꢀ2001) 1629±1642
Fig. 5. Packing diagram of III, viewed along b-axis ꢀa) and viewed along c-axis ꢀb).

J.-H. Liao et al. / Journal of Physics and Chemistry of Solids 62 ꢀ2001) 1629±1642
1637
Fig. 6. ORTEP diagram and labeling scheme of III.
Fig. 7. Layered structure of IV, viewed along a-axis ꢀa) and viewed along c-axis ꢀb).

1638
J.-H. Liao et al. / Journal of Physics and Chemistry of Solids 62 ꢀ2001) 1629±1642
Fig. 8. ORTEP diagram and labeling scheme of IV.
Table 9
Ê
Selected bond lengths ꢀA) and angles ꢀdeg) for IV. Symmetry transformations used to generate equivalent atoms: #1 2x, y 2 , z 1 1/2; #2
x,y 1 1, z; #3 2x 1 1,y, 2z 1 1/2; #4 x 1 1, y, z
Mnꢀ1)±Oꢀ1)#1
2.134ꢀ2)
2.134ꢀ2)
2.157ꢀ2)
2.157ꢀ2)
2.325ꢀ4)
2.373ꢀ4)
2.140ꢀ2)
2.140ꢀ2)
2.167ꢀ2)
88.20ꢀ9)
91.57ꢀ9)
91.57ꢀ9)
88.20ꢀ9)
175.74ꢀ13)
86.95ꢀ7)
86.95ꢀ7)
87.87ꢀ7)
87.87ꢀ7)
93.05ꢀ7)
93.05ꢀ7)
92.13ꢀ7)
92.13ꢀ7)
180
Mnꢀ2)±Oꢀ2)
2.167ꢀ2)
2.310ꢀ4)
2.402ꢀ4)
1.494ꢀ2)
1.503ꢀ2)
1.814ꢀ3)
1.491ꢀ2)
1.492ꢀ2)
1.813ꢀ4)
89.70ꢀ8)
174.25ꢀ13)
87.51ꢀ7)
87.51ꢀ7)
87.13ꢀ6)
87.13ꢀ6)
92.49ꢀ7)
92.49ꢀ7)
92.87ꢀ6)
92.87ꢀ6)
180
Mnꢀ1)±Oꢀ1)
Mnꢀ2)±Nꢀ4)#2
Mnꢀ1)±Oꢀ4)#1
Mnꢀ1)±Oꢀ4)
Mnꢀ2)±Nꢀ3)
Pꢀ1)±Oꢀ1)
Mnꢀ1)±Nꢀ2)
Pꢀ1)±Oꢀ2)
Mnꢀ1)±Nꢀ1)#2
Pꢀ1)±Cꢀ1)
Mnꢀ2)±Oꢀ3)#3
Mnꢀ2)±Oꢀ3)
Pꢀ2)±Oꢀ3)
Pꢀ2)±Oꢀ4)#4
Mnꢀ2)±Oꢀ2)#3
Pꢀ2)±Cꢀ7)
Oꢀ1)#1±Mnꢀ1)±Oꢀ4)#1
Oꢀ1)±Mnꢀ1)±Oꢀ4)#1
Oꢀ1)#1±Mnꢀ1)±Oꢀ4)
Oꢀ1)±Mnꢀ1)±Oꢀ4)
Oꢀ4)#1±Mnꢀ1)±Oꢀ4)
Oꢀ1)#1±Mnꢀ1)±Nꢀ2)
Oꢀ1)±Mnꢀ1)±Nꢀ2)
Oꢀ4)#1±Mnꢀ1)±Nꢀ2)
Oꢀ4)±Mnꢀ1)±Nꢀ2)
Oꢀ1)#1±Mnꢀ1)±Nꢀ1)#2
Oꢀ1)±Mnꢀ1)±Nꢀ1)#2
Oꢀ4)#1±Mnꢀ1)±Nꢀ1)#2
Oꢀ4)±Mnꢀ1)±Nꢀ1)#2
Nꢀ2)±Mnꢀ1)±Nꢀ1)#2
Oꢀ3)#3±Mnꢀ2)±Oꢀ3)
Oꢀ3)#3±Mnꢀ2)±Oꢀ2)#3
Oꢀ3)±Mnꢀ2)±Oꢀ2)#3
Oꢀ3)#3±Mnꢀ2)±Oꢀ2)
Oꢀ3)±Mnꢀ2)±Oꢀ2)
Oꢀ2)#3±Mnꢀ2)±Oꢀ2)
Oꢀ3)#3±Mnꢀ2)±Nꢀ4)#2
Oꢀ3)±Mnꢀ2)±Nꢀ4)#2
Oꢀ2)#3±Mnꢀ2)±Nꢀ4)#2
Oꢀ2)±Mnꢀ2)±Nꢀ4)#2
Oꢀ3)#3±Mnꢀ2)±Nꢀ3)
Oꢀ3)±Mnꢀ2)±Nꢀ3)
Oꢀ2)#3±Mnꢀ2)±Nꢀ3)
Oꢀ2)±Mnꢀ2)±Nꢀ3)
Nꢀ4)#2±Mnꢀ2)±Nꢀ3)
Oꢀ1)±Pꢀ1)±Oꢀ2)
Oꢀ1)±Pꢀ1)±Cꢀ1)
Oꢀ2)±Pꢀ1)±Cꢀ1)
Oꢀ3)±Pꢀ2)±Oꢀ4)#4
Oꢀ3)±Pꢀ2)±Cꢀ7)
Oꢀ4)#4±Pꢀ2)±Cꢀ7)
119.31ꢀ14)
107.9ꢀ2)
109.4ꢀ2)
119.24ꢀ14)
109.1ꢀ2)
108.4ꢀ2)
175.02ꢀ13)
89.70ꢀ8)
90.05ꢀ9)
90.05ꢀ9)

J.-H. Liao et al. / Journal of Physics and Chemistry of Solids 62 ꢀ2001) 1629±1642
1639
Fig. 9. Thermogravimetric analysis of I ꢀinset: XRPD of the residue) ꢀa), II ꢀb), III ꢀc), IV ꢀd).
2
2
respectively. It should be noted that [ꢀC
6
2
H
5
)HPO
2
]
in Fig. 9ꢀa)±ꢀd). I exhibits rapid weight loss above
~2008C, resulting from the removal of dpa ligands. X-
ray powder diffraction pattern of the residue suggests
the formation of silver metal. The result is consistent
with the reducing character of dipyridylamine which
2
6 5 3
instead of the starting reagent, [ꢀC H )PO ] , is found
in the product. The mechanism remains unclear so far.
2
2
The attempt to synthesize IV using [ꢀC
starting materials resulted in other products.
6
H
5
)HPO
2
]
as
II
I
was found to reduce Cu to Cu [88] at elevated
temperature. II loses its coordination water at 130±
3
.2. Thermal analysis
In order to examine the thermal stability of I±IV,
thermogravimetric analyses ꢀTGA) under air atmosphere
1
attributed to 4,4 -bpy liberation, which is followed by
508C. The second weight loss starting at ~2508C is
0
3
1
51
P
! P oxidation and subsequent dehydration process
were carried out. The TGA diagrams of I±IV are given
2 2 7
to form Co P O residue. The liberation of the water

1640
J.-H. Liao et al. / Journal of Physics and Chemistry of Solids 62 ꢀ2001) 1629±1642
Fig. 9. ꢀcontinued)
molecule at 130±1508C is reversible and account for the
weight loss of 5.8%. The yellow dehydration product
changes back to orange under saturated water vapor in
several minutes. As shown in Fig. 10, it requires 20±
4. Conclusions
This work demonstrates that the microwave technique
can be used to prepare inorganic/organic coordination poly-
mers in signi®cantly reduced reaction time. Single crystals
of reasonable size can also be grown during this short time
period. It provides a promising synthetic route to make new
hybrid materials with novel properties originated from the
combination of inorganic and organic components. The
structures presented here illustrate the structural in¯uence
by the organic component and the geometrical preference of
metal centers. The reversible removal of solvent molecules
coordinated to metal centers is observed in this work, indi-
cating potential porous catalysts with accessible metal sites
can be synthesized.
3
0 min to complete water sorption process. The fact that
no further water sorption takes place at elongated time
implies that all the adsorbed water molecules are merely
II
coordinated back to the Co sites. It was also found that
the dehydrated II adsorb CH
3 3
CN and CH OH but not
2 5
C H
OH. However, it takes several hours to complete
the process. III exhibits remarkable thermal stability
and does not decompose until ~4008C. The ®nal residue
is Zn
place in the temperature range of 150±4508C, resulting
in the formation of Mn
2 2 7
P O . The thermal decomposition of IV takes
2 4 12
P O .

J.-H. Liao et al. / Journal of Physics and Chemistry of Solids 62 ꢀ2001) 1629±1642
1641
Fig. 10. Water sorption diagram. Samples were kept in saturated water vapor at 258C for 10 min ꢀa), 20 min ꢀb), 30 min ꢀc), 40 min ꢀd) and were
then reheated to 1508C.
Acknowledgements
[14] H. Gudbjartson, K. Biradha, K.M. Poirier, M.J. Zaworotko, J.
Am. Chem. Soc. 121 ꢀ1999) 2599.
[
[
[
[
15] O.M. Yaghi, G. Li, H. Li, Nature 378 ꢀ1995) 703.
16] O.M. Yaghi, H. Li, J. Am. Chem. Soc. ꢀ1996) 118295.
17] F. Robinson, M.J. Zaworotko, Chem. Commun. ꢀ1995) 2413.
18] L.R. MacGillivray, R.H. Groeneman, J.L. Atwood, J. Am.
Chem. Soc. 120 ꢀ1998) 2676.
We thank the National Science Council of Taiwan for
nancial support.
®
[
[
[
19] P. Brunet, M. Simard, J.D. Wuest, J. Am. Chem. Soc. 119
References
ꢀ
1997) 2737.
20] B.F. Abrahams, B.F. Hoskins, D.M. Michail, R. Robson,
Nature 369 ꢀ1994) 727.
[
[
1] S.L. Stupp, P.V. Braun, Science 277 ꢀ1997) 1242.
2] T.J. Barton, L.M. Bull, W.G. Klemperer, D.A. Loy, B.
McEnaney, M. Misono, P.A. Monson, G. Pez, G.W. Scherer,
J.C. Vartuli, O.M. Yaghi, Chem. Mater. 11 ꢀ1999) 2633.
3] Z. Shi, S. Feng, S. Gao, L. Zhang, G. Yang, J. Hua, Angew.
Chem. Int. Ed. 39 ꢀ2000) 2325.
21] M. Frijita, Y.J. Kwon, S. Washgzu, K. Ogwa, J. Am. Chem.
Soc. 116 ꢀ1994) 1151.
[
[
22] T. Sawaki, Y. Aoyama, J. Am. Chem. Soc. 121 ꢀ1999) 4793.
23] K. Endo, T. Koike, T. Sawaki, O. Hayashida, H. Masuda, Y.
Aoyama, J. Am. Chem. Soc. 119 ꢀ1997) 4117.
[
[
[
[
4] Z. Shi, L. Zhang, S. Gao, G. Yang, J. Hua, L. Gao, S. Feng,
Inorg. Chem. 39 ꢀ2000) 1990.
[
[
[
[
24] K. Maruoka, N. Murase,, H. Yamamoto, J. Org. Chem. 58
ꢀ
1993) 2938.
5] D. Hagrman, R.P. Hammond, R. Haushalter, J. Zubieta,
Chem. Mater. 10 ꢀ1998) 2091.
25] Y.-B. Dong, M.D. Smith, R.C. Layland, H.-C. zur Loye,
Chem. Mater. 12 ꢀ2000) 1156.
6] D. Hagrman, C.J. Warren, R. Haushalter, C. Seip, C.J. O'Con-
nor, R.S. Rarig, K.M. Johnson, R.L. LaDuca, J. Zubieta,
Chem. Mater. 10 ꢀ1998) 3294.
26] M. Kondo, T. Yoshitomi, K. Seki, H. Matsuzaka, S. Kitagawa,
Angew. Chem., Int. Ed. Engl. 36 ꢀ1997) 1725.
27] D. Venkataraman, G.F. Gardner, S. Lee, J.S. Moore, J. Am.
Chem. Soc. 117 ꢀ1995) 11600.
[
[
[
7] K. Cheetham, G. Ferey, T. Loiseau, Angew. Chem., Int. Ed.
Engl. 38 ꢀ1999) 3268.
[
[
28] H.J. Choi, M.P. Suh, J. Am. Chem. Soc. 120 ꢀ1998) 10622.
29] D.V. Soldatov, J.A. Ripmeester, Chem. Mater. 12 ꢀ2000)
8] P.J. Hagrman, D. Hagrman, J. Zubieta, Angew. Chem., Int.
Ed. Engl. 38 ꢀ1999) 2638.
1827.
30] A. Aum uÈ ller, P. Erk, G. Klebe, S. H uÈ nig, J. von Sch uÈ tz, H.
9] O.M. Yaghi, H. Li, C. Davis, D. Richarson, T.L. Groy, Acc.
Chem. Res. 31 ꢀ1998) 474.
[
[
[
Werner, Angew. Chem., Int. Ed. Engl. 25 ꢀ1986) 740.
31] A. Aum uÈ ller, P. Erk, S. H uÈ nig, Mol. Cryst. Liq. Cryst. 156
[10] M. Munakata, L.P. Wu, T. Kuroda-Sowa, Adv. Inorg. Chem.
46 ꢀ1998) 174.
ꢀ
1988) 215.
[
[
11] M.J. Zaworotko, Chem. Soc. Rev. 23 ꢀ1994) 283.
12] Y.-B. Dong, R.C. Layland, M.D. Smith, N.G. Pschirer, U.H.F.
Bunz, H.-C. zur Loye, Inorg. Chem. 38 ꢀ1999) 3056.
13] J. Lu, T. Paliwala, S.C. Lim, C. Yu, T. Niu, A.J. Jacobson,
Inorg. Chem. 36 ꢀ1997) 923.
32] P. Erk, H.-J. Gross, U.L. H uÈ nig, H. Meixner, H.-P. Werner,
J.U. von Sch uÈ tz, H.C. Wolf, Angew. Chem., Int. Ed. Engl. 28
ꢀ
1989) 1245.
33] R. Kato, H. Kobayashi, A. Kobayashi, J. Am. Chem. Soc. 111
1989) 5224.
[
[
ꢀ

1642
J.-H. Liao et al. / Journal of Physics and Chemistry of Solids 62 ꢀ2001) 1629±1642
[
[
34] P. Aum uÈ ller, S. Erk, E. H uÈ nig, K. H aÈ dicke, H. Peters, G. von
Schnering, Chem. Ber. 124ꢀ1991) 2001.
[62] R.C. Haushalter, L.A. Mundi, K.G. Strohmaier, H.E. King Jr.,
J. Solid, State Chem. 92 ꢀ1991) 154.
35] K. Sinzger, S. H uÈ nig, M. Jopp, D. Bauer, W. Bietsch, J.U. von
Sch uÈ tz, H.C. Wolf, R.K. Kremer, T. Metzenthin, R. Bau, S.I.
Khan, A. Lindbaum, C.L. Lengauer, E. Tillmanns, J. Am.
Chem. Soc. 115 ꢀ1993) 7696.
[63] G. Huan, J.W. Johnson, A.J. Jacobson, J.S. Merola, J. Solid,
State Chem. 89 ꢀ1989) 220.
[64] G. Huan, A.J. Jacobson, J.W. Johnson, E.W. Corcoran Jr.,
Chem. Mater. 2 ꢀ1990) 91.
[
36] R. Kato, H. Kobayashi, A. Kobayashi, J. Am. Chem. Soc. 111
[65] M.E. Leonowicz, J.W. Johnson, H.F. Shannon, J.F. Brody Jr.,
J.M. Newsam, J. Solid, State Chem. 56 ꢀ1985) 370.
[66] J.-H. Liao, C. Sigala, D. Guyomard, Y. Piffard, Acta Crystal-
logr. C52 ꢀ1996) 283.
ꢀ1989) 5224.
[
[
[
37] B.F. Hoskins, R. Robson, J. Am. Chem. Soc. 112 ꢀ1990) 1546.
38] C.L. Bowes, G.A. Ogin, Adv. Mater. 8 ꢀ1996) 13.
39] K. Inoue, T. Hayamiza, H. Iwamura, D. Hashizume, Y.
Ohashi, J. Am. Chem. Soc. 118 ꢀ1996) 1803.
[67] J.-H. Liao, D. Guyomard, Y. Piffard, M. Tournoux, Acta Crys-
tallogr. C52 ꢀ1996) 284.
[
[
40] O. Kahn, C.J. Martinez, Science 279 ꢀ1998) 44.
41] é. Hatlevik, W.E. Buschmann, J. Zhang, J.L. Manson, J.S.
Miller, Adv. Mater. 11 ꢀ1999) 914.
[68] J.-H. Liao, F. Leroux, T. Drezen, D. Guyomard, Y. Piffard,
Eur. J. Solid State Inorg. Chem. 33 ꢀ1996) 411.
[69] J.-H. Liao, F. Leroux, C. Payen, D. Guyomard, Y. Piffard, J.
Solid, State Chem. 121 ꢀ1996) 214.
[
[
[
[
42] R.A. Heintz, H. Zhao, X. Ouyang, G. Grandinetti, J. Cowen,
K.R. Dunbar, Inorg. Chem. 38 ꢀ1999) 144.
[70] J.Y. Lu, B.R. Cabrera, R.-J. Wang, J. Li, Inorg. Chem. 38
ꢀ1999) 4608.
43] J.M. Manriquez, G.T. Yee, S. McLean, A.J. Epstein, J.S.
Miller, Science 252 ꢀ1991) 1415.
[71] S.M-F. Lo, S.S-Y. Chui, L.-Y. Shek, Z. Lin, X.X. Zhang, G.-
H. Wen, I.D. Williams, J. Am. Chem. Soc. 122 ꢀ2000) 6293.
[72] S.S-Y. Chui, S.M-F. Lo, J.P.H. Charmant, A.G. Orpen, I.D.
Williams, Science 283 ꢀ1999) 1148.
44] H.O. Stumpf, Y. Pei, O. Kahn, J. Sletten, J.P. Renard, J. Am.
Chem. Soc. 115 ꢀ1993) 6738.
45] H.O. Stumpf, L. Ouahab, Y. Pei, D. Grandjean, O. Kahn,
Science 261 ꢀ1993) 447.
[73] L. Pan, E.B. Woodlock, X. Wang, C. Zheng, Inorg. Chem. 39
ꢀ2000) 4147.
[
[
46] K. Inoue, H. Iwamura, J. Am. Chem. Soc. 116 ꢀ1994) 3173.
47] M. Ohba, N. Maruono, H. Okawa, T. Enoki, J.-M. Latour, J.
Am. Chem. Soc. 116 ꢀ1994) 11566.
[74] O.R. Evans, R. Xiong, Z. Wang, G.K. Wong, W. Lin, Angew.
Chem., Int. Ed. Engl. 38 ꢀ1999) 536.
[
[
[
[
[
[
[
[
[
[
[
48] S. Decurtins, H.W. Schmalle, P. Schneuwly, L.-M. Zheng, J.
Ensling, A. Hauser, Inorg. Chem. 34ꢀ1995) 5501.
49] H. Miyasaka, N. Matsumoto, H. Okawa, N. Re, E. Gallo, C.
Floriani, Angew. Chem., Int. Ed. Engl. 34 ꢀ1995) 1446.
50] M. Ohba, H. Okawa, T. Ito, A. Ohto, J. Chem. Soc., Chem.
Commun. ꢀ1995) 1545.
[75] O.M. Yaghi, H. Li, J. Am. Chem. Soc. 118 ꢀ1996) 295.
[76] O.M. Yaghi, H. Li, J. Am. Chem. Soc. 118 ꢀ1996) 10401.
[77] T.M. Reineke, M. Eddaoudi, M. Fehr, D. Kelley, O.M. Yaghi,
J. Am. Chem. Soc. 121 ꢀ1999) 1651.
[78] S.O.H. Gutschke, D.J. Price, A.K. Powell, P.T. Wood, Inorg.
Chem. 39 ꢀ2000) 3705.
51] C. Michaut, L. Ouahab, P. Bergerat, O. Kahn, A. Bousseksou,
J. Am. Chem. Soc. 118 ꢀ1996) 3610.
[79] K.-J. Lin, Angew. Chem., Int. Ed. Engl. 38 ꢀ1999) 2730.
[80] H. Yu, S. Chen, K. Wang, J. Org. Chem. 57 ꢀ1992) 4781.
[81] Q. Zhang, J. Luo, E. Vileno, S.L. Suib, Chem. Mater. 9 ꢀ1997)
2090.
52] G. de Munno, T. Poerio, G. Viau, M. Julve, F. Lloret, Y.
Journaux, E. Riviere, Chem. Commun. ꢀ1996) 2587.
53] F. Lloret, G.D. Munno, M. Julve, J. Cano, R. Ruiz, A.
Caneschi, Angew. Chem., Int. Ed. 37 ꢀ1998) 135.
54] J.A. Real, E. Andr e s, M.C. Munoz, M. Julve, T. Granier, A.
Bousseksou, F. Varret, Science 268 ꢀ1995) 265.
[82] A. Arafat, J.C. Jansen, A.R. Edaid, H. Van Bekkum, Zeolites
13 ꢀ1993) 162.
[83] B.I. Whittington, N.B. Milestone, Zeolites 12 ꢀ1992) 815.
[84] G.M. Sheldrick, SHELXL-86 Bruker Analytical X-Ray Instru-
ments Inc. Madison, Wisconsin, USA, SHELXL-86 Bruker
analytical X-ray instruments Inc, Madison, Wisconsin, USA,
1990.
55] S. Han, J.L. Manson, J. Kim, J.S. Miller, Inorg. Chem. 39
ꢀ2000) 4182.
56] M. Munakata, L.P. Wu, T. Kuroda-Sowa, M. Maekawa, Y.
Suenaga, K. Furuichi, J. Am. Chem. Soc. 118 ꢀ1996) 3305.
57] O.R. Evans, R. Xiong, Z. Wang, G.K. Wong, W. Lin, Angew.
Chem., Int. Ed. Engl. 38 ꢀ1999) 536.
[85] G.M. Sheldrick, SHELXL-93 Bruker Analytical X-Ray Instru-
ments Inc. Madison, Wisconsin, USA, SHELXL-93 Bruker
analytical X-ray instruments Inc, Madison, Wisconsin, USA,
1993.
58] C. Chen, K.S. Suslick, Coord. Chem. Rev. 128 ꢀ1993)
2
93.
[86] P. Pyykk oÈ , F. Mendizabal, Inorg. Chem. 37 ꢀ1998) 3018.
[87] J.Y. Lu, M.A. Lawandy, J. Li, T. Yuen, C.L. Lin, Inorg. Chem.
38 ꢀ1999) 2695.
[
[
59] R.C. Haushalter, L.A. Mundi, Chem. Mater. 4ꢀ1992) 31.
60] K.H. Lii, R.C. Haushalter, J. Solid, State Chem. 69 ꢀ1987)
3
20.
[88] J.Y. Lu, B.R. Cabrera, R.J. Wang, J. Li, Inorg. Chem. 37
ꢀ1998) 4480.
[
61] L.A. Mundi, R.C. Haushalter, Inorg. Chem. 29 ꢀ1990) 2879.