Synthesis, structures, and photoluminescent properties of two ligand unsupported silver(I) coordination polymers from isonicotinate anions

Article abstract of DOI:10.1039/b417363e

Assembly of isonicotinate acid (HL) and Ag(I) by a layer-separating diffusion method at ambient temperature gave rise to two novel structural coordination polymers with ligand unsupported Ag...Ag interactions, namely, [(Ag₄L₄) · H₂O · 0.5CH ₃OH]_n (1) and [(Ag₃L₂)NO ₃]_n (2). Compound 1 is the first example of double-layer architecture and features an alternative stacking mode with Ag...Ag interactions, π-π interactions and Ag...O interactions. The synthesis of compound 2 offered us an opportunity to study the role of counteranions in Ag...Ag interactions. Both compounds display intense room temperature photoluminescence in the solid state. The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2005.

Full text of DOI:10.1039/b417363e

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P A P E R
Synthesis, structures, and photoluminescent properties of two
ligand unsupported silver(I) coordination polymers from
isonicotinate anions
Zheng Liu,ab Ping Liu,* Yun Chen, Jian Wang and Meihua Huang
a
ab
a
ab
a
Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences,
Fuzhou, Fujian, 350002, P. R. China. E-mail: pliu@fjirsm.ac.cn; Fax: 86-591-83714648;
Tel: 86-591-83704960
b
Graduate School of Chinese Academy of Sciences, Beijing, 100039, P. R. China
Received (in Durham UK) 15th November 2004, Accepted 5th January 2005
First published as an Advance Article on the web 18th January 2005
Assembly of isonicotinate acid (HL) and Ag(I) by a layer-separating diffusion method at ambient
temperature gave rise to two novel structural coordination polymers with ligand unsupported Agꢀ ꢀ ꢀAg
interactions, namely, [(Ag
4
L
4
) ꢀ H
2
O ꢀ 0.5CH
3 n 3 2 3 n
OH] (1) and [(Ag L )NO ] (2). Compound 1 is the first
example of double-layer architecture and features an alternative stacking mode with Agꢀ ꢀ ꢀAg interactions,
p–p interactions and Agꢀ ꢀ ꢀO interactions. The synthesis of compound 2 offered us an opportunity to study
the role of counteranions in Agꢀ ꢀ ꢀAg interactions. Both compounds display intense room temperature
photoluminescence in the solid state.
ment. Fluorescent analyses were performed on an Edinburgh
Instruments analyzer model FL920. XRPD data were collected
on an Xpert MPD diffractometer at room temperature.
Introduction
One of the thematic issues in silver(I) chemistry is the under-
1
0
standing of close-shell d Agꢀ ꢀ ꢀAg interactions that give rise to
intriguing supramolecular motifs, crystal packing, and specific
1
photophysical properties. Recent research has shown that
direct metal–metal interactions are one of the most important
Synthesis
ꢁ
.
) H
.
O 0.5CH
[
(Ag
4
L
4
2
3
OH]
n
(1). A solution of L (0.012 g,
.10 mmol) in MeOH (5 ml), which achieved the pH value of 9
2
,3
factors for the manifestation of such properties. Particularly
due to the limitation of evidence involving the existence of
weak Ag(I)ꢀ ꢀ ꢀAg(I) attractive interactions in the absence of
0
by neutralizing KOH with HL, was carefully layered on a
solution of AgNO3 (0.017 g, 0.10 mmol) in H O (5 ml).
2
Diffusion between the two phases over a period of two weeks
produced colorless block crystals. For 1, yield: 56%. Calc. for
4
any supportive bridging ligation, the induction and modula-
tion of such metal–metal interactions has become a more
challenging field. As is already known, isonicotinate anions
possess the capability to chelate and bridge metal atoms in
various coordination modes using the carboxylate oxygen
atoms and nitrogen atom of the pyridyl ring. Unfortunately,
silver(I) complexes with such heterocyclic aromatic carboxylate
C
H 1.76, N 6.07%.
24.5
H
20Ag
4
N
4
O
9.5: C 30.85, H 2.11, N 5.87%; found: C 31.32,
5
ꢁ
3 2 3 n
[(Ag L )NO ] (2). A solution of L (0.012 g, 0.10 mmol) in
ligands exhibiting short Agꢀ ꢀ ꢀAg separations were scare, and
MeOH (5 ml), which achieved the pH value of 7 by neutralizing
KOH with HL, was carefully layered on a solution of AgNO3
(0.017 g, 0.10 mmol) in H O (5 ml). Diffusion between the two
6
,16
only a few examples have been reported.
On the other hand,
it is widely acknowledged that self-assembly of coordination
frameworks is highly influenced by factors such as the solvent
system, template, pH value of the solution, and steric require-
2
phases over a period of two weeks produced colorless block
crystals. For 2, yield: 71%. Calc. for C H Ag N O : C 22.88,
H 1.28, N 6.67%; found: C 22.27, H 1.27, N 6.66%.
1
2
8
3
3
7
7
ment of the counterion. Herein, we synthesized two new
silver(I) coordination polymers [(Ag
1), and [(Ag )NO
4
L
4
) ꢀ H
2
O ꢀ 0.5CH
3 n
OH]
(
3
L
2
3
]
n
(2) (HL ¼ isonicotinate acid) by
X-Ray crystallography
controlling the pH value of the solution. To the best of our
knowledge, 1 was the first example of double-layer architecture
until now and displays intense photoluminescence in the solid
state at room temperature.
Single crystals of complexes 1 and 2 with approximate dimen-
sions 0.18 ꢂ 0.15 ꢂ 0.12 mm (1) and 0.40 ꢂ 0.20 ꢂ 0.20 mm (2)
were used for X-ray diffraction analyses. Data were collected
on a Bruker Smart Apex CCD diffractometer with Mo–Ka
˚
radiation (l ¼ 0.71073 A) at 173(2) K. Empirical absorption
Experimental
corrections were applied by using the SADABS program for
the Siemens area detector. The structures were solved with
direct methods and all calculations were performed using the
General
8
All reagents were analytical grade and used as received. The IR
spectra were recorded as KBr discs on a Magna 750 FT-IR
spectrometer. C, H and N microanalyses were performed on a
Vario EL III elemental analyzer. Thermogravimetric analyses
were performed on a Perkin Elmer TGA/SDTA851 instru-
SHELXTL package. The structures were refined by full-
matrix least squares with anisotropic thermal parameters
for non-hydrogen atoms. For 1, water H-atom coordinates
were located from difference maps and refined isotropically,
the O–H distances involving the water molecules were refined
T h i s j o u r n a l i s & T h e R o y a l S o c i e t y o f C h e m i s t r y a n d t h e
C e n t r e N a t i o n a l d e l a R e c h e r c h e S c i e n t i f i q u e 2 0 0 5
4
74
N e w J . C h e m . , 2 0 0 5 , 2 9 , 4 7 4 – 4 7 8

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Table 1 Crystal data and refinement parameters of 1 and 2
Crystal structures
1
2
The structure of 1 has been established by crystallography. As
shown in Fig. 1, each Ag(I) ion features a T-shaped geometry,
Formula
FW
C
24.5
H
20Ag
4
N
4
O
9.5
C
629.82
12
H
8
Ag
3
N
O
3 7
ꢁ
953.93
Triclinic
ꢀ
P1
being coordinated by two oxygen atoms from different L
ꢁ
Crystal system
Space group
T/K
Triclinic
ligands and a nitrogen atom from the third L (neglecting the
ꢀ
P1
173(2)
Agꢀ ꢀ ꢀAg interaction). The bond distances of Ag–O [ranging
173(2)
from 2.233(3) A for Ag(1)–O(7) to 2.283(4) A for Ag(4)–O(2)]
and angles of O–Ag–O [ranging from 159.86(14)1 for O(5)–
Ag(2)–O(8) to 161.15(13)1 for O(4)–Ag(4)–O(2)] are compar-
able to values observed in related dimeric structures of re-
˚
˚
˚
a/A
8.6509(12)
12.618(2)
14.000(3)
8.1686(16)
10.4479(18)
10.8106(17)
62.257(7)
69.159(7)
80.817(9)
763.1(2)
2
˚
b/A
˚
c/A
a/1
b/1
g/1
U/A
Z
107.936(10)
99.633(6)
90.210(7)
1430.9(4)
2
11
ported silver(I) carboxylates. The carboxylates from two
ꢁ
different L ligands and two silver(I) centers form a slightly
twisted eight-membered ring with an Agꢀ ꢀ ꢀAg separation of
3
˚
˚
˚
2
.8031(6)
A
for Ag(1)ꢀ ꢀ ꢀAg(2) or 2.8118(6)
A
for
ꢁ1
Ag(3)ꢀ ꢀ ꢀAg(4), which are shorter than the Agꢀ ꢀ ꢀAg separation
m/mm
Reflections collected
Reflections unique
2.757
10946
6442
3.855
5762
˚
of 2.88 A in the metallic state, indicating very strong Agꢀ ꢀ ꢀAg
1
a,1b,12
ꢁ
interactions.
Each L ligand serves as a m -bridge to link
3
3399
0.0169
three silver(I) centers through a nitrogen atom and two car-
boxylate oxygen atoms, respectively, leading to a 2D square-
grid-type architecture (Fig. 2a). It should be pointed out that
there is no interpenetration between adjacent layers, which
facilitated the formation of channels with a diagonal measure-
R
R
int
a
0.0160
0.0373
0.0829
1
[I 4 2s(I)]
[I 4 2s(I)]
0.0224
0.0568
a
wR
2
3
˚
Max., min. r/e A
1.522, ꢁ1.028
¼ S||Fo| ꢁ |Fc||/S|Fo|; wR
0.869, ꢁ1.207
a
2
2 2 4 1/2
R
1
2
¼ [Sw(Fo ꢁ Fc ) /Sw(Fo )]
.
˚
ment of 10.115(53) and 9.854(39) A or 10.079(41) and
9
˚
.833(48) A based on the edges of Ag atoms (Fig. 2b).
˚
Furthermore, such channels allow the accommodation of a
great number of guest water and methanol molecules. The
crystal structure of 1 is similar to previous frameworks that do
not have interpenetrations between adjacent layers and can
provide large void spaces to accommodate solvent molecules or
with a DFIX restraint of 0.85 A. Other hydrogen atoms were
generated geometrically and treated as riding. For 2, all
hydrogen atoms were generated geometrically and treated as
riding. The crystallographic data for 1 and 2 are summarized in
Table 1, and the selected bond distances and angles are listed in
Table 2.w
1
3
ions, but it is very different from those with diverse inter-
4
penetrations filling the void space.
1
The most salient feature of 1 is that the ligand unsupported
Agꢀ ꢀ ꢀAg interactions play a crucial role in the construction of
the double-layer architecture. Interestingly, the ligand unsup-
Results and discussion
˚
ported Agꢀ ꢀ ꢀAg interactions [3.0961(7) A for Ag(2)ꢀ ꢀ ꢀAg(4)#2]
Synthesis
are present only in interlayer A (Fig. 3). Besides, together with
the Agꢀ ꢀ ꢀAg interactions, the presence of p–p interactions,
The colorless crystals 1 and 2 were both synthesized by the
ꢁ
which can be only observed between pyridyl ring A and D
˚
reaction of AgNO in H O with L in CH OH via a liquid
diffusion method. The main synthetic difference between 1 and
consisted in the value of pH, 9 for 1, and 7 for 2, respectively.
3
2
3
[the distance between the centers of rings A–A is 3.727(19) A;
those of rings D–D is 3.710(21) A], further complete the
˚
2
1
connections in interlayer A. However, in interlayer B, the
5
As demonstrated previously, it is possible to control the
deprotonation of different labile hydrogen atoms attached to
the oxygen or nitrogen atoms at different pH levels and hence
tune the coordination mode. It should be mentioned that
previously reported isonicotinate acid with Ag(I) frequently
employed no m -bridge mode, which may be ascribed to the
3
fact that related compounds were produced under a lower
reaction pH value. This fact encouraged us to adjust the
˚
Agꢀ ꢀ ꢀO [2.661(14) A for Ag(4)ꢀ ꢀ ꢀO(4)] interactions also help to
support the parallel arrangement of the coordination polymer.
This contact is slightly longer than the range of the Ag–O bond
distances (2.23–2.52 and 2.17–2.61 for silver(I) carboxylate and
9
1a
1
0
oxalate complexes, respectively), however, it is still shorter
˚
than the sum of van der Waals radii (3.24 A) of the Ag(I)
1
2
ion and oxygen atom, implying a significant Ag(I)ꢀ ꢀ ꢀO
˚
interaction. The shortest Agꢀ ꢀ ꢀAg distances [3.774(26) A for
solution acidity to obtain new silver(I) cluster-based coordina-
ꢁ
the distance of Ag(4) and Ag(4)] in interlayer B preclude any
tion polymers. As expected, L in both 1 and 2 adopted a m
bridge mode under high pH value conditions. However, the pH
3
-
1
a
metal–metal interaction. It is worth noting that this alter-
native stacking mode is the first example of this kind of 2D
infinite coordination polymers.
difference between 1 and 2 led to the fact that, according to the
number of Ag(I) in the two reaction systems, there are more m
3
-
ꢁ
The structure of 2 is shown in Fig. 4 and is similar to
bridge L s in 1 than in 2, which resulted in the phenomenon in
which every Ag(I) in 1 coordinated with two oxygen atoms
from two different ligands and one nitrogen atom from the
third ligand, instead of only two ligands coordinating with
Ag(I) in 2 by two oxygen atoms or one oxygen atom and one
nitrogen atom. This work demonstrates that, besides increasing
the coordination sites of the ligands, the change of pH value in
high scope (pH X7) could lead to a larger number of this kind
of ligands. In addition, the purity of complexes 1 and 2 was
confirmed by X-ray powder diffraction analyses, in which the
lattice parameters derived from XRPD data are almost con-
sistent with those obtained by single crystal X-ray diffraction.
[
(Ag
and his co-workers. We obtained 2 from the reaction of
isonicotinic acid with AgNO , instead of AgBF . Recently,
3 2 4 n
L )BF ] (3), which has already been reported by Burrows
1
6
3
4
1
7
according to the research for a rectangular system, the
transannular Agꢀ ꢀ ꢀAg interaction competes with the inter-
action between Ag(I) and its anions, and the strength of the
Agꢀ ꢀ ꢀAg interactions is inversely proportional to their bite
sizes. Fortunately, the comparison between 2 and 3 endowed
us with an opportunity to explore the effect of counteranions in
our system. It can be observed that most Agꢀ ꢀ ꢀAg interactions
˚
˚
in 3 [ranging from 2.969(5) A for Ag(1)ꢀ ꢀ ꢀAg(3) to 3.236(5) A
for Ag(2)ꢀ ꢀ ꢀAg(3)] are stronger than those in 2 [ranging from
˚
2
.9699(6) for Ag(2)ꢀ ꢀ ꢀAg(3) to 3.2894(6) A for Ag(1)ꢀ ꢀ ꢀAg(3)],
w CCDC reference numbers 253118 for 1 and 253117 for 2. See http://
www.rsc.org/suppdata/nj/b4/b417363e/ for crystallographic data in .cif
or other electronic format.
ꢁ
while the Agꢀ ꢀ ꢀO distance between Ag(I) and NO
3
[ranging
˚
A for
˚
from 2.653(9)
A
for Ag(2)ꢀ ꢀ ꢀO(6) to 3.129(7)
N e w J . C h e m . , 2 0 0 5 , 2 9 , 4 7 4 – 4 7 8
475

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˚
Table 2 Selected bond lengths (A) and angles (1) for 1 and 2
1
Ag(1)–O(7)
Ag(1)–O(6)
2.233(3) Ag(3)–O(1)
2.253(4) Ag(3)–O(3)
2.253(4) Ag(2)–O(5)
2.253(4) Ag(2)–O(8)
2.268(3) Ag(4)–O(4)
2.272(3) Ag(4)–O(2)
2.235(3)
2.283(4)
2.335(4)
3.0961(7)
93.76(13)
79.03(9)
82.34(9)
Ag(1)–N(1)#1
Ag(1)–Ag(2)
2.319(4) Ag(3)–N(4)#3
2.8031(6) Ag(3)–Ag(4)
2.325(4) Ag(2)–N(2)
2.8118(6) Ag(2)–Ag(4)#2
96.16(14) O(1)–Ag(3)–O(3)
2.312(4) Ag(4)–N(3)#4
3.0961(7) Ag(4)–Ag(2)#2
160.81(15) O(2)–Ag(4)–N(3)#4
O(7)–Ag(1)–O(6)
O(7)–Ag(1)–N(1)#1
O(6)–Ag(1)–N(1)#1
O(7)–Ag(1)–Ag(2)
O(6)–Ag(1)–Ag(2)
160.75(13) O(8)–Ag(2)–N(2)
100.55(14) O(5)–Ag(2)–Ag(1)
97.82(14) O(8)–Ag(2)–Ag(1)
79.50(10) O(1)–Ag(3)–N(4)#3 98.91(14) O(4)–Ag(4)–Ag(3)
85.85(9) O(3)–Ag(3)–N(4)#3 94.77(14) O(2)–Ag(4)–Ag(3)
171.24(10) O(1)–Ag(3)–Ag(4) 78.08(10) N(3)#4–Ag(4)–Ag(3)
O(5)–Ag(2)–Ag(4)#2 113.46(11) O(3)–Ag(3)–Ag(4)
79.64(9)
81.39(9)
N(2)–Ag(2)–Ag(1)
169.46(10)
112.85(9)
62.27(9)
85.01(10) O(4)–Ag(4)–Ag(2)#2
N(1)#1–Ag(1)–Ag(2) 172.35(10) O(8)–Ag(2)–Ag(4)#2 84.94(9)
O(5)–Ag(2)–O(8)
O(5)–Ag(2)–N(2)
N(4)#3–Ag(3)–Ag(4) 163.71(10) O(2)–Ag(4)–Ag(2)#2
159.86(14) N(2)–Ag(2)–Ag(4)#2 75.69(10) O(4)–Ag(4)–O(2)
96.38(14) Ag(1)–Ag(2)–Ag(4)#2 113.014(19) O(4)–Ag(4)–N(3)#4 104.08(14) Ag(3)–Ag(4)–Ag(2)#2
161.15(13) N(3)#4–Ag(4)–Ag(2)#2 84.48(10)
85.037(19)
2
Ag(1)–O(3)#1
Ag(1)–N(2)#2
Ag(1)–Ag(2)
2.1356(19) Ag(1)–Ag(3)
2.159(2) Ag(2)–O(4)#1
3.0649(6) Ag(2)–O(1)
3.2894(6) Ag(2)–Ag(3)
2.1557(19) Ag(2)–Ag(2)#3
2.1648(19)
2.9699(6) Ag(3)–O(2)
3.0776(7) Ag(3)–N(1)
2.1546(18)
2.183(2)
O(3)#1–Ag(1)–N(2)#2 175.03(9)
O(4)#1–Ag(2)–O(1) 174.24(8)
O(4)#1–Ag(2)–Ag(3) 89.70(6)
O(1)–Ag(2)–Ag(3) 85.22(6)
O(4)#1–Ag(2)–Ag(1) 78.44(5)
O(2)–Ag(3)–Ag(2)
N(1)–Ag(3)–Ag(2)
O(2)–Ag(3)–Ag(1)
N(1)–Ag(3)–Ag(1)
Ag(2)–Ag(3)–Ag(1)
74.86(6) O(4)#1–Ag(2)–Ag(2)#3 74.09(6)
100.60(6) O(1)–Ag(2)–Ag(2)#3 108.53(6)
83.45(6) Ag(3)–Ag(2)–Ag(2)#3 142.535(14)
O(3)#1–Ag(1)–Ag(2)
N(2)#2–Ag(1)–Ag(2)
O(3)#1–Ag(1)–Ag(3)
N(2)#2–Ag(1)–Ag(3)
Ag(2)–Ag(1)–Ag(3)
79.73(6)
98.19(6)
87.62(6)
94.94(7)
96.33(6) Ag(1)–Ag(2)–Ag(2)#3
58.369(14) O(2)–Ag(3)–N(1)
77.568(12)
174.83(8)
O(1)–Ag(2)–Ag(1)
96.98(6)
66.037(13)
55.593(10) Ag(3)–Ag(2)–Ag(1)
Symmetry codes: for 1 #1 x ꢁ 2, y ꢁ 1, z ꢁ 1; #2 ꢁ x þ 1, ꢁ y þ 2, ꢁ z þ 2; #3 x þ 1, y, z þ 1; #4 x þ 1, y þ 1, z; for 2 #1 ꢁ x þ 1, ꢁ y þ 1, ꢁ z ꢁ 1;
2 ꢁ x, ꢁ y, ꢁ z þ 1; #3 ꢁ x þ 1, ꢁ y, ꢁ z.
#
Ag(1)ꢀ ꢀ ꢀO(6)] in 2 is shorter than the Agꢀ ꢀ ꢀF distance between
ꢁ
˚
Ag(I) and BF
˚
4
[ranging from 2.808(6) A for Ag(1)ꢀ ꢀ ꢀF(2) to
3
.130(7) A for Ag(2)ꢀ ꢀ ꢀF(4)] in 3. (Fig. 5) By the same token,
the differences of structural data, like those of the transannular
system, can also be tentatively attributed to the felicitous
combination of size-influence with the electronic effects char-
acter. Furthermore, compared to 3, whose infrared spectrum
shows several distinct n(B–F) resonances as opposed to a single
ꢁ
broad peak, the reduction of symmetry of the NO
the solid state was not observed, as evidenced by the bond
3
anion in
˚
lengths [1.253(4) A for O(5)–N(3), 1.256(2) A for O(6)–N(3)
and 1.256(5) A for O(7)–N(3)] and infrared spectrum, n(NQO)¼
˚
˚
Fig. 2 (a) The double-layer grid structure for 1; (b) space filling views
for the channels in 1. The channels have dimensions with a diagonal
˚
measurement of 10.115(53) and 9.854(39) A or 10.079(41) and
˚
.833(48) A based on the edges of Ag atoms. (Guest water and
9
methanol molecules are omitted for clarity.)
Fig. 1 Local coordination environment around Ag atoms in 1.
N e w J . C h e m . , 2 0 0 5 , 2 9 , 4 7 4 – 4 7 8
4
76

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Fig. 3 The ligand unsupported Agꢀ ꢀ ꢀAg interactions (thick lines), and
p–p interactions (dashed lines) in interlayer A; the Agꢀ ꢀ ꢀO interactions
(dotted lines) in interlayer B.
ꢁ ꢁ
1
4ꢁ
1
be interpreted as the relatively soft nature of O in NO
384 cm . In contrast with F in BF , this phenomenon can
2
ꢁ
ꢁ
3
.
Fig. 5 A section of the structure of polymer 2 showing the inter-
anions (dotted lines).
Thermal properties
ꢁ
actions between the silver atoms and the NO
3
To study the thermal stability of compounds 1 and 2, thermo-
gravimetric analysis (TGA) was performed on polycrystalline
samples under a nitrogen atmosphere. The TGA result of 1
showed a gradual release of all guest water and methanol
molecules in the 30–72 1C temperature range (3.63% observed,
tively (Fig. 6). Noting that HL displayed no luminescence in
the solid state at ambient temperature, the intense lumines-
cence in complexes 1 and 2 may be attributed to the silver(I)
2,3,19
cluster-based centers therein.
of the impact of the relativistic effect, as well as the coordina-
To our knowledge, because
3
.57% calculated). Subsequent to this, no obvious weight loss
was observed up to 274 1C. The most significant weight loss
occurred from 274 to 302 1C, which can be attributed to the
10
tion structures, the (n þ 1)s orbits of d metal are contracted
1b,19d,20,21
and therefore have lower energy.
A possible assign-
complete deposition of the complexes to form Ag
product. Considering the formation of stoichiometric amounts
of Ag O, the conclusion is supported by 50.6% of the residues,
2
O as a final
ment for the origin of the emission involves emissive states
derived from ligand-to-metal charge transfer (LMCT) transi-
tion mixed with d–s character. Presumably, in these complexes,
the highest occupied molecular orbital (HOMO) is associated
with the silver(I) 4d orbital and the carboxylate group s
orbital, while the lowest unoccupied molecular orbitals (LU-
MOs) are mainly associated with the silver(I) unoccupied
hybrid orbital based on 4d, 5s and 5p, which is similar to the
related silver(I) cluster-based coordination complexes reported
2
which is in accordance with the expected value of 48.6%. The
TGA result of 2 showed neither weight loss nor structural
change up to about 182 1C. Immediately above this point, an
obvious weight loss continued in the 182–302 1C temperature
range, indicating the collapse of the whole framework. The last
2
residue was also Ag O (56.2% observed, 55.2% calculated).
1
9c–f
previously.
It is noteworthy that a band with higher
emission energy is observed for 1, which can be attributed to
the larger p-conjugated system in quasi-coplanar layers and the
formation of a p–p interaction and Agꢀ ꢀ ꢀO interactions be-
tween adjacent layers, resulting in the energy decrease of
HOMO and therefore a larger HOMO–LUMO gap. Hence,
the different emission bands may be attributed to different 3D
architectures featuring different intensities of supramolecular
interactions (such as a p–p interaction and a Agꢀ ꢀ ꢀAg interac-
Luminescent properties
Ag(I) complexes usually emit weak photoluminescence at low
temperatures, and only a few silver(I) complexes exhibiting
luminescent properties at room temperature have been re-
1
8
ported. Interestingly, solids 1 and 2 exhibit photolumines-
cence at room temperature with the emission maximum at ca.
5
48 and 600 nm upon excitation at 358 and 370 nm, respec-
2
2
tion), which may lead to different HOMO–LUMO gaps.
Fig. 6 Fluorescent emission spectra of 1 and 2 in the solid state upon
excitation at 358 and 370 nm at room temperature.
Fig. 4 Local coordination environment around Ag atoms in 2.
N e w J . C h e m . , 2 0 0 5 , 2 9 , 4 7 4 – 4 7 8
477

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Acknowledgements
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This work was financially supported by the NSFC (Grant Nos.
20272058 and 20472085) and the program of Science and
Technology Plan of Fujian province of China.
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