Inorganic Chemistry Communications 3 (2000) 694±696

www.elsevier.nl/locate/inoche

Synthesis and structure of a photoluminescent three-dimensional

network [AgL(MeCN)] (L ˆ 4,5-dichloro-2-cyano-3,6-dione-1,4-
cyclohexen-1-ol anion)
Ming-Liang Tong *, Xiao-Lan Yu, Xiao-Ming Chen
State Key Laboratory of Ultrafast Laser Spectroscopy and School of Chemistry and Chemical Engineering, Zhongshan University,
Guangzhou 510275, People's Republic of China
Received 4 July 2000; received in revised form 30 August 2000; accepted 9 October 2000

Abstract

A three-dimensional coordination network of ‰AgL…MeCN†Š1 (L ˆ 4,5-dichloro-2-cyano-3,6-dione-1,4-cyclohexen-1-ol anion)

has been synthesized and crystallographically characterized. The silver(I) atom in the title compound is coordinated by two chelating
oxygen atoms from one L ligand and two nitrogen atoms from an MeCN ligand and a cyano group of another L ligand at the
equatorial positions, and by one oxygen atom from the third L ligand at the apical direction, completing a distorted square py-
ramidal geometry. Each L ligand acts in l4 -mode to link three silver(I) atoms into a three-dimensional network, which shows room-
temperature emission upon photoexcitation at 350 nm. Ó 2000 Published by Elsevier Science S.A.

Keywords: Silver(I); Coordination polymer; Structure; Photoluminescence

Oligomeric or polymeric d10 metal compounds have dichloro-2-cyano-3,6-dione-1,4-cyclohexen-1-ol anion),

attracted increasing attention due to their interesting
photophysical and photochemical properties as well as
their intriguing structural diversity [1±5]. However, lu-
minescent AgI compounds are less common in contrast
to the CuI and AuI complexes, and most luminescent
AgI compounds exhibit emission at low temperature [6]
and belong to organometallic compounds using chalc-
ogenides and acetylides as the bridging ligands [1,3].
Only several oligomeric and monomeric AgI complexes
emit luminescence at room temperature [7±11], and lu-
minescent polymeric AgI complexes are rare [11±13].
Recently, we reported two novel luminescent three-di-
mensional non-interpenetrating networks using bis-
monodentate phenol groups of a Schi€-base ligand as
ÿ
bridges, namely [Ag2 (H2 L)3 ]n (X)2n (X ˆ NOÿ3 or ClO4 ;
H2 L ˆ 1,4-bis(salicylaldeneamino)butane) [11]. We re-
port here the preparation and crystal structure of a
novel three-dimensional coordination network self-as-
sembled by silver(I) salt with 2,3-dichloro-5,6-dicyano-
1,4-benzoquinone, namely ‰AgL…MeCN†Š1 …1† (L ˆ 4,5-
*
Corresponding author.
E-mail address: cestml@zsu.edu.cn (M.-L. Tong).
which exhibits a blue emission at room temperature.
An MeCN solution (10 cm3 ) of 2,3-dichloro-5,6-
dicyano-1,4-benzoquinone (0.227 g, 1.0 mmol) was
added dropwise to a stirred MeCN±H2 O (V/V 1:1) so-
lution (5 cm3 ) of AgNO3 (0.170 g, 1.0 mmol) at 50°C
over 15 min. After ®ve days at room temperature, the
solution precipitated deep-red block crystals in 75%
yield.
X-ray crystallography 1 has established that 1 con-
sists of a three-dimensional coordination network. The
Ag(I) atom displays distorted square-pyramidal coor-
dination geometry and is coordinated by three oxygen
atoms and two nitrogen atoms, as shown in Fig. 1. Two
nitrogen atoms from one MeCN and one L ligand, re-
spectively, and two bidentate-chelated oxygen atoms
from another L ligand occupy the equatorial positions
[Ag±N(L) 2.291(6) and Ag±N(MeCN) 2.243(6), Ag±
1
Crystal data: C9 H3 AgCl2 N2 O3 , is monoclinic, P21 21 21 : a ˆ
6.406(5), b ˆ 12.601(18), c ˆ 13.246(16) A,  b ˆ 102:085…4†°,
V ˆ 1069…2† A3 , Z ˆ 4. R1 …Fobs † ˆ 0:0392 and Rw …F 2 † ˆ 0:0998 for
155 parameters and 1171 observed data ‰I P 2r…I†Š at 293 K. The
absolute structure has been determined with a Flack parameter of
ÿ0.09(10).

1387-7003/00/$ - see front matter Ó 2000 Published by Elsevier Science S.A.

PII: S 1 3 8 7 - 7 0 0 3 ( 0 0 ) 0 0 1 7 7 - 5
 M.-L. Tong et al. / Inorganic Chemistry Communications 3 (2000) 694±696
Fig. 1. Perspective view of the coordination geometry.
 one oxygen atom from the
O ˆ 2.382(5) and 2.590(6) A],
third L ligand occupies the apical position [Ag±
 Within each L ligand, there are three
O ˆ 2.618(6) A].
almost identical C±O bond distances [C(1)±O(1)
1.231(6), C(6)±O(2) 1.199(7), C(3)±O(3) 1.209(7) A], 
suggesting that the quinone and phenolate groups are
not distinguishable due to the resonance e€ect.
Each L ligand connects three AgI atoms through one
chelating quinone, one monodentate phenolate and one
cyano group, resulting in a novel three-dimensional
coordination network with irregular hexagonal channels
along a-axis direction, as shown in Fig. 2. The alkyl
groups of the coordinated MeCN units occupy the
channels. Adjacent aromatic rings of the L ligands are
parallel to each other, and the o€-set face-to-face sepa-
 indicating strong p±p
rations are in the range 3.20 A,
interactions [14].
It should be noted that the L ligand is monovalent
anionic for the charge balance of the whole structure,
therefore, the reagent 2,3-dichloro-5,6-dicyano-1,4-ben-
zoquinone was changed to 4,5-dichloro-2-cyano-3,6-di-
one-1,4-cyclohexen-1-ol anion during the reaction in
Fig. 2. Perspective view of the three-dimensional network.
695
Fig. 3. Photo-induced emission spectrum in MeCN solution at room
temperature with kex ˆ 350 nm.
MeCN±H2 O mixed solution, this conversion may be
related to the addition of metal ion, however, concrete
mechanism is not unclear. It has been documented that
the study on the compounds of some d-block metal ions
(such as FeIII and MnIII ,IV) with catechol or their oxi-
dized species is very intriguing due to its biological rel-
evance [15,16], self-assembly of high-symmetry
supramolecular coordination clusters of some p-block
ones (such as GaIII , AlIII and SnIV with deprotonated
polycatechol or substituted ligands is also of current
interest due to its novel topologies [17,18]. However, no
report on AgI ion with the oxidized product of catechol
has been documented before our work, therefore, 1 may
be thought of as a silver(I) compound of a derivative
quinone and represents a good contribution to this ac-
tive area of study.
At room temperature 1 displays a blue photolumi-
nescence with emission maxima at 394 nm upon exci-
tation at 350 nm in MeCN solution, as shown in Fig. 3.
This emission may be assigned to originate from a li-
gand-to-metal charge-transfer (LMCT) transition, sim-
ilar to that (kem ˆ 385 nm in 77 K ethanol solution) of a
related coordination polymer [Ag(1,8-diisocyano-p-
menthane)2 ](PF6 ) [12,13].
Supplementary materials
Crystallographic data (excluding structure factors)
for the structures reported in this paper have been de-
posited with the Cambridge Crystallographic Data
Center. CCDC-146425.
Acknowledgements
This work was supported by the National Natural
Science Foundation of China (29625102, 29971033) and
696 M.-L. Tong et al. / Inorganic Chemistry Communications 3 (2000) 694±696
Zhongshan University. We thank the Chemistry De-
partment of The Chinese University of Hong Kong for
donation of the di€ractometer.
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