A novel hexanuclear silver(I) complex with photoluminescence properties

Article abstract of DOI:10.1016/j.poly.2016.08.002

A hexanuclear complex of d¹⁰–d¹⁰transition metal with organosulfur ligand, Ag₆(py2t)₆(py2t?=?pyrazine-2-thiol), has been synthesized using diffusion methodology at room temperature. Crystal structure was revealed using single crystal X-ray diffraction and data indicate that the complex synthesized containing Ag–Ag bonds in the silver cluster. The density function theory (DFT) calculation was performed to investigate the molecular orbital and photoluminescence potential. The photoluminescence properties of the complex have been further investigated, and a favorable fluorescence property was observed from the complex.

Full text of DOI:10.1016/j.poly.2016.08.002

Accepted Manuscript
A novel hexanuclear silver(I) complex with photoluminescence properties
Yining Wu, Xuepeng Wu, Sisi Fang, Shuai Yang, Weitao Li, Huan Wang,
Xiaoxi Yu
PII:
S0277-5387(16)30361-8
DOI:
http://dx.doi.org/10.1016/j.poly.2016.08.002
POLY 12139
Reference:
To appear in:
Polyhedron
Received Date:
Revised Date:
Accepted Date:
10 May 2016
19 July 2016
2 August 2016
Please cite this article as: Y. Wu, X. Wu, S. Fang, S. Yang, W. Li, H. Wang, X. Yu, A novel hexanuclear silver(I)
complex with photoluminescence properties, Polyhedron (2016), doi: http://dx.doi.org/10.1016/j.poly.2016.08.002
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A novel hexanuclear silver(I) complex with
photoluminescence properties
a
a*
a
a
a
c
Yining Wu, Xuepeng Wu, Sisi Fang, Shuai Yang, Weitao Li, Huan Wang,
b†
Xiaoxi Yu
a School of Petroleum Engineering, China University of Petroleum (East China),
Qingdao, Shandong, 266580, China
b School of Chemical Engineer, China University of Petroleum (East China),
Qingdao, Shandong, 266580, China
c School of Energy Resources, China University of Geosciences, Beijing 100083,
China
*
Xuepeng Wu:
Fax: +86-532-86981161; Tel: +86-532-86981183
Email: wuxuepeng@163.com
†
Xiaoxi Yu:
Fax: +86-532-86981161; Tel: +86-532-86981183
Email: wuxuepeng@163.com

Abstract
10
10
A hexanuclear complex of d -d transition metal with organosulfur ligand,
Ag (py2t) (py2t = pyrazine-2-thiol), has been synthesized using diffusion
6
6
methodology at room temperature. Crystal structure was revealed using single crystal
X-Ray diffraction and data indicate that the complex synthesized containing Ag-Ag
bonds in the silver cluster. The density function theory (DFT) calculation was
performed to investigate the molecular orbital and photoluminescence potential. The
photoluminescence properties of the complex have been further investigated, and a
favorable fluorescence property was observed from the complex.
Key Words: Silver complex, Ag-Ag interaction, DFT calculation, photoluminescence
Introduction
During the past decades, more and more attention has been paid to the construction of
metal-organic complexes. One of the main reasons for the current interest in those
complexes is their remarkable structural variations[1] and potential for many areas as
luminescent materials,[2] and drug delivery[3]. Besides, such complexes can be
applied to explain the active sites of some metalloproteins.[4, 5] Among the large
numbers of works reporteds, luminescent transition-metal complexes are under
substantial investigations due to their versatile metal-metal interactions, leading to
different spectroscopic behaviors and emission energies.[6, 7] In fact, a rapid growth
10
of interest has been shown in the development of luminescent materials based on d
10
metal. Different from the noble and rare earth metals, d metals used in synthesizing
1
0
the luminescent complexes are much more abundant and cheaper. d metals including
copper(I), silver(I), gold(I), zinc(II), and cadmium(II) have been utilized in most
research works and many complexes with attractive luminescence properties and
potentials as novel luminescent materials have been synthesized.[8-11]
In this work, the synthesis of a silver complex with a pyrazine-2-thiol as a ligand
was carried out. The system was chosen for several reasons. Among a wide range of

ligands applied, electron-rich sulfur-containing ligands have superior ability of
generating different novel structural motifs.[12] Therefore, a diversity of complex
structure in can be achieved. The presence of sulfur in the silver clusters enhances the
luminescence properties due to the electron transition between the metal ligand. In the
meantime, the orbital energies of sulfur and silver are better matched and there will be
greater delocalization of the spin electron density towards the bridging atoms.[13, 14]
The chemistry of silver-sulfur complex has attracted significant attention due to the
ability to adopt geometries of variable nuclearity and great structural complexity.
S. Natarajan and co-workers[15] reported several new inorganic coordination
polymers using Ag
6
S
6
6
N core as metalloligands through a sequential crystallization.
In the work of Singh,[16] new homoleptic hexanuclear silver(I) was synthesized and
characterized. Although many silver complexes of silver(I) mono- and multinuclear
complexes have been studied,[17] little research has been reported on the polymeric
neutral silver(I) complexes with pyrazine-2-thiol as a ligand. The three-dimensional
strucutres of such complexes is barely seen due to the poor solubility and the
difficulties in obtaining highly-diffracted single crystals.
In this investigation, the synthesis and properties of a hexanuclear silver complex
with a pyrazine-2-thiol as a ligand is reported. The ligand is chosen due to rigid
structure and rich coordination atoms. The density function theory (DFT) calculation
was performed to investigate the molecular orbital. Further study of
6 6
photoluminescence properties shows that the silver complex Ag (py2t) (py2t =
pyrazine-2-thiol) produces red emission at room temperature.
Experimental
Materials and instrumentation
All chemicals were purchased from standard commercial sources and used as received.
Solvents were reagent grade and used without further purification. All the synthesis in
this work were carried out under autogenous pressure. The elemental analysis was

performed on EA 3100 elemental analyzer. Raman spectrum was recorded from 100
to 1000 cm-1 with a Raman instrument. The phase purity and crystallinity of the
product were checked by powder X-ray diffraction (PXRD) using a diffractiometer
with Cu-K radiation. The fluorescence spectrum was measured with crystalline
α
samples at room temperature using Fluoromax-4 (USA).
Computational Details
All the theoretical calculations were performed using the Gaussian 09 program.[18]
The ground-state equilibrium geometries of the complex were fully optimized using
the hybrid functional B3P86 and the LANL2DZ ECP basis set.
Synthesis of pyrazine-2-thiol (py2t)
A mixture of 2-chloropyrazine (28.6 g, 0.25 mol) and thiourea (19 g, 0.25 mol) were
added into 200 mL ethanol. The mixture was refluxed for 3 h under vigorous stir in a
500 mL three-necked flask. After alcohol was removed by the evaporation, diluted
sodium hydroxide solution (30 wt%, 300 g) was gradually added into the flask. The
mixture was heated with reflux for another 5 hours and a large amount of ammonia
was released. After cooled to ambient temperature, the pH of the solution was
adjusted to 6.5 by adding quantitatively diluted hydrochloric acid. Extraction was
carried out with dichloromethane. Dichloromethane layer was collected and washed
with water for several times. Yellow powder was obtained through evaporation in 68%
(
wt) yield. The whole synthesis is illustrated in Scheme 1. The elemental analysis
result for C HN S in mass %: C, 35.82; H, 2.25; N, 20.89. Experiment: C, 36.13; H,
.01; N, 20.56.
4
2
2
Scheme 1. Preparation of pyrazine-2-thiol (py2t).
6 6
Preparation of Ag (py2t)

The yellow crystals of complex Ag
6 6
(py2t) were prepared by diffusion method.
AgNO (34 mg, 0.2 mmol) and pyrazine-2-thiol (28 mg, 0.25 mmol) were mixed in a
3
MeOH/MeCN solution (4:1, 5 mL) under vigorous stir in a radius flask. Triethylamine
was added later. The mixture was stirred at 90 °C for 2 hours, and a yellow colored
solution was obtained via filtration afterwards. The resulting solution was subjected to
diffusion of anhydrous ether and crystals were generated after 7 days. The yellow
crystals of the complex were collected and washed with MeCN and MeOH. The
crystals obtained were stable in air, water and common organic solvents and the yield
was 14%.
Crystal structure determination
Single crystals of the complex were carefully selected and separated. Crystal structure
data were measured on an Agilent Super nova and a Bruker APEXII CCD
diffractometer with Mo-Kα radiation source (λ = 0.71073 Å). The absorption
corrections were employed by the program SADABS.[19] Structure was solved by
2
direct method and refined by full-matrix least-squares on F using the SHELXTL-97
program.[20] The SQUEEZE procedure was applied to eliminate the disordered
solvent molecules. The crystal structure was inspected through the Addsym
subprogram of PLATON[21] to ensure that no attached symmetry should be used for
the models. The topological analysis and graphs were generated by applying the
TOPOS program. [22] The crystallographic data and refinement are summerized in
Table 1.
Table 1 Crystallographic data of the Ag
6 6
(py2t)
Empirical formula
Formula weight
Crystal system
Space group
C
24
H
18Ag
6
N
12
S
6
F(000)
1248
1314.08
Crystal size / mm
Temperature / K
θ range for date
collection / (°)
0.1*0.1*0.2
293(2)
Monoclinic
P21/c
3.10 to 28.53

a / Å
b / Å
8.2259(2)
Limiting indices
-11≤h≤10,
29≤k≤26,
12≤l≤11
-
-
22.3698(6)
Reflections
9763 / 3966
collected / unique
[R(int) = 0.0434]
(
Rint)
c / Å
Volume / Å
γ / (°)
9.5415(3)
1730.72(9)
90
Goodness-of-fit on
F 2
1.046
3
Final R indices
R
1
= 0.0569,
wR = 0.1607
= 0.0919,
wR = 0.1918
(
I>2σ(I))
2
R indices (all dates)
R
1
2
Z
2
Absorption
coefficient µ
Mo-Kα) / mu
3.730
-1
(
= ꢂ ꢃꢄꢅ ꢄ − ꢄꢅ ꢄꢃꢉꢄꢂ ꢈꢄ. ꢊꢀ = ꢌꢂꢍꢊꢎꢅ − ꢅ ꢏ ꢐꢉꢂꢍꢑꢎꢅ ꢏ ꢐꢒꢁꢉꢋ.
ꢋ
ꢋ ꢋ
ꢋ ꢋ
ꢀꢁ
ꢆ ꢇ ꢋ ꢆ ꢇ ꢆ
Results and Discussion
Synthesis and Characterization
Ag(I) complex was obtained in good yield by the treatment of a solution of the ligand
py2t and metal salt AgNO . The complex is air- and moisture-stable and insoluble in
water, common organic solvents including alcohols, acetonitrile, acetone, DMSO and
3
-
1
DMF. The Raman spectrum of the complex (Fig. S1) shows two bands at 750 cm
-
1
and 650 cm , which can be assigned to the breathing vibration of the C-N ring. Phase
purity of the complex was confirmed by comparison of the powder diffraction pattern
(
Fig. S2) with the data calculated from the single-crystal X-ray study, despite minor
differences can be seen in the intensities and widths of some peaks.
Crystal Structure of [Ag (py2t)
6
6
]
6 6
The exact structure of Ag (py2t) was revealed by single crystal X-ray

6 6
crystallography. The ORTEP diagram of Ag (py2t) with 30% thermal ellipsoids and
hydrogen atoms omitted for clarity is shown in Fig. 1. The selected bond distances
and angles are given in the Table S1. Single-crystal analysis has revealed that the
6 6
hexanuclear cluster Ag (py2t) has six Ag centers bridged by the py2t ligands which
exhibits as a distorted octahedron as shown in Fig. 2. As can be seen from the
structure, each Ag(I) is bonded by two sulfur atoms and one nitrogen atom from three
py2t ligands, yielding an approximately monoclinic geometry. Such three-coordinate
metal center is not common for Ag(I), even though similar core structures have, been
found with 2-mercaptobenzothiazole in hexanuclear Ag(I) complexes. With
pyrazine-2-thiol in Ag(I) complex is much less frequent and has not been reported.
The py2t molecule works as a µ
3
-bridging ligand to link three Ag(I) ions. The nitrogen
atom from the py2t molecule links to one Ag(I) ion and the axial µ
2
-sulfur to two Ag(I)
ions, forming one face of the octahedron and shortening the distances between Ag(I)
ions.
Fig. 1 An ORTEP view of the structure of complex with 30% thermal ellipsoids,
hydrogen atoms omitted for clarity.

Fig. 2 The molecular structure of complex.
The Ag-S bond distances of complex Ag
.511(3) Å (Table S2), which are similar to those distances found in other silver
complexes.[23-25] The Ag-N bond distances of complex Ag (py2t) are in the range
of 2.198(6) ~ 2.338(7) Å, which are in consistence with the reported complex
{Ag(SR)} ] (2.331(11) Å).[23, 26] The Ag···Ag distances in the Ag (py2t) complex
6 6
(py2t) are within the range of 2.346(3) ~
2
6
6
[
6
6
6
are in a wide range from 2.969 to 3.789 Å. The L(S, N)-Ag(3)-L(S, N) angles are in
#
the range of 91.80(19) ~ 153.67(19)°. The Ag(4, 5)-Ag(3)-Ag(5, 5 ) angles are in the
range of 62.13(3) ~ 82.66(3)°. All the bond lengths and angles are consistent with the
2 2
similar complexes, such as [Ag Cl (4-pdtH)].[27]
In order to make the hexanuclear silver cluster more clear, the distorted octahedron
consisting of six Ag(I) without other atoms is shown in Fig. 3. The Ag-Ag distances
vary from 2.969 Å to 3.789 Å, and are mostly shorter than the sum of the Van der
Waals radii of two Ag atoms (3.44 Å).The interaction of Ag-Ag might be best
considered as weak interactions, since some of the values are very close to those
presented in metallic silver (2.88 Å).[28] This indicates reasonable argentophilic
(
Ag···Ag) interactions, which have been observed in other related structures as
well.[29, 30]

Fig. 3 Distorted octahedral Ag cluster formed by the hexanuclear cores in complex
When expanding the molecules to a bulk network in the b axis, it can be clearly
6 6
observed in Fig. 4(a) that the stack of the Ag (py2t) with Ag···S interaction and the
weak π···π stack interaction produce a three-dimensional network structure. The
distance between two adjacent aromatic ring centers and the distance between
nitrogen atom and the adjacent aromatic ring were determined and considered to be
the versatile Ag···S interaction and the aromatic ring π···π stack interaction,
respectively. The weak Ag···S interaction between the adjacent complexes was further
evaluated and a Ag···S distance of 3.1218 Å was found as shown in Fig. 4(b). In a
word, the self-assembly of supramolecular networks of the complex is driven by the
multiple intermolecular Ag···S interactions between Ag(I) centers and sulfur atom of
ligands as well as the weak π···π interaction.

Fig. 4 (a) Two adjacent complexes showing the very weak π-π stack interaction.
Fig. 4 (b) The Ag-S interaction of adjacent complexes.
As shown in Fig. 5, the formation of bulk structure may be a result from the weak
π···π interactions between different one-dimensional chain structures. This may be
considered as a new synthetic strategy of framework coordination in contrast with the
existing methods, self-assembled with simple rigid linear ligands, and therefore may
contribute to a better understanding of inorganic crystal design for predictable,
multi-dimensional infinite networks of various topologies.
Fig. 5 View down the crystallographic b axis of CDHAB of the packing diagram

Theoretical studies
Density function theory (DFT) calculations were performed with the ground-state
geometries adapted from the analytical processing X-ray data. Geometry was
optimized using the B3P86 functional with two bases set: 3-21g for C, H, N, S atoms
and LanL2DZ for Ag atom. According to the frontier molecular orbital theory, HOMO
(
the highest occupied molecular orbital) and its nearby occupied orbits can give
priority to donor electron, while LUMO (the lowest unoccupied molecular orbital)
and its nearby free orbits are easy to be the acceptor. The energy gap between these
orbitals has significant influences on the activity of the compounds. Therefore, the
relationships between the aforementioned orbits are very important because they are
related to not only the charge transfer properties but also the photoluminescent
properties of the complex.
As shown in Fig. 6, the LUMO mainly composed of s orbitals of Ag(I), while the
I
HOMO mainly consists of p orbitals of ligand py2t as well as d orbitals of Ag . The
photoluminescent properties of this complex are mainly due to the intramolecular
electron transition. Therefore, when excited, the electron density has moved from Ag
d orbitals together with py2t p orbitals to Ag s orbitals. It is assumed that the emission
of Ag
6
(py2t) is a ligand to metal charge transfer.
6
Fig. 6 Electron-density distribution of LUMO (left) and HOMO (right) frontier
orbitals of the complex

Photoluminescent properties
For further evaluation on the solid-state photoluminescent properties of the complex,
6 6
the fluorescence excitation and emission properties of Ag (py2t) were investigated at
room temperature. It is reported that only few of luminescence silver(I) compounds
are luminescent at room temperature, while most of them exhibit such property at
lower temperature.[31] Nevertheless, in this investigation, the red emission band with
a maximum peak at 695 nm for complex Ag
6
(py2t) appeared clearly at room
6
temperature. The excitation band with a peak at 372 nm, and a wide stokes shift 323
nm were observed. The fluorescence-emission of free ligand was investigated as well
and no fluorescence emission peak of ligand was observed in all the experiments of
excitation wavelength. The main reason of this property is ascribed to the chelation of
nitrogen and sulphur atoms to the central metals and the increase of conjugation upon
metal silver coordination.
Fig. 7 Solid-state excitation and emission spectra for complex 1 at room temperature
Conclusion

1
0
10
6 6
In summary, a hexanuclear d -d transition metal complex Ag (py2t) was
synthesized with organosulfur ligands using diffusion method at ambient temperature.
The exact structure was characterized by single crystal X-ray diffraction analysis.
Meanwhile, the DFT calculation was used to characterize the electronic transition
between HOMO and LUMO of Ag
6
(py2t) . Photoluminescent property analysis
6
reveals that the complex exhibits a strong fluorescence in the solid state at room
temperature. The study provides a practical origin of photoluminescence materials.
Based on the study above, further exploration of coinage metals and thiolate ligands is
in progress.
Appendix A. Supplementary data
CCDC <1478950> contains the supplementary crystallographic data for <
C24H18Ag6N12S6>. These data can be obtained free of charge via
http://www.ccdc.cam.ac.uk/conts/retrieving.html,
Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: (+44)
223-336-033; or e-mail: deposit@ccdc.cam.ac.uk.
or
from
the
Cambridge
1
Acknowledgement
We thank Deng Li for providing the helpful of Gaussian. Allocation of computer
time from SCCAS is gratefully acknowledged.

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a
4
2
a

Two adjacent complexes showing the very weak π-π stack interaction.
Electron-density distribution of LUMO (left) and HOMO (right) frontier orbitals of
complex

1
0
10
A hexanuclear complex of d -d transition metal with organosulfur ligand has been
synthesized using diffusion methodology at room temperature. The DFT and
photoluminescence properties of complex have been investigated, and a favorable
fluorescence property was observed from the complex.