Polyhedron
Transition metal coordination networks based on 1,3-bis(1,2,4-triazol-1-
yl)benzene and isophthalic acid: Luminescence and magnetic properties
⇑
Xiu Juan Shi, Peng Yun Chen, Zhen Ming Yin, Tuo Li, Ming Ze Wu, Li Tian
Tianjin Key Laboratory of Structure and Performance for Functional Molecule, Key Laboratory of Inorganic-Organic Hybrid Functional Material Chemistry,
Ministry of Education, Tianjin Normal University, Tianjin 300387, PR China
a r t i c l e i n f o
a b s t r a c t
Article history:
3 2
Solvothermal reactions of 1,3-bis(1,2,4-triazol-1-yl)benzene (btb), isophthalic acid (H ip) with M(NO )
2
Received 27 September 2017
Accepted 10 November 2017
Available online 24 November 2017
2+
2+
2+
2+
2+
(M = Co (1), Cu (2), Cd (3)) afforded three coordination polymers, [M(btb)(ip)]
n
(Co (1), Cu (2))
and [Cd (btb)(ip) O] O (3), respectively. Both compounds 1 and 2 show 2D networks with bin-
uclear paddle-wheel structures, however 3 is confirmed as 1D double-chain ladder. For complex 1, weak
ferromagnetic interactions are detected between Co ions of Co2 unit without long-range magnetic
ordering. Antiferromagnetic interactions are found between the Cu centers in complex 2. In addition,
2
2
ꢀ4H
2
n
ꢀ4H
2
II
Keywords:
Crystal structure
II
complex 3 shows red-shifted luminescence spectra with obviously higher intensity owning to the more
1
,3-Bis(1,2,4-triazol-1-yl)benzene
rigid arrangement of the
p systems.
Isophthalic acid
Luminescent property
Magnetic property
Ó 2017 Elsevier Ltd. All rights reserved.
1
. Introduction
Coordination polymers have obtained extensive interest not
[M(btb)(ip)]
n
(Co2+(1), Cu2+(2)) and [Cd
2
(btb)(ip)
2
ꢀ4H
2
O]
n
ꢀ4H
2
O
(3) were fabricated and structurally characterized by X-ray single
1
0
crystal analyses. In particular, d metal centers and the conjugated
only because of the structural diversity but also their attractive
properties, such as luminescence, chemical sensing, magnetism,
catalysis, and gas storage or separation [1–11]. One of the main
steps for preparation of polymeric metal complexes with fascinat-
ing applications is to select the multidentate bridging ligands or
mixed multidentate ligands [12–16]. A lot of N-donor bridging
ligands (like containing pyridine, imidazole, pyrazole and triazole
rings) have been widely used to construct coordination polymers
with fascinating architectures and interesting properties [17–24].
Among the various N-donor bridging ligands, triazole N-donor
ligands have been proven to be good candidates for the construc-
tion of coordination polymers with versatile topologies and
functional properties [25–28]. 1,3-Bis(1,2,4-triazol-1-yl)benzene
p
systems containing aromatic rings favor the development of
fluorescent materials.
2
. Experimental
2.1. General considerations
The reagents used in the syntheses were of analytical grade,
except that the solvent used was dried ((CH
ular sieve) and distilled prior to use. The elemental analyses
C, H, and N) were carried out on a Perkin–Elmer elemental
3 2
) SO over 4 Å molec-
(
analyzer. Powder X-ray diffraction measurements were recorded
on a D/Max-2500 X-ray diffractometer using Cu Ka radiation.
The fluorescent spectra were measured on a Varian Cary Eclipse
Fluorescence spectrophotometer.
(
abbreviated as btb) is a rigid ligand, which contains two triazole
ring and can act as bridging ligand. On the other hand, organic aro-
matic polyoxometalates play an important role in the formation of
coordination polymers with fascinating structures [29–33]. Among
2.2. Synthesis of ligand 1,3-bis(1,2,4-triazol-1-yl)benzene (btb)
2
them, isophthalic acid (H ip), in which the two carboxylate moi-
eties are predisposed at 120°, is a good oxygen donor for building
metal–organic networks. In this contribution, we choose btb
1
,3-Dibromobenzene (0.75 g, 3.2 mmol), triazole (2.18 g, 12.8
mmol), K CO (2.96 g, 21.0 mmol), CuI (0.03 g, 0.13 mmol) and 7
2
3
2
incorporated with isophthalic acid (H ip), as the building blocks,
drops of N, N’-dimethyl ethane amine were mixed in 15 ml dry
DMSO solution and heated at 150 °C for 36 h under a nitrogen
atmosphere. The mixture was cooled to room temperature, filtered
and the solid was washed with DMSO. The filtrate was distilled
under reduced pressure to remove the solvent and the residue
and three new complexes with various topological structure,
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277-5387/Ó 2017 Elsevier Ltd. All rights reserved.
0