Journal of Organometallic Chemistry
Two novel olefin-copper(I) coordination polymers with DHDAB as
building blocks
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Department of Chemical Engineering, Zhenjiang College, Zhenjiang 212000, People's Republic of China
School of Environmental & Chemical Engineering, Jiangsu University of Science & Technology, Zhenjiang 212000, People's Republic of China
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a r t i c l e i n f o
a b s t r a c t
Article history:
Received 28 November 2014
Received in revised form
As stable organometallic moieties, olefin-copper(I) coordination polymers are of interesting properties.
In this study, bioactive benzo[d]imidazol derivative 2,2 -(1,2-dihydroxyethane-1,2-diyl) bis(1,3-diallyl-
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H-benzo[d]imidazol-1-ium) bromide (DHDAB) and CuCl reacted at different temperatures under hy-
drothermal reaction condition to afford two olefin-Cu(I) coordination polymers with novel structural
features, 3D [(DHDAB)Cu Br Cl frame network and 1D [(DHDAB)Cu Cl infinite chain,
respectively. The dielectric constants were measured at different frequencies with temperature variation.
2015 Elsevier B.V. All rights reserved.
12 January 2015
Accepted 18 January 2015
Available online 11 February 2015
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Keywords:
Olefin-Cu(I) coordination polymer
Hydrothermal synthesis
Permittivity
Introduction
[d]imidazol-1-ium) bromide (DHDAB) was prepared by Phillips
condensation of -tartaric acid with 1,2-diaminobenzene in hydro-
L
Molecular architecture and self-assembly of coordination poly-
mers have attracted much attention in coordination and organo-
metallic chemistry in recent years [1e5], among which olefin-
copper(I) complexes play important roles in biochemistry and
modern organic chemistry and are employed as active species in
copper catalysis [6]. In the past few years, synthesis of highly stable
olefin-Cu(I) coordination polymers has been highlighted [7e11].
Benzo[d]imidazol and its analog, as active components in vivo,
play crucial roles in biological metabolism [12]. Possessing two or
more coordination sites, the above compounds are also popular
among coordination chemists. Williams et al. [13] reported some
polynuclear copper complexes with 1,2-bis(benzimidazol-2-yl)-
chloric acid, followed by N-allylation with allyl bromide in the
presence of sodium hydride. Under hydrothermal reaction
conditions, DHDAB reacted with CuCl in methanol and water at
different temperatures to afford two olefin-Cu(I) coordination
polymers with novel structural features, a 3D complex (1) and a 1D
complex (2), respectively, and the dielectric constants were
measured at different frequencies with temperature variation.
Experimental section
Materials and physical measurement
1
,2- ethanediol and its N-methylated analog as building blocks, all
DHDAB was prepared as described in Scheme 1. Other reagents
were obtained from commercial sources and used without further
purification. Mass spectrum was measured on a Finnigan LCQ™
spectrometer. FT-IR spectra were recorded on a Bruker VECTOR-22
spectrometer. Elemental analysis was determined by Elementar
Vario EL III analyzer. Dielectric constant was measured using an
automatic impedance Tonghui-2828 Analyzer with frequencies of
10 kHz, 90 kHz and 1 MHz, and pellet sample was made at 8 MPa.
of which contained a planar Cu lozenge as a central element and
2 2
O
in which the bridging oxygen belonged to an alkoxy group of the
ligand. However, N-allylated compound of 1,2-bis(benzimidazol-2-
yl)-1,2-ethanediol has never been employed for coordination
hitherto. In order to investigate the bond formation between olefin
and cuprous ion, a new ligand containing olefin functional group
was designed and synthesized as a continuation of our project. The
0
ligand 2,2 -(1,2-dihydroxyethane-1,2-diyl) bis(1,3-diallyl-3H-benzo
Synthesis of DHDAB
1
,2-Di(1H-benzo[d]imidazol-2-yl) ethane-1,2-diol was prepared
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according to the literature [14] with modification. 2-aminoaniline
022-328X/© 2015 Elsevier B.V. All rights reserved.
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