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JournalofFluorineChemistry206(2018)48–53
Journal of Fluorine Chemistry
Solvent effect on 3D topology of hybrid fluorides: Synthesis, structure and
luminescent properties of Zn(II) coordination compounds
Vanessa Pimentaa, Marine Ogera, Guillaume Salekb, Annie Hemon-Ribauda, Marc Leblanca,
Gilles Dujardina, Vincent Maisonneuvea,⁎, Jérôme Lhostea
a
LUNAM Université, Université du Maine, CNRS UMR 6283, Institut des Molécules et Matériaux du Mans (IMMM), Avenue Olivier Messiaen, 72085 Le Mans Cedex 9,
France
b
Institut de Chimie de la Matière Condensée de Bordeaux (ICMCB), Université de Bordeaux, CNRS UPR 9048, 87 Avenue du Dr Albert Schweitzer, Pessac 33608 Cedex,
France
A R T I C L E I N F O
A B S T R A C T
Keywords:
Hybrid fluoride
Tetrazole
The mixture ZnF2/HFaq./Hamtetraz (Hamtetraz = 5-aminotetrazole) with the molar ratio 10/80/10 reacts at
160 °C in different solvents (methanol/water and water respectively) to give two new 3D compounds:
(Zn4F4(amtetraz)4)∙H2O (1) and (Zn4F4(H2O)(amtetraz)4)·H2O (2). The structures, determined by single crystal X-
ray diffraction, exhibit neutral 3D-frameworks with narrow cavities that contain water molecules. Each network
is built up from two types of parallel chains connected by aminotetrazolate ligands. The comparison of 1 and 2
with literature compounds shows that the nature of the polar solvent, aprotic or protic, influences the network
characteristics, as well as the condensation of inorganic species or the bridging mode of the organic moieties.
The luminescence properties of the zinc fluoro-aminotetrazolates are discussed.
MOF
Solvothermal synthesis
Microwave heating
1. Introduction
influence of the synthesis parameters in azole based fluorinated net-
works, for instance, the molar ratio between the starting reactants and
Porous coordination compounds, also known as Metal-Organic
Frameworks (MOFs), have emerged during the last two decades. These
hybrid compounds are nowadays considered as a new generation of
multifunctional materials for potential applications in several fields,
such as gas storage, health, catalysis or luminescent devices [1–4]. The
desired properties can be tuned by combining the inorganic units,
commonly built up from 3d metals or lanthanides [5–8] and the organic
linkers, mainly carboxylic acids or azoles [9,10]. Azole ligands are
extremely versatile linkers due to their heterocyclic character, in par-
ticular tetrazole derivatives [11]. Four nitrogen atoms, available in
tetrazole rings, allow a broad range of bridging modes, opening the way
to the design of new porous crystalline buildings with a remarkable
structural diversity [10].
Whether the nature of the organic and inorganic entities plays a key
role [12–15], it has been demonstrated that reaction conditions such as
the synthesis temperature, the solvent or the pH [16–18] can strongly
influence on framework design. Although very numerous examples of
MOFs based on carboxylic acid linkers are available [19,20], fewer
studies are reported for azole based networks [21,22], and those on
fluorinated being downright scarce [23].
the synthesis temperature. We have shown that for fluorine rich com-
positions, hybrids with covalent bonds between the organic and in-
organic entities and with high dimensionalities are favoured [24,25].
Moreover we have demonstrated the key role of the synthesis tem-
perature on the topology of fluorinated MOFs [26]. At high tempera-
tures and in solvothermal conditions, dimethylformamide solvent
(DMF) hydrolyses into dimethylammonium cation [Hdma]+ and for-
mate anion (HCOO)− [27,28]. The fragments produced by the DMF
decomposition can either enter into the coordination sphere of the
metal cation or act as a template. The network dimensionality can also
be tuned by increasing the synthesis temperature, as demonstrated for
hybrid fluorozincates prepared in acetonitrile (MeCN) [29].
Herein, we highlight the determining role of the solvent in the
crystallization of zinc fluoro-aminotetrazolates. The solvothermal re-
action of identical starting mixtures of ZnF2/HFaq/Hamtetraz was ex-
plored in different solvents. Two new hybrid fluorides
(Zn4F4(amtetraz)4)·H2O (1) and (Zn4F4(H2O)(amtetraz)4)·H2O (2) were
identified in methanol/water and water, respectively. Their structures
are
compared
to
the
previously
reported
networks
[Hdma]·(Zn4F5(amtetraz)4) and [NH4]·(Zn4F5(amtetraz)4)·3H2O, respec-
Our recent work has been focused on the deep understanding of the
tively prepared in dimethylformamide and acetonitrile [24,29]. Lastly
⁎
Corresponding author.
Received 18 July 2017; Received in revised form 6 December 2017; Accepted 7 December 2017
Availableonline09December2017
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