| As a new class of hybrid organic-inorganic supramolecular materials, themetal-organic frameworks (MOFs) based on ordered networks formed from metalcations and organic electron donor linkers. They can exhibit tunable pore size andfunctionality, as well as extremely high surface areas, and can act as hosts for avariety of guest molecules. Since their discovery, MOFs have received muchextensive exploration, with applications such as gas storage and separations, guestcatalysts, drug delivery and electronic and optical applications. The syntheses of atypical MOF involve heating a mixture of metal salt and ligand in solvent for 12–48 h.In despite of this procedure can yield high quality crystals, it suffers from too longreaction times and can be very difficult to scale above 1 g. In scale up, the solvents,especially the oft-employed diethylformamide (DEF), can be expensive. In addition,the again use causes difficulty. Mueller and coworkers at BASF were the first tosearch the procedures of scale up for MOFs. They used almost 6 L of DEF tosynthesis MOF-5 on a 50 g scale. Thus, methods that decrease the amount of solventand reaction times required are highly desirable for not only laboratory scaleexperiments, but also for commercialization of MOF materials. At present, thesynthesis routes of the MOFS mainly involved the microwave, sonochemical, andmechanochemical syntheses as well as methods for catenation control andpostsynthetic modification. In this work, a series of porous zinc/copper metal-organicframeworks were synthesized, and their crystal structures and properties werecharacterized. The main results are as followings.1. We have synthesized and characterized the crystal structure of apoly[(μ3-camphorato- k3O:O':O'')(2-methyl-1H-imidazole-kN3)zinc(II)] complexe(Zn(C10H14O4) (C4H6N2)]n), in which each ZnIIion is coordinated by one N atom from one 2-methyl-1H-imidazole ligand and three O atoms from two camphorate(cap)ligands in a distorted tetrahedral geometry. In one of the cap ligands, one methylgroup is disordered between positions 1 and 3 in a 0.518 (12):0.482 (12) ratio. Eachcap ligand bridges three ZnIIions, forming two-dimensional layers, which interactfurther via N—H…O hydrogen bonds.The thermogravimetric analysis (TGA) result showed that the compound isstabilized up to a temperature of 100°C.The fluorescence analysis showed that the compound has two emission peaks at406nm and 464nm, respectively, where a wide emission peak is observed at406nm.The fluorescence emission in the compound can be attributed to the ligand tometal charge transfer (LMCT).The XRD results showed that ,the compound 1 is a pure phase.2. We have synthesized and characterized a {[Zn(NCS)2(C24H20N6)] 0.28H2O}ncomplexes, using Zn(OAc)2 2H2O, KSCN and1,2-bis{[2-(2-pyridyl)-1H-imidazol-1-yl]- methyl}benzene (hereafter L) as precursors.The ZnIIion showed a distorted octahedral coordination geometry and is coordinatedby two N atoms from two SCN anions and four N atoms from two organic ligands.The L ligands act as bridging bischelating ligands with cis coordination modes at theZnIIion. One-dimensional coordination polymers are arranged into layers byπ–πstacking interactions between the imidazole rings of adjacent chains, with aninterplanar distance of 3.46 (1) and centroid distances of 3.8775 (16) . One of thethiocyanate ligands is disordered over two positions with an occupancy factor of0.564 (3) for the major component. The partially occupied water molecule forms anO—H…S hydrogen bond with the disordered thiocyanate group.The TGA result showed that the compound is stabilized up to a temperature of79°C.The fluorescence analysis showed that the compound had two emission peaks at382nm and 480nm, respectively. The fluorescence emission at 382nm can beattributed to the charge transition in ligands, whereas the fluorescence emission at480nm can be assigned to the LMCT. The XRD results showed that ,the compound 2 is a pure phase.3. We have synthesized and characterized a [Cu(C9H6N3O2)(OH)(H2O)2]n,adopts a chain motif along [010] in which the CuIIatoms are bridged by hydroxygroups and 4-(1,2,4-triazol-4-yl)benzoate (tab) ligands. The CuIIatom lies on aninversion center and is sixcoordinated by two N atoms from two tab ligands, twohydroxy groups and two water molecules, giving a distorted octahedral geometry. Thehydroxy group and the tab ligand are located on a mirror plane. One of H atoms in thewater is disordered over two positions with equal occupancy factors. IntermolecularO—H…O hydrogen bonds extend the chains into a layer parallel to (100) andC—H…O hydrogen bonds connect the layers into a three-dimensional network.The TGA result indicated that the compound is stable up to a temperature of 68oC.The fluorescence analysis showed that the compound has two emission peaks at414nm and 458nm, respectively.The magnetic susceptibility result showed that the antiferromagnetic effect isdominant within molecules for the compound. As the temperature decreases fromroom to 100 K, the value ofχmT decreases continuously. Below 100 K, the value ofχmT decreases rapidly, meaning that antiferromagnetic effect is dominant in the wholemolecules. These results indicate that the compound has good magnetic properties.The XRD results showed that ,the compound 3 is a pure phase.
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