The Green Synthesis, Structure Characterization Of Bio-MOFs, As Well As The Synthesis Of Carboxylate MOFS

In-situ solvents vapour-assisted aging is a conceptually novel approach, which is a green, mild and easy scalable method for the synthesis of metal-organic frameworks.A brief review of the research, classification, applications and synthesis methods of the Bio-MOFs.We demonstrate that a microporous bio-MOF [Cu(ade)(OAc)]·xH2O·yHOAc (1, ade=adeninate) is obtained quantitatively by water or HOAc vapour-assisted aging (VAG) of adenine and Cu(OAc)2·H2O for12or0.5hours at room temperature. As an alternative to VAG synthesis, complex1can be produced efficiently by liquid-assisted grinding (LAG) for one minute in the presence of small amounts of water. Furthermore, the products1obtained from both VAG and LAG synthesis are analytically pure and possess good thermal stability and relatively high specific surface area.Biomoleculars fumaric acid and niacin acid, biocompatible moleculars isonicotinic acid, EDTA, benzenetricarboxylic acid,4,4’-bipyridine, terephthalic acid were used as organic ligands to react with ZnO or CoCl·H2O or Cu(OAc)2·H2O or Gd2(CO3)3in water or methanal or DMF-VAG condition,16coordination polymers [Zn(fum)(1),[Zn(fum)]·2H2O(2),[Zn(fum)].4H2O(3),[Zn2(fum)2(bpy)](4),[Zn(NA)2(H2O)4](5),[Zn(NA)2](6),[Gd(C10H12N2O8)(H20)3]-·5H2O(7),[Cu3(BTC)2](8),[Co(bipy)Cl2]n(9),[Zn(INA)2(H2O)4](10),[Cd(INA)].4H2O(11),[Zn(INA)](12),[Cu(INA)](13)[Zn(BDC)·(H2O)2](14),[Zn(BDC)·(H2O)]-DMF(15),[Zn(BDC)·(H2O)](16)were obtained successfully. Furthermore,[Zn(fum)]·xH2O can reversible formal dehydration to the extended network structure1by further VAG in the non-aqueous condition of MeOH and vice versa. We can also synthesis4by DMF-VAG the mixture of1or [Zn(fum)]·xH2O and4,4’-bipyridine. Similarly,5and6can also transmute into each other in proper VAG condition. Besides, compound15,16and17also converted to each other in proper vapour condition.By using a flexible tetracarboxylic acid (H4L), and a new flexible dicarboxylic ligand H2L and three N-donor rigid co-ligands, fourteen coordination polymers,[Cu(4bipy)2](H2L)(1),[Cd2(L)(2bipy)2]·5H2O (2),[Cd2(L)(H2O)6]·2H2O (3),[Mn2(L)(H2O)6]·4H2O (4),[Co2(L)(H2O)6]·4H2O (5),[Zn2(L)(2bipy)2]·3H2O (6),[Zn2(L)(phen)2]·2H2O (7),[Ni2(L)(2bipy)2(H2O)2]·2H2O (8), and [Cu2(L)(phen)2(H2O)2](9),[Zn2(L)(phen)2(H2O)2](10)(4bipy=4,4’-bipyridine,2bipy=2,2’-bipyridine, and phen=1,10-phenanthroline)[Zn4O(L)3·(DMF)·(H2O)]·(DMF)2.5·(H2O)2(11),[Cu(L)·H2O]n·H2O (12),[Mn2(L2)·(C2H6O)·(H2O)5]n·(CH4O)2·(H2O)i.5(13),[Ni(HL)·(CH4O)2·(H2O)3]·(C14H8O2)0.5·(CH4O)·H2O (14) have been synthesized and structurally characterized by elemental analysis, IR, single-crystal X-ray diffraction and thermogravimetric analysis. The single crystal of ligand H4L reveals that there are two pairs of hydrogen bonds between two H4L molecules, which lead to a1-D linear supramolecular chain. Compound1shows a three-dimensional (3D) two-fold interpenetrated Cu2+-4bipy cationic host framework,[Cu(4bipy)2]2+with the4-connected dia net, in which there are1-D guest supramolecular chains formed by the intermolecular hydrogen bonds between adjacent (H2L)2-anions.2exhibits a two-dimensional (2D)4-connected{44.62} uninodal sql/Shubnikov tetragonal plane network. Compounds3-10display a new2D2-nodal (2,4)-connected network with a{84.122}{8}2topology. Compounds3-5,9and10generate a3D supramolecular structure by the hydrogen bonds between adjacent layers. Compound6-8form a3D network through strong π...π stacking interactions between adjacent layers. The co-ligands effect on the complex structures was studied. The single crystal of compound11exhibits a Zr4O coordination model, each L2-ligand bridge two Zn4O core and each Zn4O core connect with six L2-ligand, thus forming a1D chain. These chains are extended to2D layers by strong π...π interactions between the anthracene ring. Compound12exhibits2,4-connect2-nodal2D layers which containing "paddle-wheel" dinuclear units. These layers are connected by strong π...π interactions into a three dimensional supramolecular structure with3,4-connected fsh topology. Compound13shows a one-dimensional2-connected{0} uninodal chain network and generate a2D supramolecular network by the π...π interactions between the chains. Compound14shows zero-dimensional mononuclear structure with one carboxylate group of H2L coordinating to Ni(Ⅱ), while the other carboxylate group is protonated. Furthermore, their solid-state fluorescence was studied at room temperature.