Synthesis, Characterization And Properties Of The Complexes Constructed From Chiral Amino Acid Derivates

In recent years, the design and synthesis of metal-organic frameworks (MOFs) have afforded a great deal of interest because of their various structures and extensive applications in the filed of functional materials such as catalysis, luminescence and etc. This paper summarizes the research advances of chiral coordination polymers. A series of coordination polymers constructed by chiral amino derivatives have been synthesized, and their crystal structures and properties were determined. In this paper, the main results are as follows:First, eleven coordination compounds constructed by (+)-N-Tosyl-L-glutamic acid: {[M (tsgluO)(2,4'-bipy)2(H₂O)2]·5H₂O}n (M= Ni,1; Co,2), {M(tsgluO)(4,4'-bipy)·0.5H₂O}n (M= Ni,3; Co,4), {[Cu(tsgluO)(H₂O)]₂·3H₂O}n (5), {Cu(tsgluO)(2,2'-bipy)}n (6), {Zn(imi)(H₂O)(tsgluO)}n (7), {[Zn(2,4'-bipy)(H₂O)](tsgluO)}n (8), [Mn(4,4'-bipy)₂(H₂O)₄](HtsgluO)₂·2H₂O (9), {Zn(bpp)₂(tsgluO-Me)₂}n (10), {Zn(bpp)(tsgluO-Me)₂}n (11) (H₂tsgluO = (+)-N-Tosyl-L-glutamic acid, bipy= bipyridine, imi= imidazole, bpp= 1,3-bis(4-pyridyl)propane) have been synthesized and characterized by X-ray diffraction analysis, elemental analysis, IR, thermal analysis, and their fluorescent and magnetic properties and asymmetric catalysis were also studied. Unexpectedly, tsgluO-Me2 (12) was obtained.Compounds 1 and 2 are isostructural and crystallize in the acentric monoclinic space group Cc, forming the same 1D chain structures. The chains are further connected byÏ€-Ï€stacking and hydrogen bonds interactions to form 3D supramolecular network. Compound 3 shows the chiral space group P21, forming a homochiral 2D architecture, which is further connected by hydrogen bonding interactions to form three-dimensional supramolecular network. Compound 4 crystallizes in the space group P-1 and is composed of binuclear [Co2O6N2]n4- units, which presents a 2D bilayer framework and is further connected by hydrogen bonding andÏ€-Ï€packing interactions to form three-dimensional supramolecular network containing one-dimensional channels with lattice water molecules. Compound 5 crystallizes in the space group P21 and contains a paddle-wheel dicopper(II) structure, which is featuring 1D double chains. The chains are further self-assembled through the non-covalent interactions of weakÏ€-Ï€stacking and hydrogen bond to form pseudo-3D supramolecular structures with 1D channels, where the guest water molecules are located. Compounds 6 crystallizes in the chiral space group P212121 and is giving ladder-like 1D double chains. Compounds 7 crystallizes in the chiral space group P21 and shows ladder-like 1D double chains. The double chains are further connected by hydrogen bonding to form two-dimensional supramolecular network. Compound 8 crystallizes in the space group P21/c and is giving a 1D single chain, which is self-assembled to form 2D supramolecular structures through hydrogen bonding interactions. Compound 9 crystallizes in the space group P-1 and is connected byÏ€-Ï€stacking and hydrogen bonding interactions to form 3D supramolecular network. Compounds 10 and 11 crystallize in the space group P-1 and display 1D chain structures. What different is that compound 10 is a 1D bpp-connected Zn–bpp–Zn double chain and further hydrogen-bonded into 2D networks. The formation of the tsgluO-Me2 moiety in compound 12 results from an in situ esterification reaction between tsgluO-H₂ and methanol and is driven by an excess of methanol and anhydrous conditions. Additionally, magnetic properties study indicates that compounds 1-4 show weak antiferromagnetic interactions. Compound 5 shows antiferromagnetic interactions between the Cu(II) centers of each dicopper unit. Compounds 7-11 show intense fluorescence at room temperature. Catalytic study indicates that compound 5 shows well-catalytic properties.Second, seven coordination compounds constructed by phthalyl-L-valine acid: [Mn(phen)₂(HL)₂·3.5H₂O] (13), [Mn(phen)₂(phth)(H₂O)·4H₂O] (14), {Cu(phen)(H₂O)(phth)·CH3OH}n (15), {[Cu(2,2'-bipy)(H₂O)](phth)·3.5H₂O}n (16), {Zn(phen)(phth)(H₂O)·1.125H₂O}n (17), {[M(4,4'-bipy)(H₂O)₂](phth)·2H₂O}n (M= Zn,18; Mn,19) (H₂L = phthalyl-L-valine acid, H₂phth = phthalic acid, bipy = bipyridine, phen = 1,10-phenanthroline) have been synthesized and characterized by X-ray diffraction analysis, elemental analysis, IR, thermal analysis, and their fluorescent and magnetic properties.Compound 13 crystallizes in the space group C2/c and is further connected byÏ€-Ï€stacking and hydrogen bonds interactions to form 3D supramolecular network containing 1D channels with lattice water molecules. Compound 14 crystallizes in the space group P21/c and is further extended into 1D chain throughÏ€-Ï€stacking. Compound 15 crystallizes in the space group Pbcm and exhibits a 1D chain structure, which is further hydrogen-bonded into 2D networks. But unfortunately, the phthalyl-L-valine acid decomposed into the phth2- ligand in the formation of compounds 16, 17, 18 and 19. Compound 16 crystallizes in the space group P21/c and shows a 1D chain structure, which is further extended into 3D supramolecular network throughÏ€-Ï€stacking and hydrogen bonds interactions. Compound 17 crystallizes in the space group P21/c and is a 1D helix chain structure, which is further linked into 2D networks throughÏ€-Ï€stacking. Compounds 18 and 19 are isostructural and crystallize in the space group P2/c. They exhibit the same 2D layers, which are further connected by hydrogen bonds interactions to form 3D supramolecular network. Magnetic properties study indicates that compounds 14, 15, 16 and 19 show weak antiferromagnetic interactions.