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

Owing to their potential applications in luminescence, magnetism, catalysis, etc., metal-organitic coordination polymers have received more and more attention. This paper summarizes the research advances of coordination polymers based on amino acid and their derivatives. A series coordination compounds constructed by (+)-N-Tosyl-L-glutamic acid and L-O-Phosphoserine were synthesized and their crytal structures and properties were determined. In this paper, the main results are as follows: {Zn(tsgluO)(4,4'-bipy)(H₂O)}n(1),{Zn(tsgluO)(bpe)0.5}n(2),{Zn(tsgluO)(bpe)}n(3),{Zn(tsgluO)(2,2'-bipy)(H₂O)}2·2H₂O(4),{Zn(tsgluO)(2,2'-bipy)(H₂O)}2·2H₂O (5),{[Zn(tsgluO)(bpp)]·0.5H₂O}n(6),{Cd(tsgluO)(4,4'-bipy)(H₂O)}n(7),{[Cd(tsgluO)(bpe)1.5]·H₂O}n(8),{[Cd2(tsgluO)2(bpp)4]·2.5H₂O}n(9),{[Mn(tsgluO)(bpe)(H₂O)2]·H₂O}n(10),{Ag(HtsgluO)(bpp)}n(11),{Co(tsgluO)(bpp)}n (12),{Cu(OPSer)(phen)(H₂O)}·3H₂O(13) (H2tsgluO = (+)-N-Tosyl-L-glutamic acid, OPSer=L-O-Phosphoserine, bipy= bipyridine, bpe= 1,2-bis(4-pyridyl)methane, bpp= 1,3-bis(4-pyridyl)propane, phen= 1,10-phenanthroline) have been synthesized and characterized by X-ray diffraction analysis, elemental analysis, IR, thermal analysis, and their fluorescent properties were also studied.Compounds 1,6,7,11 crystallize in the chiral space group P21. The 2D architecture of compounds 1,7,11 are further connected by hydrogen bonds interactions to form 3D supramolecular network. Crystal structure of compound 1 is similar to compound 7, which may be due to that they belong to the same subgroup. Compound 6 crystallize in the chiral space group P21 and is giving 2D layer structure containing right handed helical double-chains. Compounds 2,3,8,9 show the centrosymmetric space group P2₁/c. Compound 2 is giving 3D microporous architecture with a channels'aperture about 5.8×7.7 along b direction . It is noticeable that the channels are not occupied by the guest molecular. Compounds 3,8,9 present a 2D network structure and compound 3 is further connected by hydrogen bonding to form three-dimensional supramolecular network. Compounds 4,5,10 crystallize in the centrosymmetric space group P-1. Cmpound 4 are further self-assembled through the non-covalent interactions of hydrogen bond andÏ€-Ï€stacking to form pseudo-2D supramolecular structures, but compound 5 are further self-assembled through the non-covalent interactions of hydrogen bonding andÏ€-Ï€stacking to form pseudo-3D supramolecular structures. Compound 10 is giving 1D double-line structure which further cnnected by hydrogen bonding to form three-dimensional supramolecular network.Compounds 12 and 13 both crystallize in the chiral space group P212121 and compound 12 presents 2D layer structure with right handed helical chains along a direction. Compound 13 is self-assembled through the non-covalent interactions of hydrogen bonding andÏ€-Ï€stacking to form pseudo-3D supramolecular structures.The ligand H2tsgluO adopts versatile coordination modes to coordinate with metal ions, which may be in correlation with the kinds of the metal ions. The N-donor ancillary rigid 4,4'-bipyridine ligand and flexible bpe,bpp ligands tend to act as birdging-ligand to form high dimentional complexes. The flexible ancillary ligand bpe,bpp meet the coordination number of the metal ions by subtle manipulation their modes.The solvent has some influence on the H2tsgluO ligand coordination mode.Among the compounds hydrothermally synthesized, only compounds 1 and 7 crystallize in chiral space group P21, while the rest is centrosymmetric, which may be in correlation with the ancillary ligand and temperature. Four compounds synthesized at room temperature all crystallize in chiral space group, which may due to the low temperature is conductive to the maintenance of chiral ligand.Fluorescent properties of compounds 1,2,7,8 in solid state at room temperature were studied. When excited with 365nm compounds 1,2,7,8 show emissions at about 440, 422, 442, 428nm, respectively. Results of luminescent studies of compounds 3, 4, 5, 6, 9, 11 in ethanol solution indicate that they are all potential fluorescent materials. The adsorption properties of compound 2 for N2 have been meatured, which show that there are weak interaction between the microporous materials and N₂.