Kai-Bei Yu

Self-Assembly of Frameworks with Specific Topologies: Construction and Anion Exchange Properties of M3L2 Architectures by Tripodal Ligands and Silver(I) Salts

Three five-component architectures, compounds 3, 4, and 5 were obtained by self-assembly of tripodal 1,3,5-tris(imidazol-1-ylmethyl )-2,4,6-trimethylbenzene (6) and 1,3,5-tris(benzimidazol-2-ylmethyl)benzene (7) ligands with silver(I) salts. The structures of these novel complexes have been determined by X-ray crystallography. The results of structural analysis indicate that these frameworks have same M3L2 components, but different structures. Compounds 3 and 4 are both M3L2 type cage-like complexes, while the 5 is an open trinuclear complex. The complex 3 is a cylindrical cage with simultaneous inclusion of a perchlorate anion inside of the cage as a guest molecule. Such guests can be exchanged for other anions through the open edge of the cage as evidenced by crystal structure of 4. The results demonstrate that the molecular M3L2 type cage can act as a host for anions and provide a nice example of supramolecular architectures with interesting properties and possible applications.

A two-dimensional network constructed via 72-membered heart-shaped macrocycles, a copper(II) complex with 1,3,5-tris(imidazol-1-ylmethyl)-2,4,6-trimethylbenzene and diethylenetriamine ligands

A new flexible aryl-heterocyclic tripodal ligand, 1,3,5-tris(imidazol-1-ylmethyl)-2,4,6-trimethylbenzene ( titb ) was prepared. It reacts with [Cu(dien)(im)](ClO 4 ) 2 to form a novel two-dimensional network complex, [{Cu 3 (dien) 3 ( titb ) 2 }(ClO 4 ) 6 (CH 3 CN) 0.5 (H 2 O) 0.25 ] n , where dien=diethylenetriamine. The complex crystallizes in triclinic, space group P 1 with a =13.630(3), b =15.837(2), c =21.105(3) A, α =70.860(10), β =86.700(10), γ =64.900(10)°, V =3879.7(11) A 3 and Z =2. There are two kinds of conformation of the titb ligand in the titled complex, one is cis , trans , trans , the other is cis , cis , cis . The [Cu(dien)] 2+ units bind with the titb ligands to form condensed 72-membered (Cu 6 C 42 N 24 ) heart-shaped macrocycles and result in a two-dimensional network. The sheets stack in a center-symmetric mode between every two adjacent sheets and generate channels which contain the perchlorate anions, acetonitrile solvent and water molecules.

Synthesis, crystal structure and spectroscopic characterization of silver(I), cadmium(II) complexes with the Schiff base derived from pyridine-2-carboxaldehyde and 4-[(E)-2-phenyldiazenyl]aniline

The bidentate Schiff-base L is synthesized by condensation of pyridine-2-carboxaldehyde with 4-[(E)-2-phenyldiazenyl]aniline. Hydrothermal reaction of L with AgNO3 and Cd(ClO4)2·6H2O afforded complexes AgLNO3 (1) and [CdL2(H2O)ClO4]ClO4 (2), respectively, which are characterized by elemental analysis and IR spectroscopy. The single crystal X-ray diffraction analyses reveal that both 1 and 2 are mononuclear. In 1, Ag(I) is coordinated by two N atoms from the Schiff-base ligand and one O atom from group in a distorted trigonal geometry. In 2, the cadmium(II) is coordinated in a distorted octahedral geometry, with an equatorial plane composed of four nitrogen atoms from two bidentate Schiff-base ligands, and the apical position occupied by one O atom from aqua ligand and one O atom from perchlorate.

The synthesis, crystal structure and spectroscopic properties of a new two-dimensional silver(I) coordination network

A flexible tetradentate ligand 1,6-bis(4%-pyridyl)-2,5-diazahexane (BPDH) reacts with tetrakis(acetonitrile)silver(I) tetrafluoroborate to form a novel two-dimensional network complex [Ag(BPDH)]BF4·CH3CN. The compound crystallizes in monoclinic, space group P21:n with a14.121(2), b7.0410(10), c19.803(3) A, , b 94.700(10)°, V 1962.3(5) A, 3 and Z 4. The solvate acetonitrile molecule and counter anions are incorporated in the channels formed between two adjacent sheets through CH···F, NH···F and NH···N hydrogen bonds. The spectroscopic properties of the complex as luminescent, thermogravimetric and electrospray mass spectrometry were also described.

The first X-ray structurally characterized M3L2 cage-like complex with tetrahedral metal centres and its encapsulation of a neutral guest molecule

The first X-ray structurally characterized M3L2 cage-like complex with tetrahedral metal centres [Zn3(tib)2- (OAc)6]·xH2O [tib = 1,3,5-tris(imidazol-1-ylmethyl)benzene, x ≈ 4] obtained by reaction of zinc(II) acetate with the tripodal ligand tib exhibits guest inclusion properties of neutral molecule such as synthetic camphor in aqueous solution.

Synthesis and crystal structure of N-(1-phenyl-3-methyl-4-benzal-pyrazolone-5)-N'-salicylidene hydrazine

A novel Schiff base compound, N-(1-phenyl-3-methyl-4-benzal-pyrazolone-5)-salicylidene hydrazine (PMBP-SAH), has been synthesized and characterized by X-ray diffraction: monoclinic, space group C2/c with a = 21.796(5) Å, b = 18.370(3) Å, c = 20.843(3) Å, β = 95.440(10)°, V = 8308(3) Å3, and Z = 16. The title compound contains two kinds of tautomers: the red compound is the keto form and the other is the enol form. Changes in color are due to the isomerization of the enol and keto forms by the intramolecular proton transfer.

SYNTHESIS OF TWO NOVEL HETEROBIMETALLIC CLUSTER COMPOUNDS [NEt4]4[MS4Cu4I6] (M = Mo, W). CRYSTAL STRUCTURE OF [NEt4]4[MoS4Cu4I6]

Abstract Two new cluster compounds [NEt4]4[MS4Cu4I6] (1: M = Mo; 2: M = W) have been obtained by the reaction of [NH4]2[MS4] (M = Mo, W), CuBr, [NEt4]I and [Bu 4 nN]I in the solid state. Dark red crystals of 1 are monoclinic, space group C2/m with cell dimensions a = 29.686(6), b = 12.778(2), c = 15.308(3) A, β = 99.53(2)°, Z = 4, Dcalc = 2.04g cm−3, R = 0.052 for 4021 observed reflections. The X-ray analysis shows that four edges of the tetrahedral MoS4 2- core are coordinated by four copper atoms, giving a MoS4Cu4 aggregate of approximate C 2v symmetry. The Mo—Cu lengths range from 2.650(2) to 2.686(1) A.

Synthesis and crystal structure of Schiff base transition metal complex [Co(PMBP-smdtc)2].2H2O

A cobalt(II) complex, [Co(PMBP-smdtc)2]⋅2H2O, in which PMBP-smdtc is the l-phenyl-3-methyl-4-benzoyl-5-pyrazolone Schiff base of S-methyldithiocarbazate, has been synthesized and characterized by IR spectrum and single crystal X-ray diffraction. The crystal is monoclinic: space group C2/c, with a = 12.455(2) Å, b = 16.024(2) Å, c = 20.513(3) Å, β = 101.18(1)°, V = 4016.3(10) Å3, and Z = 4. The cobalt ion is octahedrally coordinated by two tridentate Schiff base ligands with ONS donor atoms. The molecules are bridged together by two water molecules through H-bond along b axis and one-dimensional indented chain structure is formed.

Tetraaqua(1,10-phenanthroline)zinc(II) sulfate dihydrate

A novel monomeric phenanthroline (phen) zinc complex, [Zn(C 12 H 8 N 2 )(H 2 O) 4 ]SO 4 .2H 2 O, has been characterized by X-ray analysis. The Zn atom is coordinated in a slightly distorted octahedral geometry by two N atoms from 1,10-phenanthroline and four O atoms from water ligands. The Zn-N bond lengths are in the range 2.136 (3)-2.156 (2) A and the Zn-O bond lengths are in the range 2.083 (2)-2.130 (2) A. Hydrogen bonds stabilize the structure.

Synthesis and crystal structure of three-coordinated silver(I) and copper(I) complexes with N2P binding set containing a novel tripodal ligand: 1,3,5-tris(benzimidazol-2-ylmethyl)benzene

Assembly of a novel tripodal ligand, 1,3,5-tris(benzimidazol-2-ylmethyl)benzene (tbib), and triphenylphosphine with silver(I) and copper(I) salts gave the corresponding mononuclear complexes, which were characterized by electrospray mass spectrometry and 31P NMR spectroscopy. The structure of the silver(I) complex, [Ag(tbib)(PPh3)]NO3 ·CH3OH·H2O, determined by X-ray crystallography, indicates that the silver(I) atom is coordinated by two nitrogen atoms of one tbib ligand and one phosphorus atom of triphenylphosphine. Another nitrogen atom of the tbib ligand is uncoordinated. The complex provides another example of a structurally characterized silver(I) complex with N2P binding set.