Yongjiang Liu

Hydrothermal synthesis, crystal structure and third-order non-linear optical property of a discrete decanuclear iodocuprate(I) [CuI10H2I16]4- with [NiII(phen)3]2+ as a template

Abstract The title compound [NiII(phen)3]2[Cu10H2I16] 1 (phen=1,10-phenanthroline, C12H8N2) was hydrothermally synthesized from a simple reaction of CuI–NiCl2·6H2O–phen·H2O–H2O. X-ray analysis revealed that it consists of NiN62+ core cation and decanuclear iodocuprate(I) anion together with two dissociative H+ ions. In anionic unit, the discrete decanuclear iodocuprate(I) is formed by crystallographically independent five monovalent copper atoms and eight iodine atoms via an inversion center. There exist two types of Cu(I) coordination sites; only one copper(I) atom is in a highly distorted triangular planar site, and the other four copper(I) atoms display the tetrahedral geometries. It deserves to be noted that four types of bridging modes of I− ions in which two are ordinary μ2- and μ3-bonding modes can be found. But the other two are the rectangle planar geometry and the novel μ4-bridge like an “umbrella”, and both of them are rather rare in the halocuprates(I). Compound 1 was crystallized in triclinic space group P 1 with a=11.6861(17), b=14.590(2), c=14.649(2)xa0A, α=76.370(2), β=70.830(2), γ=81.320(3)o, R=0.075, and was characterized by elemental analysis, IR spectrum and UV-VIS spectrum. The third-order non-linear optical property of 1 was also investigated and the compound exhibits the reverse saturable absorption and self-defocusing performance.

Preparation, crystal structures and magnetic properties of 12-metallacrown-4 complexes with the donors on the organic periphery of molecule

As the precursors of molecular magnets, three metallacrown analogous complexes, [Cu(II)(12-MC Cu(II)N(ahpha) -4)]·(NO 3 ) 2 ·4H 2 O ( 1 ), [Cu(II)(12- (II)N(hbha) -4)]·(NO 3 ) 2 ·8H 2 O ( 2 ) and [Cu(II)(12-MC Cu(II)N(mha) -4)]·(OH) 2 ·12H 2 O ( 3 ) (H 2 ahpha=3-amino-3-hydroximino propanoic hydroximic acid, H 2 hbha=3-hydroximino butanoic hydroximic acid and H 2 mha=malonic hydroximic acid) have been prepared and 1 and 2 are characterized structurally. The number of donors on the organic periphery of the molecular sheet is modified with additional hydroxy and R group of ligands for modulating the intermolecular architecture of metallacrown molecules and enhancing intermolecular magnetic interaction. Solid-state magnetic susceptibility studies 5–300 K of 1 and 2 show a strongly antiferromagnetic intramolecular exchange between the five Cu(II) centers and weakly antiferromagnetic intermolecular interaction. The fitting of H =−2 J 1 xa0∑ 4 i =1 S i · S 5 −2 J 2 xa0∑ 4 i ≠ j =1 S i · S j to the experimental magnetic susceptibilities give g =2.066(3), J 1 =−119.9(7), J 2 =−79.0(4), zJ ′=−0.69(7) cm −1 for 1 and g =2.089(3), J 1 =−163(2), J 2 =−85.1(6), zJ ′=−0.61(7) cm −1 for 2 .

Synthesis, crystal structure and magnetic properties of A[Ni(mnt)2] complexes [A = 1-(4-nitrobenzyl)quinolinium or 1-benzylpyridinium; mnt2− = maleonitriledithiolate]

Two new ion-pair complexes A[Ni(mnt)2], [A = 1-(4-nitrobenzyl)quinolinium (1), and 1-benzylpyridinium (2)] have been prepared and characterized. The crystal structure of (1) has been determined by X-ray diffraction analysis. In the solid state, anions and cations of (1) form completely segregated stacking columns, with the Ni···Ni distances alternating between 3.890(4) and 4.965(5) Å in the [Ni(mnt)2]− stacking column. The variable temperature magnetic susceptibilities of (1) and (2) have been measured over the 77–300 K range and the results reveal that (1) is diamagnetic and that (2) shows a weak antiferromagnetic spin exchange interaction between the metal ions. The e.p.r. spectra of (1) and (2) in MeCN at room temperature were similar, the g-values being almost identical.

New double-1,2-amide-bridged calix[4]arenes by aminolysis of calix[4]arene esters

A new facile method—aminolysis of calix[4]arene esters to obtain lower rim double-1,2-amide-bridged calix[4]arenes is described. We also report the single crystal structure of compound 3 which forms a long chain supramolecule in the solid state via intermolecular hydrogen bonding.

Synthesis, crystal structure, and properties of [Cu(LH)]2[M(mnt)2] [M = Ni or Cu; H2L = 3,3′-(1,3-propanediyldinitrilo)-bis(2-butanone oxime); mnt2− = maleonitriledithiolate] complexes containing bridging cyano groups

Interesting complexes containing a mnt2− bridge, based on the reaction of [M(mnt)2]2− [M = Ni or Cu] with [Cu(LH)]+, have been prepared and characterized by e.s.m.s., i.r and u.v–vis. spectroscopic techniques and by electrochemistry. The complexes show weak antiferromagnetic interactions between magnetic centers. The X-ray analysis of the molecular structure of [Cu(LH)]2[Ni(mnt)2] has been completed. It structurally features the CN group of mnt2− which can act as a bridging ligand between two transition metals.

Syntheses, crystal structures and spectroscopic properties of the novel complexes [M(MOBPT)*2 (H2O)2](ClO4)2 · 4H2O (M = CoII and NiII)

The novel cobalt(II) and nickel(II) complexes with 4-(p-methoxyphenyl)-3,5-bis(pyridin-2-yl)-1,2,4-triazole (MOBPT) have been synthesized and their molecular structures determined by X-ray analysis, i.r. and by ESI-MS spectroscopy. The metal atom is in a distorted octahedral environment. Two bidentate chelating ligands (MOBPT) coordinate to the metal center equatorially and two water molecules coordinate axially. Each MOBPT entity coordinates via one triazole nitrogen and one pyridine nitrogen atom. Magnetic measurements show that the complexes are high-spin species in the 75–300 K range.

Synthesis, spectroscopic characterization and X-ray crystal structure of vanadylpolymolybdophosphates with monocapped Keggin polyanion [PMo5V7O40(VO)]7−

Abstract The preparation of the heteropolyoxometalates K6[HPMo5V7O40(VO)]·16H2O (1), (n-Bu4N)4[H3PMo5V7O40(VO)] (2) and (CN3H6)6[HPMo5V7O40(VO)]·4H2O (3) is described. Compounds 2 and 3 have been characterized by X-ray diffraction methods. Both compounds contain a monocapped Keggin anion. For compound 2 the capping Vue605O group is disordered in six sites, while there are two types of sites for the capping Vue605O group for compound 3. The IR spectra have been investigated.

μ-[1,1'-(1,2-Ethanediyl)bis(1H-1,2,4-triazole)]-N4 :N4'-bis{bis[1,1,1-trifluoro-3-(2-thenoyl)acetonato-O, O']copper(II)}

The crystal structure determination of the title complex, [Cu 2 (C 8 H 4 F 3 O 2 S) 4 (C 6 H 8 N 6 )] or [Cu(TTA) 2 ] 2 btrz, where TTA is 1,1,1-trifluoro-3-(2-thenoyl)acetone and btrz is μ-[1,1-(1,2-ethanediyl)bis( 1H-1,2,4-triazole)], shows that the btrz ligand links two Cu II ions, forming a binuclear complex. Each Cu atom is in a distorted square-pyramidal coordination environment.

A Facile Method of Synthesis of a Calix[4]arene Amide and the Crystal Structure of a Self-assembled Calix[4]arene Amide via van Der Waals Interaction

A new facile method of synthesis of calix[4]arene amide via the aminolysis of the calix[4]arene esters was reported. One ethyl ester of the compound (2) was aminolysized byn-butylamine. The crystal structure of compound (1)shows that one ethyl ester of compound (1) enters into thecavity of another compound (1) forming a long chainhost-guest supramolecule. From the 2D NMR data, the compound(1) does not assemble in THF or CHCl3 solution. The CH-π interaction and crystallization energy might be theimportant driving forces for forming the self-assembledcalix[4]arene.

Crystal structure and magnetic properties of a new polymer [Cu(PzdcH)2·2H2O]n

Two different products are obtained when 2,3-pyrazinedicarboxylic acid (PzdcH2) reacts separately with two copper(II) salts: Cu(OAc)2 and CuCl2. One product is a mononuclear CuII complex Cu(PzdcH)2·2H2O, the other is a linear polymeric copper(II) complex [Cu(PzdcH)2·2H2O]n, whose structure has been determined by X-ray diffraction at room temperature. The polymeric complex is composed of copper(II) ions, PzdcH- anions and crystal water molecules. The Cu(1) atom is located in elongated octahedral coordination environment with six donor atoms: O(1), N(1), O(1a), N(1a), O(3b) and O(3c) from four different PzdcH- anions. The two oxygen atoms O(3b) and O(3c) come from the carboxylic acid group of the PzdcH- anion of the upper and lower layers, so that an infinite chain constitutes the crystal lattice. There are very strong hydrogen bond interactions between chains which lead to a three-dimensional structure. The magnetic susceptibility of the polymeric complex [Cu(PzdcH)2·2H2O]n has been determined in the 1.5–300K range. A study of magnetic properties shows that a weak antiferromagnetic interaction exists between two copper(II) ions.