Two Fluorescent Complexes Assembled by Schiff Base 2-Methoxy-6-(phenyliminiomethyl) Phenolate Ligand

Two d10 metal complexes Zn（NCS）2（C14HI3NO2）2 （1） and [Cd（NO3）2（CI4HI3NO2）2]. 4H20 （2） assembled by 2-methoxy-6-（phenyliminiomethyl） phenolate ligand （C14H13NO2, HL） have been synthesized and characterized by elemental analysis, IR and TG The single-crystal X-ray diffraction studies demonstrated that complex 1 crystallizes in monoclinic, P21/c space group with a = 17.321（7）, b = 11.781（0）, c = 15.593（2） A, fl = 110.273（6）°, V = 2984.95 A3, Z = 4, C30H26N404SzZn, Mr = 636.04, F（000） = 1312, Dc = 1.415 g/cm3,μ（MoKa） = 1.004 mm＂1, the final R = 0.0403 and wR = 0.0900 for 21441 observed reflections with I 〉 20（/）. Complex 2 is of monoclinic system, space group C2/c with a = 16.7767（2）, b = 10.8989（2）, c = 17.4928（2） A, fl = 90.614（9）°, V= 3198.37 A3, Z = 4, C28H34N4O14Cd, Mr= 731.25, F（000） = 1528, Dc = 1.568 g＇cm^-3, μ（MoKa） = 0.757 mm-1, the final R = 0.0361 and wR = 0.0857 for 19811 observed reflections with I 〉 2σ（I）. The two complexes were formed by Schiff base 2-methoxy-6-（phenyliminiomethyl） phenolate ligand and formed a 3D supramolecular architecture by π-πstacking interactions. Moreover, the complexes are luminescent in the solid state. These observations indicate that the complexes are promising system for the development of potential photoactive materials.

SVNTHESES AND CHARACTERIZATION OF TWO HIGH VALENCE VANADIUM COMPLEXES (?) SCHIFF-BASE LIGAND WITH RICH PHENOLATE OXVGEN AND THEIR CONVERSION

Two vanadium complexes of schiff base vith rich phenolate oxygen,o-(?)-salicylideneamino- methylphenol,had been synthesized and characterized.One is a V(Ⅳ)complex with an interaction via vanadyl oxygen and the other is a novel dinuclear V(V,V)complex with an oxo bridge.The conversion between the two complexes had been discussed.

Synthesis and Photochemical Properties of a New Substituted Phenol Covalently Linked to Ruthenium (Ⅱ) Tris-bipyridine Containing Four Ester Groups as Sensitizer

As photosensitizer for solar cell, a new ruthenium (Ⅱ) complex with four ester groups hadbeen synthesized, in which a phenol substituted by {[(2-hydroxy-5-tert-butylbenzyl)(pyridyl-2-methyl)amino]methyl} is covalently linked to ruthenium (Ⅱ) tris-bipyridine. The structures ofthe new compounds were confirmed by NMR and ESI-MS spectra. The electrochemical andphotochemical properties were also studied.

Aluminum Complexes Stabilized by Piperazidine-Bridged Bis（phenolate） Ligands： Syntheses, Structures, and Applica- tion in the Ring-Opening Polymerization of ε-Caprolactone

The synthesis and characterization of aluminum alkoxide and alkyl complexes stabilized by piperazidine- bridged bis（phenolate） ligands are described. Treatment of ligand precursors Hz[ONNO]^1 {Hz[ONNO]^1= 1,4-bis（2-hydroxy-3-tert-butyl-5-methylbenzyl）piperazidine} and Hz[ONNO]2 {H2[ONNO]2=1,4-bis（2-hydroxy3,5-di-tert-butylbenzyl）piperazidine} with A1Et2（OCH2Ph） and A1Etz（OPr-i）, which were generated in situ by the reactions of AIEt3 with equivalent of the corresponding alcohols, in a 1： 1 molar ratio in THF gave the corresponding aluminum alkoxide complexes [ONNO]IAI（OCH2Ph） （1） and [ONNO]2Al（OPr-i） （2）, respectively. The reaction of H2[ONNO]^1 with A1Etz（OCHzPh） in a 1 ： 2 molar ratio in THF afforded a mixture of monometallic aluminum ethyl complex [ONNO] 1A1Et （3） and complex 1, which can be isolated by stepwise crystallization. Similarly, Hz[ONNO]2 reacted with A1Etz（OPr-0 in a 1： 2 molar ratio in THF to give a mixture of aluminum ethyl complex [ONNO]2AlEt （4） and complex 2. Complexes 1 and 2 were also available via treatment of complexes 3 and 4 with 1 equiv, of benzyl alcohol and isopropyl alcohol, respectively. All of these complexes were fully characterized including X-ray structural determination. It was found that complexes 1 to 4 can initiate the ring-opening polymerization of e-caprolactone, and complexes 1 and 2 showed higher catalytic activity in comparison with com- plexes 3 and 4.

Bimetallic amine-bridged bis(phenolate) lanthanide aryloxides and alkoxides: synthesis, characterization, and application in the ring-opening polymerization of rac-lactide and rac-β-butyrolactone

A series of neutral bimetallic lanthanide aryloxides p-C6H4[OLnL(THF)n]2 [Ln = Y(1), Yb(2), Sm(3)(n = 1) and La(4)(n = 2), L = Me2NCH2CH2N{CH2-(2-O–C6H2–tBu2-3,5)}2] and alkoxides p-C6H4CH2[OLnL(THF)]2 [Ln = Y(5), Yb(6)] supported by an amine-bridged bis(phenolate) ligand have been synthesized through one-pot reactions of Ln(C5H5)3(THF), LH2 with p-benzenediol and 1,4-benzenedimethanol, respectively. All complexes have been fully characterized by elemental analyses, single-crystal X-ray diffraction analysis, and IR and multi-nuclear NMR spectroscopy(in the cases of 1, 4 and 5). Study of their catalytic behavior revealed that, in general, all complexes are efficient initiators for the polymerization of rac-lactide(LA) and rac-β-butyrolactone(BBL), except for 3 and 4 in the case of BBL. The influence imposed by lanthanides of different ionic radii and initiating groups of different structures on the activity, controllability, and stereoselectivity of polymerization were systematically studied and compared. Highly heterotactic PLA(Pr up to 0.99) and syndiotactic PHB(Pr ≈ 0.81) with high molecular weight and narrow polydispersity formed and were automatically capped with hydroxyl functionality at both ends.