Photoinduced Ba2+ release and thermal rebinding by an azacrown ether linked by an alkynyl pyridine to a (bpy)Re(CO)3 group

A novel complex in which an azacrown ether is linked by an alkynyl pyridine to a (bpy)Re(CO)3 group acts as a light-controlled ion switch: Ba2+ bound to the azacrown is released in ca. 10 ns on UV excitation, and rebinds thermally from bulk solution in ca. 1 micros.     

Ground and excited state resonance Raman spectra of an azacrown-substituted [(bpy)Re(CO)3L]+ complex: characterization of excited states, determination of structure and bonding, and observation of metal cation release from the azacrown

A [(bpy)Re(CO)3L+] complex (bpy = 2,2'-bipyridine) in which L contains a phenyl-azacrown ether that is attached to Re via an amidopyridyl linking group has been studied by steady state and nanosecond time-resolved resonance Raman spectroscopy. Vibrational band assignments have been aided by studies of model complexes in which a similar electron-donating dimethylamino group replaces the azacrown or in which an electron-donor group is absent, and by density functional theory calculations. The ground state resonance Raman spectra show nu(bpy) and nu(CO) bands of the (bpy)Re(CO)3 group when excitation is exclusively in resonance with the Re --> bpy metal-to-ligand charge-transfer (MLCT) transition, whereas L ligand bands are dominant when it is in resonance with the strong intra-ligand charge-transfer (ILCT) transition present for L ligands with electron-donor groups. Transient resonance Raman (RR) spectra obtained on single color (385 nm) pulsed excitation of the complexes in which an electron-donor group is absent show bpy*- bands of the MLCT excited state, whereas those of the complexes with electron-donor groups show both bpy*- bands and a down-shifted nu(CO) band that together are characteristic of an L-to-bpy ligand-to-ligand charge-transfer (LLCT) excited state. Samples in which a metal cation (Li+, Na+, Ca2+, Ba2+) is bound to the azacrown in the ground state show bands from both excited states, consistent with a mechanism in which the LLCT state forms after metal cation release from the MLCT state. Nanosecond time-resolved RR spectra from two-color (355 nm pump, 500 nm probe) experiments on the electron-donor systems show L-ligand bands characteristic of the LLCT state; the same bands are observed from samples in which a metal cation is bound to the azacrown in the ground state, and their time dependence is consistent with the proposed mechanism in which the rate constant for ion release in the MLCT state depends on the identity of the metal cation.     

Soluble poly (aryl ether)s containing naphthalene pendant group: synthesis, characterization and electrospinning

Two soluble poly(aryl ether)s were prepared conveniently from bis(4-hydroxy-3,5-dimethylphenyl)naphthylmethane (1) and two activated dihalide monomers including 4,4′-difluorobenzophenone and bis(4-chlorophenyl)sulfone by an aromatic nucleophilic substitution. The bulky naphthyl and tetramethyl pendant groups in the polymer backbone could decrease the packing density and intermolecular interaction of macromolecular chain and make these poly(aryl ether)s show a good solubility. They all could be dissolved in CHCl₃, CH₂Cl₂ and tetrahydrofuran at room temperature with a dissolvability of more than 10 wt%. Furthermore, the poly(aryl ether)s could be electrospun into microfiber (10–15 μm) with nanopores (200–350 nm). The morphologies of these fibers were characterized by scanning electron microscopy. The porous morphology on the fiber surface was also investigated using scanning probe microscope.     

Microwave-assisted three component synthesis of novel bis-fused quinazolin-8(4H)-ones linked to aliphatic or aromatic spacer via amide linkages

Abstract

A novel series of bis(tetrahydro[1,2,4]triazolo[5,1-b]quinazolin-8-ones) and bis(tetrahydrobenzo[4,5]imidazo[2,1-b]quinazolinones) containing amide linkages were regionselectively prepared via a three-component reaction of bis(aldehydes) with dimedone and 3-amino-1,2,4-triazole (or 2-aminobenzimidazole) under conventional heating as well as under microwave irradiation.     

Reactive iron carbonyl reagents via reaction of metal alkoxides with Fe(CO)5 or Fe2(CO)9: synthesis of cyclobutenediones via double carbonylation of alkynes

Alkoxy bases such as t-BuOK react with Fe(CO)(5) to give reactive iron carbonyl intermediates that in turn react with alkynes at 70 °C in THF to give 1,2-cyclobutenediones in 70-93% yields after CuCl(2)·2H(2)O oxidation. A novel 1,2-diacyloxyferrole derivative was isolated in the reaction of diphenylacetylene with Fe(CO)(5)/t-BuOK in the presence of acetyl chloride in contrast to the formation of a 1,4-diacyloxyferrole complex formed in the reaction using Fe(CO)(5)/Me(3)NO. The Fe(2)(CO)(9)/t-BuOK reagent system also converts the alkynes to corresponding cyclobutenediones in 63-90% yields under similar reaction conditions.     

The synthesis of heteronuclear cluster compounds containing M(PR3) (M = Cu,Ag, or Au; R = alkyl or aryl) units via Group IB metal exchange reactions

Treatment of dichloromethane solutions of the heteronuclear cluster compounds [M₂Ru₄(μ₃-H)₂{μ-Ph₂P(CH₂)₂PPh₂}(CO)₁₂] (M = Cu or Ag) with dichloromethane solutions containing the appropriate quantities of the complex [Ag(NCMe)₄]PF₆ or [AuCl(SC₄H₈)] results in the replacement of either one or both of the Group IB metals M by silver or gold atoms. The products from the Group IB metal exchange reactions are obtained in ca. 65–75% yield.     

A novel crown ether generation containing different heteroaromatic cations: synthesis, characterization, solid-phase (13)C NMR, X-ray crystal structure, and selective amino acid recognition

The synthesis and structural characterization of a novel generation of crown ethers, 3, 5 and 6 containing pyrilium, thiopyrilium, and pyridinium subunits, respectively, are reported. The crown ether unit is potentially capable of forming host-guest complexes with inorganic and organic cations, while the heteroaromatic cationic unit is suitable to bind with anions. A variety of physicochemical methods including electrospray mass spectrometry, UV-vis spectroscopy, solution and solid-phase NMR, and X-ray crystallography were applied for structural characterization of the new crown ether derivatives. The (1)H and (13)C NMR studies indicate rapid rotation of the B9C3 unit about the C-C bond that connects the two units to each other. Single crystals for 3, 4, and 5 were successfully obtained, and their X-ray crystal structures were resolved. The perchlorate anion in 3 (orthorhombic, space group P2(1)2(1)2(1)) and 5 (orthorhombic, space group P2(1)) is far from O(+) and close to S(+). The solid-phase structure of 3 and 5 show small deviation from planarity for the four aromatic rings, whereas two of the aromatic rings in 4 are out of heteroaromatic ring. Spectrophotometric studies in methanol solution revealed that the ligand 3 can be successfully applied to selective amino acid recognition.     

The synthesis and characterization of ( E,E )-dioxime and its transition metal complexes containing 12-membered macrocycles linked to ferrocenyl-methyl groups

13,14-bis(Hydroxyimino)-4,7-bis(ferrocenylmethyl)-2,3,4,5,6,7,8,9-octahydrobenzo[k]-4, 7-diaza-1,10-dithiacyclododecine[13,14-g]-quinoxaline (H₂L) has been prepared from (E,E)-dichloroglyoxime and 12,13-diamino-4,7-bis(ferrocenylmethyl)-2,3,4,5,6,7,8,9-octahydrobenzo[k]-4,7-diaza-1,10-dithiacyclododecine which was synthesized from 12,13-dinitro-4,7-bis(ferrocenylmethyl)-2,3,4,5,6,7,8,9-octahydrobenzo[k]4,7-diaza-1,10-dithia cyclododecine. Mononuclear nickel(II) and copper(II) complexes of H₂L have a metal-ligand ratio of 1?:?2 and the ligand coordinates through two nitrogen atoms, as do most (E,E)-dioximes. The homotrinuclear [Cu(L)₂Cu₂(dipy)₂](NO₃)₂ compound coordinates to the other two copper(II) ions through deprotonated oximate oxygens and two 2,2′-dipyridyl as an end-cap ligand to yield the trinuclear structure. The ligand and its complexes have been characterized on the basis of ¹H, ¹³C NMR, IR and MS spectroscopy and elemental analyses.     

Effect of intramolecular pi-pi and CH-pi interactions between ligands on structure, electrochemical and spectroscopic properties of fac-[Re(bpy)(CO)3(PR3)]+(bpy = 2,2'-bipyridine; PR3= trialkyl or triarylphosphines)

Intramolecular pi-pi and CH-pi interactions between the bpy and PR3 ligands of fac-[Re(bpy)(CO)3(PR3)]+ affect their structure, and electrochemical and spectroscopic properties. Intramolecular CH-pi interaction was observed between the alkyl groups on the phosphine ligand (R =nBu, Et) and the bpy ligand, and intramolecular pi-pi and CH-pi interactions were both observed between the aryl group(s) on the phosphorus ligand (R =p-MeOPh, p-MePh, Ph, p-FPh, OPh) and the bpy ligand, while no such interactions were found in the trialkylphosphite complexes (R = OiPr, OEt, OMe). The intramolecular interactions distort the pyridine rings of the bpy ligand as long as 3.7 x 10(-2)A in crystals. Molecular orbital calculations of the bpy ligand suggest that this distortion decreases the energy gap between its pi and pi* orbitals. An absorption band attributed to the pi-pi*(bpy) transition of the distorted rhenium complexes, measured in a KBr pellet, was red-shifted by 1-5 nm compared to the complexes without the distorted bpy ligand. Even in solution, similar red shifts of the pi-pi*(bpy) absorption were observed. The redox potential E1/2(bpy/bpy*-) of the complexes with the trialkylphosphine and triarylphosphine ligand are shifted positively by 110-120 mV and 60-80 mV respectively, compared with those derived from the electron-attracting property of the phosphorus ligand. In contrast with these properties, three nu(CO) IR bands, which are sensitive to the electron density on the central rhenium because of pi-back bonding, were shifted to higher energy, and a Re(I/II)-based oxidation wave was observed at a more positive potential according to the electron-attracting property of the phosphorus ligand.     

M(CO)4~(2+)(M=Ni,Pd,Pt)的几何结构与自旋态的理论研究

对标题化合物的几何结构和可能的自旋态在密度泛函DFT-BP86和从头算的水平上进行了研究.计算结果表明:作为16电子配合物阳离子,Pd(CO)_4~(2+)和Pt(CO)~(2+)都以低自旋态平面四边形构型存在,这与实验事实相符,计算得到的键长Pd-C和Pt-C相对趋势也与实验数据一致.而对于Ni(CO)_4~(2+)阳离子计算,在低自旋态平面四边形构型和高自旋态的(扭曲)四面体之间无法给出明确的答案,因为CCSD(T)//BP86和CCSD(T)//MP2水平下得到的两种结构之间的能量差几乎可以忽略.     

New synthetic routes to biscarbonylbipyridinerhenium(I) complexes cis,trans-[Re(X2bpy)(CO)2(PR3)(Y)n+ (X2bpy = 4,4'-X2-2,2'-bipyridine) via photochemical ligand substitution reactions, and their photophysical and electrochemical properties

Photochemical ligand substitution of fac-[Re(X2bpy)(CO)3(PR3)]+ (X2bpy = 4,4'-X2-2,2'-bipyridine; X = Me, H, CF3; R = OEt, Ph) with acetonitrile quantitatively gave a new class of biscarbonyl complexes, cis,trans[Re(X2bpy)(CO)2(PR3)(MeCN)]+, coordinated with four different kinds of ligands. Similarly, other biscarbonylrhenium complexes, cis,trans-[Re(X2bpy)(CO)2(PR3)(Y)]n+ (n = 0, Y = Cl-; n = 1, Y = pyridine, PR'3), were synthesized in good yields via photochemical ligand substitution reactions. The structure of cis,trans-[Re(Me2bpy)(CO)2[P(OEt)3](PPh3)](PF6) was determined by X-ray analysis. Crystal data: C38H42N2O5F6P3Re, monoclinic, P2(1/a), a = 11.592(1) A, b = 30.953(4) A, c = 11.799(2) A, V = 4221.6(1) A3, Z = 4, 7813 reflections, R = 0.066. The biscarbonyl complexes with two phosphorus ligands were strongly emissive from their 3MLCT state with lifetimes of 20-640 ns in fluid solutions at room temperature. Only weak or no emission was observed in the cases Y = Cl-, MeCN, and pyridine. Electrochemical reduction of the biscarbonyl complexes with Y = Cl- and pyridine in MeCN resulted in efficient ligand substitution to give the solvento complexes cis,trans-[Re(X2bpy)(CO)2(PR3)(MeCN)]+.     

Facile synthesis of poly(ether carbonate)s via copolymerization of CO2 and propylene oxide under combinatorial catalyst of rare earth ternary complex and double metal cyanide complex

Poly(ether carbonate)s (PPCs) with carbonate unit (CU) content ranging from 57.8 to 97.1% and number average molecular weight (M_n) around 100 kg/mol were conveniently prepared via copolymerization of CO₂ and propylene oxide under combinatorial catalyst of rare earth ternary (RET) complex and double metal cyanide (DMC) complex. Enhancement of catalytic activity and reduction of propylene carbonate byproduct were realized due to synergetic effect of the two metal catalysts, where DMC can be activated in the presence of RET. Solubility fractionation confirmed that the obtained PPCs were copolymers, not physical blends of each polymer. Thermal performances of the PPCs were closely related to their CU content, their glass transition temperatures (T_g) were tunable in the range of 6.7–36.3 °C, which decreased with decreasing CU content, while their thermal stabilities were enhanced significantly, an increase of 50.5 °C in 50% weight loss temperature was observed when CU content decreased from 97.1 to 57.8%. Both shear storage modulus and complex viscosity increased with increasing CU content, which became more obvious at lower frequency, featuring well with the CU content in the PPCs. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Re(CO)(3) complexes synthesized via an improved preparation of aqueous fac-[Re(CO)(3)(H(2)O)(3)](+) as an aid in assessing (99m)Tc imaging agents. Structural characterization and solution behavior of complexes with thioether-bearing amino acids as tridentate ligands

Parallel studies of the preparation of Re and (99m)Tc agents aid in interpreting the nature of tracer (99m)Tc radiopharmaceuticals. Aqueous solutions of the fac-[(99m)Tc(CO)(3)(H(2)O)(3)](+) cation are gaining wide use and are readily prepared, but such solutions of the fac-[Re(CO)(3)(H(2)O)(3)](+) cation (1) are not so easily accessible. Herein we describe a new, reliable, and straightforward preparation of aqueous solutions of 1, characterized by HPLC and ESI-MS. Treatment of solutions of 1 with thioether-bearing amino acids, AAH = S-methyl-l-cysteine (MECYSH), S-propyl-l-cysteine (PRCYSH), and methionine (METH), gave high yields of fac-Re(CO)(3)AA complexes. X-ray crystallographic and NMR analyses indicated that MECYS(-), PRCYS(-), and MET(-) were bound in fac-Re(CO)(3)AA complexes as tridentate monoanionic ligands through amino, thioether, and alpha-carboxyl groups. In CD(3)OD, (1)H NMR spectra have broad signals but have two sets of signals at -10 degrees C, consistent with two isomers with different configurations at the pyramidal sulfur; these interconvert slowly on the NMR time scale at low temperatures. Indeed, the crystal structure of the fac-Re(CO)(3)(PRCYS) reveals a mixture of the two possible diastereoisomers. S-(Carboxymethyl)-l-cysteine (CCMH(2)) and 1 gave two products, 5A (kinetically favored) and 5B (thermodynamically favored). X-ray crystallographic analyses of a crystal of 5B and of a 1:1 cocrystal of 5A and 5B showed that 5A and 5B are diastereoisomers with the CCMH(-) alpha-carboxyl group dangling. In addition to the amino and thioether groups, the S-(carboxymethyl) carboxyl group is coordinated, a feature that slows interconversion of diastereoisomers relative to the other fac-Re(CO)(3)AA complexes because interconversion can now occur only after the rupture of Re-ligand bonds. These N, O, and S tridentate adducts are quite stable, and the grouping has promise in (99m)Tc(CO)(3) tracer development.     

Substituted metal carbonyls: [{{(p-MeOC6H4)2Te}M(CO)4}]2 (M = Mn or Re) in the presence of an O-atom transfer reagent

Two novel telluroether-disubstituted metal carbonyls, [(R₂Te)M(CO)₄]₂(M = Mn or Re; R = p-MeOC₆H₄), were prepared from [M₂(CO)₁₀] by an oxygen atom transfer. The axial CO is replaced by the telluroether when [M₂(CO)₁₀] reacts with a new kind of oxygen transfer reagent, R₂TeO, under mild conditions. The products were characterized by elemental analysis, i.r., ¹H- and ¹³C-n.m.r., and FAB-mass spectra. The configuration of the substituted carbonyl is unique, i.e. the 1, l-diax isomer.     

A new approach to synthesis of layered fluorites containing molecular anions: synthesis of Ln2O2CO3, K(LnO)CO3, and Ln2O2CrO4 via metathesis reactions

A new synthetic approach is suggested for preparation of layered rare-earth oxide compounds containing [Ln2O2] slices and molecular anion sheets (CO32-, SO42-, and CrO42-). It is based on exchange reactions of rare-earth oxychlorides, [Ln2O2]Cl2, and alkali carbonates, sulfates, or chromates. Five new rare-earth oxychromates [Ln2O2]CrO4 (Ln=Pr-Gd) have been prepared which adopt a new, probably layered, structure type. In addition, significantly easier and more efficient synthetic pathways were found to the known compounds [Ln2O2]K2(CO3)2 and [La2O2]CrO4. The structure of the latter compound has been determined from neutron powder diffraction data. Factors affecting reaction pathways and products are discussed, as well as prospects for applying the approach to more complex layered compounds.     

(eta 5-C5H5)Fe(CO)2]2B(2,4,6-Me3C6H2): synthesis,spectroscopic and structural characterization of a transition metal complex containing an unsupported bridging borylene ligand

The synthesis and characterisation of the dinuclear iron complex [(eta 5-C5H5)Fe(CO)2]2B(2,4,6-Me3C6H2) containing an unsupported bridging borylene ligand are reported.     

Fluorescent chemosensor for mercury(II) cations in an aqueous solution based on 4-acetylamino-1, 8-naphthalimide derivative containing the N-phenylazadithia-15-crown-5-ether receptor

The 4-acetylamino-1,8-naphthalimide derivative containing the N-phenylazadithia-15-crown-5-ether fragment in the N-aryl substituent at the imide nitrogen atom of the naphthalimide core was synthesized, and its cation-dependent spectral properties were studied. The resulting compound in the photoexcited state exhibits low-intensity fluorescence due to the process of electron transfer from the N-aryl group to the naphthalimide residue, which is confirmed by the data of quantum chemical calculations performed using the PM6 method. The binding of Hg²⁺ in an aqueous acetate buffer solution at pH 6.0 is accompanied by the formation of a 1: 1 metal—ligand complex in which the electron transfer is suppressed leading to fluorescence enhancement. The observed spectral changes were used for the determination of the stability constant K of the complex (logK = 6.51±0.03). The found limit of Hg²⁺ detection using the synthesized sensor (28 nmol L^?1) is fairly close the maximum permissible concentration for mercury in drinking water. The study of the selectivity of complexation showed that the presence of Cu²⁺, Zn²⁺, Ni²⁺, Pb²⁺ Cd²⁺, Ca²⁺, Mg²⁺, and Fe²⁺ cations did not impede the determination of Hg²⁺. The presented results indicate that the synthesized chemosensor is promising as a selective and highly sensitive fluorescent reagent for Hg²⁺ ions in an aqueous solution.

     

Synthesis and reactions of azomethines containing an m-phenoxyphenyl group: III. N,N’-bis(m-phynoxybenzylideneamino)arenes,-alicyclenes and-polymethylenes, synthesis and properties

Bis(m-phenoxybenzylideneamino)arenas,-alicyclenes, and polymethylenes were prepared, and the possibility to use them as ingredients of polymer compositions was investigated.