发光铱(Ⅲ)配合物抗肿瘤活性研究及应用

铱(Ⅲ)配合物因其发光量子产率高且波长易调控、发光寿命长和光稳定性好的特点,在发光材料领域备受关注。铱(Ⅲ)配合物细胞渗透能力强,能靶向多种细胞组织并影响其结构和功能,表现出独特的抗肿瘤活性,是目前金属抗肿瘤药物特别是PDT光敏剂方向的研究热点。本文重点关注铱(Ⅲ)配合物的结构对其发光性能与抗肿瘤性能的影响,综述了近期铱(Ⅲ)配合物在生物成像、探针与传感、抗肿瘤诊疗等领域的研究进展,并对目前研究中存在的问题及其应用前景进行探讨和展望。     

Cyclopentadienyl rhodium(III) complexes as catalysts for the insertion of phenyldiazoacetate into E−H bonds

Rhodium(III) complexes catalyze the insertion of carbenoids generated from diazo compounds into E?H bonds (E = B, Si, N, but not C), although less efficiently than classical rhodium(II) carboxylates, despite formally higher oxidation state of the metal.     

Helicate tris(aryl)carbinolates bearing pendant NR2 donors – a new family of supporting ligands for the synthesis of Sc3+ alkyl complexes

The reactions of aryllithium reagents o-LiC₆H₄CH₂NR₂ with (MeO)₂CO afford two new tris(aryl)carbinols bearing pendant-NR₂ donor groups in the side chain [o-R NCH C H ] COH [R = Me, R + R = (CH) ]. These alcohols feature helical chirality due to differently inclined aromatic fragments and are presented in a crystalline cell as two M and P enantiomers. Carbinol (R = Me) readily reacts with (Me3SiCH2)3Sc(THF)2 to give a scandium bis(alkyl) complex [(o-C₆H₄CH₂NMe₂)₃CO]Sc(CH₂SiMe₃)₂ featuring rigid binding of the alkoxy anion through a κ¹-O, κ²-N chelating coordination mode     

Encapsulated Neutral Ruthenium Catalyst for Substrate-Selective Oxidation of Alcohols

The neutral complex dichloro-{diethyl[(5-phenyl-1,3,4-oxadiazol-2-ylamino)-(4-trifluoro-methylphenyl)methyl]phosphonate} (p-cymene)-ruthenium(II) was encapsulated inside a self-assembled hexameric host obtained upon reaction of 2,8,14,20-tetra-undecyl-resorcin[4]arene and water. The formation of an inclusion complex was inferred from a combination of spectral measurements (MS, UV/Vis spectroscopy, ¹H and DOSY NMR). The ³¹P and ¹⁹F NMR spectra are consistent with motions of the ruthenium complex inside the self-assembled capsule. Molecular dynamics simulations carried out on the inclusion complex confirmed these intra-cavity movements and highlighted possible supramolecular interactions between the ruthenium first coordination sphere ligands and the inner part (aromatic rings) of the capsule. The embedded ruthenium complex was assessed in the catalytic oxidation (using NaIO₄ as oxidant) of mixtures of three arylmethyl alcohols into the corresponding aldehydes. The reaction kinetics were shown to vary as a function of the substrates’ size, with the oxidation rate varying in the order benzylalcohol >4-phenyl-benzylalcohol >9-anthracenemethanol. Control experiments realized in the absence of hexameric capsule did not allow any discrimination between the substrates.     

Self-oscillating gels based on novel catalyst for the Belousov–Zhabotinsky reaction

We report on the synthesis of new Ru(bpy)₂(phen) catalyst for the oscillatory Belousov–Zhabotinsky chemical reaction and on the preparation of novel Ru(bpy)₂(phen)-based self-oscillating gels. The synthesized gels exhibit high-amplitude autonomous mechanical oscillations when the Belousov–Zhabotinsky reaction proceeds inside these gels     

Solid-state luminescence of Au(I) complexes with external stimuli-responsive properties

In the last decade, the field of stimuli-responsive luminescent materials have been intensely emerged because of the high potential application to functional sensors or photoelectronic devices. In particular, luminescent molecular crystals constructed from Au(I) complexes have produced a wide range of examples of luminescent alterations when some external stimulations, such as heat, mechanical stress, vapor (or solvents), were applied to the solid samples. In this review, we describe the recent progress through a summary of the reported Au(I) complexes based on their utilized stimuli-responsive mechanisms, which are categorized in crystal phase transitions (“crystal-to-amorphous”, “crystal-to-crystal” and “single-crystal-to-single-crystal” transitions) and molecular rotation in crystalline media, respectively.     

Bidentate Boron Lewis Acids: Selectivity in Host–Guest Complex Formation

Bidentate boron Lewis acids based on 1,8‐diethynylanthracene were synthesised in two steps by initial stannylation of the terminal alkynes and subsequent tin–boron exchange with different chloroboranes. The reactions were very selective, and the target compounds were obtained in high purity and good to excellent yields. Complexation experiments of 1,8‐bis[(diphenylboranyl)ethynyl]anthracene with nitrogen bases (pyridine, pyrimidine, TMEDA) afforded three stable adducts, which were structurally characterised by X‐ray diffraction. Competition experiments demonstrated the selective exchange of guests, and quantum‐chemical calculations provided information on their energetics. NMR experiments at low temperature gave insight into the dynamic behaviour of the TMEDA adduct.     

Substitution‐Pattern‐ and Counteranion‐Depending Ion‐Pairing Assemblies Based on Electron‐Deficient Porphyrin–AuIII Complexes

Porphyrin–Au^III complexes, which were partially or totally modified with C₆F₅ at the meso positions, were synthesized. The highly electron‐withdrawing substituents induced electron‐deficient states and Lewis acid properties. Single‐crystal X‐ray analysis of the ion pairs revealed ion‐pairing assemblies with characteristics dependent on the number and substitution pattern of the C₆F₅ units and the geometries of the anions.     

“能干而低调”的钨元素

较为详细地介绍了钨元素的发现历程，钨金属与合金、含钨杂多配合物、氧化钨、碳化钨、钨硫族化合物和含有W-W四重键的化合物的应用。