A Molecular Analogue of the C−H Activation Intermediate of the Silica-Supported Ga(III) Single-Site Propane Dehydrogenation Catalyst: Structure and XANES Signature

Propane dehydrogenation is an important field of research due to an increasing world-wide demand of propene while classical production routes through naphtha cracking are in decline. In that context, silica-supported Ga(III) sites, synthesized from surface organometallic chemistry principles, show high selectivity and stability in the propane dehydrogenation reaction. This performance is in significant contrast to the reported fast deactivation and lower selectivity of most Ga₂O₃ and CrO₃ based materials. The Ga-catalyzed propane dehydrogenation reaction is proposed to proceed through the formation of Ga alkyl intermediates for which it would be desirable to have detailed structural and spectroscopic information. Here, we prepare a consistent series of Ga(III) molecular complexes with varying numbers of alkyl and siloxide ligands; they are characterized by single crystal X-Ray diffraction and X-Ray Absorption Near Edge Structure analysis, which is known to be highly sensitive to the Ga coordination environment. We report in particular the structure and the spectroscopic signatures of [Ga(ⁱPr)(OSi(O^tBu)₃)₂(HOSi(O^tBu)₃)], a molecular mimic of the key proposed reaction intermediates in the Ga-catalyzed PDH reaction.     

Fundamental Characterization,Photophysics and Photocatalysis of a Base Metal Iron(II)-Cobalt(III) Dyad

A new base metal iron-cobalt dyad has been obtained by connection between a heteroleptic tetra-NHC iron(II) photosensitizer combining a 2,6-bis[3-(2,6-diisopropylphenyl)imidazol-2-ylidene]pyridine with 2,6-bis(3-methyl-imidazol-2-ylidene)-4,4′-bipyridine ligand, and a cobaloxime catalyst. This novel iron(II)-cobalt(III) assembly has been extensively characterized by ground- and excited-state methods like X-ray crystallography, X-ray absorption spectroscopy, (spectro-)electrochemistry, and steady-state and time-resolved optical absorption spectroscopy, with a particular focus on the stability of the molecular assembly in solution and determination of the excited-state landscape. NMR and UV/Vis spectroscopy reveal dissociation of the dyad in acetonitrile at concentrations below 1 mM and high photostability. Transient absorption spectroscopy after excitation into the metal-to-ligand charge transfer absorption band suggests a relaxation cascade originating from hot singlet and triplet MLCT states, leading to the population of the ³MLCT state that exhibits the longest lifetime. Finally, decay into the ground state involves a ³MC state. Attachment of cobaloxime to the iron photosensitizer increases the ³MLCT lifetime at the iron centre. Together with the directing effect of the linker, this potentially makes the dyad more active in photocatalytic proton reduction experiments than the analogous two-component system, consisting of the iron photosensitizer and Co(dmgH)₂(py)Cl. This work thus sheds new light on the functionality of base metal dyads, which are important for more efficient and sustainable future proton reduction systems.     

A Molecular Photosensitizer in a Porous Block Copolymer Matrix-Implications for the Design of Photocatalytically Active Membranes

Recently, porous photocatalytically active block copolymer membranes were introduced, based on heterogenized molecular catalysts. Here, we report the integration of the photosensitizer, i. e., the light absorbing unit in an intermolecular photocatalytic system into block copolymer membranes in a covalent manner. We study the resulting structure and evaluate the orientational mobility of the photosensitizer as integral part of the photocatalytic system in such membranes. To this end we utilize transient absorption anisotropy, highlighting the temporal reorientation of the transition dipole moment probed in a femtosecond pump-probe experiment. Our findings indicate that the photosensitizer is rigidly bound to the polymer membrane and shows a large heterogeneity of absolute anisotropy values as a function of location probed within the matrix. This reflects the sample inhomogeneity arising from different protonation states of the photosensitizer and different intermolecular interactions of the photosensitizers within the block copolymer membrane scaffold.     

类姜黄素-芳基钌配合物的合成、结构和光照激活抗癌活性

合成了3种含姜黄素衍生物(L¹~L³)和1,3,5-三氮杂-7-磷金刚烷(PTA)配体的芳基钌配合物[(η⁶-p-cymene)Ru(L)(PTA)]PF6(1~3,L=L¹~L³),通过X射线单晶衍射、核磁共振波谱、高分辨质谱、元素分析等方法表征了这些配合物的结构,并用MTT法研究了它们在λ>400 nm的光照辅助下对Hep G2人肝癌细胞的增殖抑制活性。结果表明,这3个配合物均为半三明治型结构;光辅助下,配合物抗癌活性明显提高,其中配合物3对HepG2细胞的IC50值从(60.3±1.1)μmol·L^-1降低至(45.0±6.1)μmol·L^-1。说明光照可以有效提高此类配合物的抗肿瘤活性。     

1，1'-二羟基-5，5'-联四唑的镧系金属配合物的合成、表征及热行为

以1,1′-二羟基-5,5′-联四唑(H_2BTO)为配体,镧系金属离子作为金属中心,采用溶剂热法制备了5种金属配合物:[La_2(BTO)_3(H_2O)_8]·2H_2O (1)、[Ce_2(BTO)_3(H_2O)_8]·2H_2O (2)、[Pr_2(BTO)_3(H_2O)_8]·2H_2O (3)、[Sm_2(BTO)_3(H_2O)_8]·2H_2O (4)和[Nd_2(BTO)_3(DMF)_4]·6H_2O (5)。通过单晶X射线衍射和元素分析对5种配合物的结构进行了表征。结果表明,5种配合物均属于单斜晶系,P2_1/n空间群。利用差示扫描量热法研究了配合物1～4的热稳定性,采用Kissinger法和Ozawa法分别计算了其热分解动力学参数。     

Platinum Indolylphosphine Fluorido and Polyfluorido Complexes: An Interplay between Cyclometallation,Fluoride Migration,and Hydrogen Bonding

The reaction of [PtCl₂(COD)] (COD=1,5-cyclooctadiene) with diisopropyl-2-(3-methyl)indolylphosphine (iPr₂P(C₉H₈N)) led to the formation of the platinum(ii ) chlorido complexes, cis-[PtCl₂{iPr₂P(C₉H₈N)}₂] ( 1 ) and trans-[PtCl₂{iPr₂P(C₉H₈N)}₂] ( 2 ). The cis-complex 1 reacted with NEt₃ yielding the complex cis-[PtCl{κ²-(P,N)-iPr₂P(C₉H₇N)}{iPr₂P(C₉H₈N)}] ( 3 ) bearing a cyclometalated κ²-(P,N)-phosphine ligand, while the isomer 2 with a trans-configuration did not show any reactivity towards NEt₃. Treatment of 1 or 3 with (CH₃)₄NF (TMAF) resulted in the formation of the twofold cyclometalated complex cis-[Pt{κ²-(P,N)-iPr₂P(C₉H₇N)}₂] ( 4 ). The molecular structures of the complexes 1–4 were determined by single-crystal X-ray diffraction. The fluorido complex cis-[PtF{κ²-(P,N)-iPr₂P(C₉H₇N)}{iPr₂P(C₉H₈N)}] ⋅ (HF)₄ ( 5 ⋅ (HF)₄) was formed when complex 4 was treated with different hydrogen fluoride sources. The Pt(ii ) fluorido complex 5 ⋅ (HF)₄ exhibits intramolecular hydrogen bonding in its outer coordination sphere between the fluorido ligand and the NH group of the 3-methylindolyl moiety. In contrast to its chlorido analogue 3 , complex 5 ⋅ (HF)₄ reacted with CO or the ynamide 1-(2-phenylethynyl)-2-pyrrolidinone to yield the complexes trans-[Pt(CO){κ²-(P,C)-iPr₂P(C₉H₇NCO)}{iPr₂P(C₉H₈N)}][F(HF)₄] ( 7 ) and a complex, which we suggest to be cis-[Pt{C=C(Ph)OCN(C₃H₆)}{κ²-(P,N)-iPr₂P(C₉H₇N)}{iPr₂P(C₉H₈N)}][F(HF)₄] ( 9 ), respectively. The structure of 9 was assigned on the basis of DFT calculations as well as NMR and IR data. Hydrogen bonding of HF and NH to fluoride was proven to be crucial for the existence of 7 and 9 .     

Extended X‐ray absorption fine structure and multiple‐scattering simulation of nickel dithiolene complexes Ni[S2C2(CF3)2]2n (n = −2, −1, 0) and an olefin adduct Ni[S2C2(CF3)2]2(1‐hexene)

A series of Ni dithiolene complexes Ni[S₂C₂(CF₃)]₂ⁿ (n = ?2, ?1, 0) ( 1 , 2 , 3 ) and a 1‐hexene adduct Ni[S₂C₂(CF₃)₂]₂(C₆H₁₂) ( 4 ) have been examined by Ni K‐edge X‐ray absorption near‐edge structure (XANES) and extended X‐ray absorption fine‐structure (EXAFS) spectroscopies. Ni XANES for 1 – 3 reveals clear pre‐edge features and approximately +0.7 eV shift in the Ni K‐edge position for `one‐electron' oxidation. EXAFS simulation shows that the Ni—S bond distances for 1 , 2 and 3 (2.11–2.16 Å) are within the typical values for square planar complexes and decrease by ～0.022 Å for each `one‐electron' oxidation. The changes in Ni K‐edge energy positions and Ni—S distances are consistent with the `non‐innocent' character of the dithiolene ligand. The Ni—C interactions at ～3.0 Å are analyzed and the multiple‐scattering parameters are also determined, leading to a better simulation for the overall EXAFS spectra. The 1‐hexene adduct 4 presents no pre‐edge feature, and its Ni K‐edge position shifts by ?0.8 eV in comparison with its starting dithiolene complex 3 . Consistently, EXAFS also showed that the Ni—S distances in 4 elongate by ～0.046 Å in comparison with 3 . The evidence confirms that the neutral complex is `reduced' upon addition of olefin, presumably by olefin donating the π‐electron density to the LUMO of 3 as suggested by UV/visible spectroscopy in the literature.     

Surface Roughness Characterization of Poly(methylmethacrylate) Films with Immobilized Eu(III) β-Diketonates by Fractal Analysis

The structural complexity of the 3-D surface of poly(methylmethacrylate) films with immobilized europium β-diketonates was studied by atomic force microscopy and fractal analysis. Fractal analysis of surface roughness revealed that the 3-D surface has fractal geometry at the nanometer scale. Poly(methylmethacrylate) (PMMA) as immobilization matrix is dense and uniform, and a tendency for formation of chain structures was observed. Fractal analysis can quantify key elements of 3-D surface roughness such as the fractal dimensions D _f determined by the morphological envelopes method of the Eu(DBM)₃ and Eu(DBM)₃ · dpp nanostructures, which are not taken into account by traditional surface statistical parameters.     

A Pencil Graphite Electrode In Situ Modified by Monovalent Copper: a Promising Tool for the Determination of Methylxanthines

A pencil graphite electrode (PeGE) exhibits a promising tool for the electrochemical analysis of xanthine (Xan) and its N‐methyl derivatives (1‐, 3‐, 7‐ and 9‐mXan). The changes in their level in blood, serum, urine, as products of purine catabolism, can indicate the development of some diseases. Sensitivity‐enhanced voltammetric detection of mXans was achieved by forming of complex with Cu(I) and application of elimination procedure. The Cu(I)‐mXan complex was identified by means of titration of electrochemically produced cuprous ions by mXan. Our approach enables separation of overlapped mXan oxidation signals. Based on the obtained results, we found that the effect of methyl group position on the xanthine skeleton was significant and it was also discussed.     

The mass spectrometric study on aminohydroxamic acids‐based metallacrowns

Electrospray ionization mass spectrometry (MS) has been widely used to detect noncovalent interactions in supramolecular compounds, especially in biological systems. In our work, we present the application of the electrospray ionization MS technique to characterize the metallamacrocycles, known as metallacrowns. This project involves investigations of the aminohydroxamic acids structure and chirality influence on formation of ternary 12‐metallacrown‐4 complexes. For our experiments, we used a series of β‐aminohydroxamic acids and derivatives of histidinehydroxamic acid. A high stability of the studied supramolecular systems in the gas phase was confirmed by MS/MS experiments. We also proposed the fragmentation pathways for the studied compounds. Obtained results reveal that the ternary 12‐metallacrown‐4 formation process is not selective, and ligands of various structures and chiralities can be incorporated into these systems. Copyright © 2014 John Wiley & Sons, Ltd.