Coexistence of Spin–Lattice Relaxation and Phonon-Bottleneck Processes in GdIII–Phthlocyaninato Triple-Decker Complexes under Highly Diluted Conditions

Gd³⁺ complexes have been shown to undergo unusual slow magnetic relaxation processes similar to those of single-molecule magnets (SMMs), even though Gd³⁺ does not exhibit strong magnetic anisotropy. To reveal the origin of the slow magnetic relaxation of Gd³⁺ complexes, we have investigated the magnetic properties and heat capacities of two Gd³⁺-phthalocyaninato triple-decker complexes, one of which has intramolecular Gd³⁺–Gd³⁺ interactions and the other does not. It was found that the Gd³⁺–Gd³⁺ interactions accelerate the magnetic relaxation processes. In addition, magnetically diluted samples, prepared by doping a small amount of the Gd³⁺ complexes into a large amount of diamagnetic Y³⁺ complexes, underwent dual magnetic relaxation processes. A detailed dynamic magnetic analysis revealed that the coexistence of spin–lattice relaxation and phonon-bottleneck processes is the origin of the dual magnetic relaxation processes.     

Integrating Biomass into the Organonitrogen Chemical Supply Chain: Production of Pyrrole and d-Proline from Furfural

Production of renewable, high-value N-containing chemicals from lignocellulose will expand product diversity and increase the economic competitiveness of the biorefinery. Herein, we report a single-step conversion of furfural to pyrrole in 75 % yield as a key N-containing building block, achieved via tandem decarbonylation–amination reactions over tailor-designed Pd@S-1 and H-beta zeolite catalytic system. Pyrrole was further transformed into dl -proline in two steps following carboxylation with CO₂ and hydrogenation over Rh/C catalyst. After treating with Escherichia coli, valuable d -proline was obtained in theoretically maximum yield (50 %) bearing 99 % ee. The report here establishes a route bridging commercial commodity feedstock from biomass with high-value organonitrogen chemicals through pyrrole as a hub molecule.     

pH-Dependent Hydration Change in a Gd-Based MRI Contrast Agent with a Phosphonated Ligand

The heptadentate ligand L was shown to form an extremely stable Gd complex at neutral pH with a pGd value of 18.4 at pH 7.4. The X-ray crystal structures of the complexes formed with Gd and Tb displayed two very different coordination behaviors being, respectively, octa- and nonacoordinated. The relaxometric properties of the Gd complex were studied by field-dependent relaxivity measurements at various temperatures and by ¹⁷O NMR spectroscopy. The pH-dependence of the longitudinal relaxivity profile indicated large changes around neutral pH leading to a very large value of 10.1 mm ⁻¹⋅s⁻¹ (60 MHz, 298 K) at pH 4.7. The changes were attributed to an increase of the hydration number from one water molecule in basic conditions to two at acidic pH. A similar trend was observed for the luminescence of the Eu complex, confirming the change in hydration state. DOSY experiments were performed on the Lu analogue, pointing to the absence of dimers in solution in the considered pH range. A breathing mode of the complex was postulated, which was further supported by ¹H and ³¹P NMR spectroscopy of the Yb complex at varying pH and was finally modeled by DFT calculations.     

l‐Proline‐functionalized Fe3O4 nanoparticles as a novel magnetic chiral catalyst for the direct asymmetric Mannich reaction

l ‐Proline has been successfully anchored on the surface of magnetic nanoparticles and characterized using powder X‐ray diffraction, scanning electron microscopy, vibrating sample magnetometry and Fourier transform infrared spectroscopy. These nanoparticles as a chiral catalyst have been employed to promote the direct asymmetric Mannich reaction. The corresponding products are obtained in high yields with high level of diastereoselectivity (up to 99:1 dr) in the presence of Fe₃O₄– l ‐proline. Also this heterogeneous catalyst can be recovered easily and reused many times without significant loss of its catalytic activity. Copyright © 2015 John Wiley & Sons, Ltd.     

Promising solid electrolyte material for an IT‐SOFC: crystal structure of the cerium gadolinium holmium oxide Ce0.8Gd0.1Ho0.1O1.9 between 295 and 1023 K

The crystal structure of Ce_0.8Gd_0.1Ho_0.1O_1.9 (cerium gadolinium holmium oxide) has been determined from powder X‐ray diffraction data. This is a promising material for application as a solid electrolyte for intermediate‐temperature solid oxide fuel cells (IT‐SOFCs). Nanoparticles were prepared using a novel sodium alginate sol‐gel method, where the sodium ion was exchanged with ions of interest and, after washing, the gel was calcined at 723 K in air. The crystallographic features of Gd and Ho co‐doped cerium oxide were investigated around the desired operating temperatures of IT‐SOFCs, i.e. 573 ≤ T ≤ 1023 K. We find that the crystal structure is a stable fluorite structure with the space group Fmm in the entire temperature range. In addition, the trend in lattice parameters shows that there is a monotonic increase with increasing temperature.     

Facile solvent-free synthesis and structural elucidation of styrylcyclohex-2-enone derivatives

A remarkably efficient procedure for the synthesis of styrylcyclohex-2-enone derivatives at room temperature is described using a mild reaction medium consisting of lithium perchlorate and N-(trimethylsilyl)diethylamine. Several compounds of this class are synthesized conveniently and rapidly. Spectroscopic and X-ray diffraction experiments confirm the proposed structures. Correspondence: Mohammad M. Mojtahedi and Mohammad Saeed Abaee, Organic Chemistry Laboratory, Chemistry and Chemical Engineering Research Center of Iran, P.O. Box 14335-186, Tehran, Iran.     

Magnesium perchlorate as efficient Lewis acid for the Knoevenagel condensation between β-diketones and aldehydes

A new protocol for the Knoevenagel condensation between β-diketones and aliphatic and aromatic aldehydes promoted by Mg(ClO₄)₂ under mild conditions is reported.     

氢过碘酸）合银（III）配离子氧化L-脯氨酸的反应动力学及机理

L-脯氨酸独有的亚胺基使其在生物医药领域具有许多独特的功能,并广泛用作不对称有机化合物合成的有效催化剂。本文在碱性介质中研究了二（氢过碘酸）合银（III）配离子氧化 L-脯氨酸的反应。经质谱鉴定,脯氨酸氧化后的产物为脯氨酸脱羧生成的 γ-氨基丁酸盐;氧化反应对脯氨酸及Ag(III) 均为一级;二级速率常数 k′ 随 [IO₄^-] 浓度增加而减小,而与 [OHˉ] 的浓度几乎无关;推测反应机理应包括 [Ag(HIO₆)₂]^5-与 [Ag(HIO₆)(H₂O)(OH)]^2-之间的前期平衡,两种Ag（III）配离子均作为反应的活性组分,在速控步被完全去质子化的脯氨酸平行地还原,两速控步对应的活化参数为： k₁ (25 ^oC)＝1.87±0.04（mol·L^-1)^-1s^-1,∆ H₁^≠＝45±4 kJ · mol^-1, ∆ S₁^≠＝-90±13 J· K^-1·mol^-1 and k₂ (25 ^oC) ＝3.2±0.5（mol·L^-1)^-1s^-1, ∆ H₂^≠＝34±2 kJ · mol^-1, ∆ S₂^≠＝-122 ±10 J· K^-1·mol^-1。本文第一次发现 [Ag(HIO₆)₂]^5-配离子也具有氧化反应活性。     

Endohedral gadolinium-containing metallofullerenes in the trifluoromethylation reaction

An efficient method for the synthesis of trifluoromethyl derivatives of endohedral gadolinium-containing metallofullerenes was proposed. High-purity (98–99%) trifluoromethyl derivatives Gd@C₈₂(CF₃)₅ (two isomers) and Gd₂@C₈₀(CF₃) have been synthesized for the first time. They were isolated and characterized by HPLC, MALDI-TOF mass spectrometry, and UV-Vis spectroscopy. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1457–1462, July, 2008.