Dalton Transactions

doi: 10.1039/C8DT90095Gpmid: N/A

doi: 10.1039/c8dt90095gpmid: N/A

doi: 10.1039/c8dt90096epmid: N/A

doi: 10.1039/C8DT90096Epmid: N/A

Shiga, Takuya; Newton, Graham N.; Oshio, Hiroki

doi: 10.1039/c8dt00822apmid: 29667675

This perspective reviews our recent efforts towards the self-assembly of polynuclear clusters with ditopic and tritopic multidentate ligands HL1 (2-phenyl-4,5-bis{6-(3,5-dimethylpyrazol-1-yl)pyrid-2-yl}-1H-imidazole) and H2L2 (2,6-bis-[5-(2-pyridinyl)-1H-pyrazole-3-yl]pyridine), both of which are planar and rigid molecules. HL1 was found to be an excellent support for tetranuclear [Fe4] complexes, [FeII4(L1)4](BF4)4 ([FeII4]) and [FeIII2FeII2(L1)4](BF4)6 ([FeIII2FeII2]). The homovalent system was found to exhibit multistep spin crossover (SCO), while the mixed-valence [FeIII2FeII2] complex shows wavelength-dependent tuneable light-induced excited spin state trapping (LIESST). For H2L2, a variety of polynuclear complexes were obtained through complexation with different transition metal ions, allowing the isolation of rings, grids, and helix structures. The rigidity of the ligand, difference in its coordination sites, and affinity for different metal ions dictates its coordination behaviour. In this paper, we summarise these ligand pre-programmed self-assembled clusters and their diverse physical properties.

Chen, Xiao-Xiang; Ma, Fang; Xu, Mei-Xing; Bi, Jin-Cheng; Sun, Hao-Ling; Wang, Bing-Wu; Gao, Song

doi: 10.1039/c8dt01102hpmid: 29770394

An approximately equatorial three-coordinated dysprosium(iii) complex DyL2[N(SiMe3)2] (L = bis(2-(2,5-dimethyl-1H-pyrrol-1-yl)ethyl)amine) with an additional neutral auxiliary pyrrole ligand was synthesised and structurally characterized. The magnetic property measurement shows that it is an equatorial charge distributed field-induced single-molecule magnet. Ab initio calculations reveal that the neutral pyrrole ligand plays an important role in stabilizing the ground doublet and thus enhancing the magnetic anisotropy.

Arikawa, Yasuhiro; Hiura, Junko; Tsuchii, Chika; Kodama, Mika; Matsumoto, Naoki; Umakoshi, Keisuke

doi: 10.1039/c8dt01208cpmid: 29770405

A synthetic NO reduction cycle (2NO + 2H+ + 2e− → N2O + H2O) on a dinuclear platform {(TpRu)2(μ-pz)2} (Tp = HB(pyrazol-1-yl)3) was achieved, where an unusual N–N coupling complex was included. Moreover, an interesting photo-induced conversion of the N–N coupling complex to an oxido-bridged complex was revealed.

Liu, Xianyu; Lin, Ning; Cai, Wenlong; Zhao, Yingyue; Zhou, Jianbin; Liang, Jianwen; Zhu, Yongchun; Qian, Yitai

doi: 10.1039/c8dt01060apmid: 29770414

In a simple and convenient way, mesoporous germanium nanoparticles (mp-Ge NPs) are prepared by a “metathesis” reaction of magnesium germanide (Mg2Ge) and zinc chloride (ZnCl2) in an autoclave at 300 °C. Investigated as anode materials for lithium-ion batteries, the prepared mp-Ge NPs exhibit a high capacity retention of 1048 mA h g−1 at 1 C after 1000 cycles and a high rate capacity of 727.1 mA h g−1 at 10 C in Li–Ge half cells. Additionally, a 3.4 V lithium-ion full cell (Ge-LiCoO2) with an energy retention of 85% (∼268.8 W h kg−1) over 100 cycles is achieved.

Zhou, Kang; Zhang, Wen-Jin; Luo, Yuan-Zhang; Pan, Chun-Yang

doi: 10.1039/c8dt01077cpmid: 29770810

A 3D inorganic–organic hybridized skeleton cadmium borate [Cden][B5O8(OH)] (1) (en = ethylenediamine) has been solvothermally synthesized. By calcining it, specific shape carbon dots (C-dots) with abundant free radicals were observed. In addition, C-dots in the ethanol phase exhibited variable photoluminescence and showed rare turn on or off effects to Cr3+ ions and CdSe/ZnS quantum dots, but only a turn on effect to Cs+ ions and a turn off effect to CsPbBr3 quantum dots.

Wang, Si-Yuan; Jin, Wan-Ting; Chen, Hong-Bin; Zhou, Zhao-Hui

doi: 10.1039/c8dt00278apmid: 29786717

Glycolato and R,S-lactato imidazole molybdenum(iv) complexes [Mo3SO3(glyc)2(im)5]·im·H2O (1), Na2[Mo3SO3(R,S-lact)3(im)3]·10H2O (2), and [Mo6O10(R,S-lact)2(im)10]·16H2O (3) have been isolated and characterized (H2glyc = glycolic acid, H2lact = lactic acid, im = imidazole). α-Alkoxy coordination with molybdenum [Mo–Oα-alkoxy 1.993(7)av Å] in 1 and 2 showed obvious differences to their counterpart with α-hydroxy coordination [MoIV3S4(PPh3)3(Hlact)2(lact)] [2.204(4)av Å] as shown in M. N. Sokolov, S. A. Adonin, A. V. Virovets, P. A. Abramov, C. Vicent, R. Llusar and V. P. Fedin, Inorg. Chim. Acta, 2013, 395, 11–18. This was also true for the 36 reported structures of FeMo-cofactors in the RCSB protein data bank (Mo–Oav 2.272 Å), which can serve as indirect evidence for the protonation of homocitrate in FeMo-co. The C–OHα-hydroxy bonds were longer than the short C–Oα-alkoxy bonds. Trinuclear Mo3SO3 cores were stabilized by imidazoles and/or α-hydroxycarboxylates, whereas only two glycolates were present in 1. α-Hydroxycarboxylates in 1 and 2 acted as bidentate ligands of Mo(iv) atoms through α-alkoxy and α-carboxy groups, while the imidazoles coordinated monodentately with nitrogen atoms. The lactates in 3 coordinated with Mo(iv) atoms through two oxygen atoms of α-carboxy groups, leaving the α-hydroxy group free. Furthermore, novel hexanuclear oxomolybdenum(v) malate Na6[(Mo2O4)3(mal)4]·5H2O (4) was also isolated (H3mal = malic acid). Solid-state and solution 13C NMR resonances of carbon atoms in α-alkoxy groups appeared in a high-field region (71.6, 77.4 ppm), indicating that α-alkoxy groups were easy to protonate.