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Inverse-sandwich samarium and ytterbium biphenyl complexes were synthesized by the reduction of their trivalent halide precursors with potassium graphite in the presence of biphenyl. While the samarium complex had a similar structure as previously reported rare earth metal biphenyl complexes, with the two samarium ions bound to the same phenyl ring, the ytterbium counterpart adopted a different structure, with the two ytterbium ions bound to different phenyl rings. Upon the addition of crown ether to encapsulate the potassium ions, the inverse-sandwich samarium biphenyl structure remained intact; however, the ytterbium biphenyl structure fell apart with the concomitant formation of a divalent ytterbium crown ether complex and potassium biphenylide. Spectroscopic and computational studies were performed to gain insight into the electronic structures and bonding interactions of these samarium and ytterbium biphenyl complexes. While the ytterbium ions were found to be divalent with a 4f14 electron configuration and form a primarily ionic bonding interaction with biphenyl dianion, the samarium ions were in the trivalent state with a 4f5 electron configuration and mainly utilized the 5d orbitals to form a δ-type bonding interaction with the π* orbitals of the biphenyl tetraanion, showing covalent character.

Inverse-sandwich samarium and ytterbium biphenyl complexes were synthesized by the reduction of their trivalent halide precursors with potassium graphite in the presence of biphenyl. While the samarium complex had a similar structure as previously reported rare earth metal biphenyl complexes, with the two samarium ions bound to the same phenyl ring, the ytterbium counterpart adopted a different structure, with the two ytterbium ions bound to different phenyl rings. Upon the addition of crown ether to encapsulate the potassium ions, the inverse-sandwich samarium biphenyl structure remained intact; however, the ytterbium biphenyl structure fell apart with the concomitant formation of a divalent ytterbium crown ether complex and potassium biphenylide. Spectroscopic and computational studies were performed to gain insight into the electronic structures and bonding interactions of these samarium and ytterbium biphenyl complexes. While the ytterbium ions were found to be divalent with a 4f14 electron configuration and form a primarily ionic bonding interaction with biphenyl dianion, the samarium ions were in the trivalent state with a 4f5 electron configuration and mainly utilized the 5d orbitals to form a δ-type bonding interaction with the π* orbitals of the biphenyl tetraanion, showing covalent character.

Our group has focused on the organometallic chemistry of rare-earth metals and actinides for a decade. By installing ferrocenediamide ligands at electropositive metal centers, we have been able to disclose unprecedented reactivity toward aromatic N-heterocycles, arenes, and other small molecules such as P4. Systematic studies employing X-ray crystallography, spectroscopy, cyclic voltammetry, and density functional theory calculations revealed that the ferrocene backbone could stabilize the electron-deficient metal through a donor-acceptor-type interaction. Most noteworthy is that this interaction can be readily turned on or off by the addition or removal of a Lewis base. In addition to its flexible coordination, the redox-active nature of the ferrocene backbone enabled us to explore redox-switchable transformations. The introduction of ferrocene-based ligands into organolanthanide chemistry not only helped us to study intriguing fundamental problems but also led to fruitful chemistry including small-molecule activation and controlled copolymerization reactions.

Rare-earth metal complexes of reduced π ligands are reviewed with an emphasis on their electronic structure and bonding interactions. This perspective discusses reduced carbocyclic and acyclic π ligands; in certain categories, when no example of a rare-earth metal complex is available, a closely related actinide analogue is discussed. In general, rare-earth metals have a lower tendency to form covalent interactions with π ligands compared to actinides, mainly uranium. Despite predominant ionic interactions in rare-earth chemistry, covalent bonds can be formed with reduced carbocyclic ligands, especially multiply reduced arenes.

Inverse sandwich biphenyl complexes [(NN(TBS))Ln]2(μ-biphenyl)[K(solvent)]2 [NN(TBS) = 1,1'-fc(NSi(t)BuMe2)2; Ln = Gd, Dy, Er; solvent = Et2O, toluene; 18-crown-6], containing a quadruply reduced biphenyl ligand, were synthesized and their magnetic properties measured. One of the dysprosium biphenyl complexes was found to exhibit antiferromagnetic coupling and single-molecule-magnet behavior with Ueff of 34 K under zero applied field. The solvent coordinated to potassium affected drastically the nature of the magnetic interaction, with the other dysprosium complex showing ferromagnetic coupling. Ab initio calculations were performed to understand the nature of magnetic coupling between the two lanthanide ions bridged by the anionic arene ligand and the origin of single-molecule-magnet behavior.

© 2015 Elsevier Inc. This review discusses C. H bond activation of hydrocarbons mediated by rare-earth metal complexes with an emphasis on type of mechanisms. The review is organized as follows: in the first part, C. H bond activations mediated by rare-earth metals and actinides following traditional reaction pathways, such as σ-bond metathesis and 1,2-addition, are summarized; in the second part, nontraditional C. H bond activation examples are discussed in detail in order to understand the underlying mechanisms. The scope of the review is limited to rare-earth metals and actinides, but, in some cases, closely related reactivity of group 4 metals will be included for comparison. The purpose of the review is not only to provide a brief overview of C. H bond activation by f-elements but also to bring to attention unusual C. H bond cleavage reactivity following mechanisms different than σ-bond metathesis and 1,2-addition.

Reliable transformation of low-cost rare-earth metal oxides to organometallic rare-earth metal complexes is a prerequisite for the advancement of non-aqueous rare-earth metal chemistry. We have recently developed an in situ method to prepare rare-earth alkyl and halide precursors supported by a diamidoferrocene NNTBS, 1,1′-fc(NSiMe2tBu)2, as an ancillary ligand. Herein, we extended the scope of this method to other lanthanide ions including those that are redox active, such as cerium, praseodymium, samarium, terbium, thulium, and ytterbium. Specifically, samarium trisbenzyl could be generated in situ and then converted to the corresponding samarium benzyl or iodide complexes in good yield. However, it was found that ytterbium trisbenzyl could not be formed cleanly and the consequent conversion to ytterbium iodide complex was low yielding. By adapting an alternative route, the desired ytterbium chloride precursor could be obtained in good yield and purity.

A new type of C-H bond activation mediated by rare-earth metals under reducing conditions is reported. The synergy between reductants and rare-earth-metal complexes allows the cleavage of unactivated aromatic C-H bonds. The reaction between rare-earth-metal iodides supported by a 1,1'-ferrocenediamide ligand and potassium graphite in benzene leads to the formation of a 1:1 metal molar ratio of the corresponding metal hydride and metal phenyl complex. A proposed mechanism involving an inverse sandwich arene bimetallic intermediate is supported by experimental and computational studies.

Group 3 metal (E)-stilbene complexes supported by a ferrocene diamide ligand were synthesized and characterized. Reactivity studies showed that they behave similar to analogous naphthalene complexes. Experimental and computational results indicated that the double bond was reduced and not a phenyl ring, in contrast to a previously reported uranium (E)-stilbene complex.

Two rare-earth (La and Lu) naphthalene complexes supported by a ferrocene diamide ligand activate P4 under ambient conditions to form M 3P7 species exclusively. The resulting complexes feature a Zintl-type polyphosphide P73- unit stabilized by three lanthanide fragments. The reported metal complexes were characterized by X-ray crystallography, multinuclear NMR spectroscopy, and elemental analysis. © 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Perovskite nanocrystals (NCs), such as MAPbX3 (MA+ = methylammonium; X = Cl, Br, or I), have received attention owing to their excellent optoelectronic properties and ease of integrating with flexible substrates. Lanthanide ion doping is widely used as an effective strategy to enhance the optoelectronic performance of perovskite NCs. However, incorporating the lanthanide dopant and ensuring the emission stability of the perovskite NCs in high‐performance optoelectronic devices remains a major challenge. Herein, the synthesis of Eu2+‐doped MAPbBr3 NCs within the channels of SBA‐15 is presented to improve their stability. The doped MAPbBr3 NC@SBA‐15 composites exhibit significantly improved stability than that of undoped MAPbBr3 NCs. The doped MAPbBr3 NC@SBA‐15 composites exhibit moderate PL quantum yields and excellent stability under ambient conditions and UV irradiation. In addition, the MAEu0.3Pb0.7Br3 NC@SBA‐15 composite applied in white‐light‐emitting diodes (WLEDs) achieves a color rendering index of 73.5. Moreover, MAEu0.3Pb0.7Br3 NC@SBA‐15 can be combined with styrene‐ethylene‐butylene‐styrene to fabricate a flexible direct X‐ray detector, realizing a high sensitivity of 7592.2 µC Gyair−1 cm−2 and a low detection limit of <77 nGyair s−1; this is an outstanding value for a NC‐based flexible direct X‐ray detector. This work serves as a guide for the design of perovskite NCs for both WLEDs and flexible X‐ray detectors. [ABSTRACT FROM AUTHOR]

Defects within perovskite have been known to act as the nonradiative recombination centers, negatively impacting the carrier transport, which degrades the photovoltaic performance of perovskite solar cells (PSCs). Therefore, preparing a high‐quality perovskite film is of vital significance. To this end, a room‐temperature molten salt, dimethylamine formate (DMAFa), is introduced into perovskite precursor solution to regulate the crystallization process of CsPbI3 films. DMAFa can coordinate with Pb2+ as HCOO−‐Pb2+ in the early stages, then HCOO−‐Pb2+ is gradually displaced by I−‐Pb2+ due to its decomposition during the subsequent annealing, thus delaying the crystallization rate, meanwhile, the DMA+ can interact with the uncoordinated Pb2+ to passivate defects of perovskite films, thereby, forming a high‐quality CsPbI3 film with large grain size and low‐defect density. As a result of this strategy, the power conversion efficiency is increased to 20.40%, and the open‐circuit voltage is up to 1.21 V. These findings indicate that the introduction of DMAFa offers a fundamental way to achieve high‐performance CsPbI3 PSCs. [ABSTRACT FROM AUTHOR]

At present, the evaluation index for low carbon manufacturing was mainly focused on the relationship between carbon emission and economic benefits or removal volume. But there was rarely comprehensive evaluation index to evaluate the carbon utilisation level of processing. Based on this, this paper presented the carbon utilisation efficiency as the comprehensive evaluation index in low carbon manufacturing. The carbon utilisation efficiency was defined as the ratio of the carbon emission of materials removal to the whole carbon emission in manufacturing process. A carbon utilisation efficiency model was established in milling process, based on flow characteristics and removal mechanism of carbon emission during milling. Then a multi-objective optimisation model was established based on Particle Swarm Optimisation, and the minimum processing time and high carbon utilisation efficiency were set as the optimisation objectives. And the experiment was performed to confirm the undetermined constant in the optimisation model and verify the effectiveness of the optimisation model. The optimised milling parameters were verified to reduce the processing time and improve the carbon utilisation efficiency. [ABSTRACT FROM AUTHOR]