Design, Tuning

• Mn3+ in Trigonal Bipyramidal Coordination: A New Blue Chromophore

Journal of the American Chemical Society

Smith, Mizoguchi, Delaney, Spaldin, Sleight and Subramanian

2009 131 (47), pp 6

Abstract: We show that trivalent manganese, Mn3+, imparts an intense blue color to oxides when it is introduced at dilution in trigonal bipyramidal coordination. Our optical measurements and first-principles density functional theory calculations indicate that the ...

• From M(BH4)3 (M = La, Ce) Borohydride Frameworks to Controllable Synthesis of Porous Hydrides and Ion Conductors

Inorganic Chemistry

Ley, Jørgensen, Černý, Filinchuk, and Jensen

2016 55 (19), pp 9748–9756

Abstract: Rare earth metal borohydrides show a number of interesting properties, e.g., Li ion conductivity and luminescence, and the series of materials is well explored. However, previous attempts to obtain M(BH4)3 (M = La, Ce) by reacting MCl3 and LiBH4 yielded ...Synthetic approaches are presented for the isolation of -/-M(BH4)3 (M = La, Ce). The cubic -Ce(BH4)3 (Fm3̅) contains empty voids (∼59 Å3) in the open framework structure. Additionally, M(BH4)3 can be combined with LiCl in an addition reaction to form Li4[M4(BH4)12Cl4], containing the unique tetranuclear cluster [M4(BH4)12Cl4]4− and shows high Li-ion conductivity. This reaction pathway opens a way to synthesize a series of A4[M4(BH4)12X4] compounds with different anions (X) and metal ions (A).

• High-Pressure Synthesis and Ferrimagnetic Ordering of the B-Site-Ordered Cubic Perovskite Pb2FeOsO6

Zhao, Liu, Dai, Deng, Yin, Zhou, Yang, Hu, Agrestini, Chen, Pellegrin, Valvidares, Nataf, Baudelet, Tjeng, Yang, Jin, and Long

2016 55 (19), pp 9816–9821

Abstract: Pb2FeOsO6 was prepared for the first time by using high-pressure and high-temperature synthesis techniques. This compound crystallizes into a B-site-ordered double-perovskite structure with cubic symmetry Fm3̅, where the Fe and Os atoms are orderly ...A novel oxide Pb2FeOsO6 was synthesized by using high-pressure techniques. This is the first observation of a B-site-ordered cubic double perovskite in the A2FeOsO6 family. The antiferromagnetic interaction occurring between the half-filled 3d orbitals of Fe and t2g orbitals of Os instead of the empty Os eg ones leads to a long-range ferrimagnetic ordering near 280 K via the 180° Fe−O−Os interaction pathways.

• Effect of Co Substitution on the Crystal and Magnetic Structure of SrFeO2.75−δ: Stabilization of the “314-Type” Oxygen Vacancy Ordered Structure without A-Site Ordering

Marik, Chennabasappa, Fernández-Sanjulián, Petit, and Toulemonde

2016 55 (19), pp 9778–9789

Abstract: A study of the structure–composition–properties correlation is reported for the oxygen-deficient SrFe1–xCoxO2.75−δ ( = 0.1–0.85) materials. The introduction of Co in the parent SrFeO2.75 (Sr4Fe4O11) structure revealed an interesting structural ...A study of the structure−composition−properties correlation is reported for the oxygen-deficient SrFe1−xCoxO2.75−δ ( = 0.1−0.85) materials. At room temperature (RT), orthorhombic (Cmmm, 2√2p × 2ap×√2ap) → tetragonal (4/mmm, p × p × 2p type) → tetragonal (4/mmm, 2p × 2p × 4ap) structural transformation is observed with increasing Co content. Further, the stabilization of the “314-type” superstructure is related to the ordering of oxygen vacancies in the oxygen-deficient Co−O layers, and the same assists in forming Co3+ spin-state ordering.

• Post-Synthesis Modification of the Aurivillius Phase Bi2SrTa2O9 via In Situ Microwave-Assisted “Click Reaction”

Wang, Delahaye, Leuvrey, Leroux, Rabu, and Rogez

2016 55 (19), pp 9790–9797

Abstract: A new strategy for the functionalization of layered perovskites is presented, based on the in situ post-synthesis modification of a prefunctionalized phase by copper(I)-catalyzed alkyne–azide cycloaddition (CuAAC). The microwave-assisted protonation and ...Fast and efficient in situ modification of the interlayer functionalization of a layered perovskite can be achieved via microwave-assisted post-synthesis click reaction. This strategy allows to overcome the limitations of insertion/grafting approaches to the synthesis of layered perovskite hybrids.

• Determination of the Local Environment of Mn3+ and In3+ in the YInO3–YMnO3 Solid Solution, Which Exhibits an Intense Blue Color

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