An innovative method of synthesis is reported for the large and diverse (RE)6(TM)x(Tt)2S14 (RE = rare-earth, TM = transition metals, Tt = Si, Ge, and Sn) family of compounds (~2000...

Complex polymorphic relationships in the LnSiP3 (Ln = La and Ce) family of compounds are reported. An innovative synthetic method was developed to overcome differences in the reactivities of the...

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This research combined machine-learning methodology, first-principles calculations, and solid-state synthesis to discover novel inorganic compounds. A machine-learning model was developed to predict the DFT-calculated formation energy of compounds as an essential factor in their thermodynamical stability. This approach was then validated by studying four ternary composition diagrams, Y-Ag-Tr (Tr = B, Al, Ga, In), leading to the discovery of YAg 0.65 In 1.35 . The success of this work is to accelerate materials discovery by directing synthesis efforts.

Non‐linear optical materials must possess a balanced combination of laser‐induced damage threshold (LDT) and second‐harmonic generation (SHG) and be phase matchable. In our previous work, chiral and polar La3CuGeS7 was identified as a promising non‐linear optical material. Herein, we report the optimization of non‐linear optical properties through replacement of La with smaller lanthanides. It is determined that Gd3CuGeS7 exhibits the best combination of SHG (1.6× AgGaS2 at 88–105 μm particle size) and LDT (3× AgGaS2, 89 MW/cm2) and is phase matchable. Based on changes in metal‐sulfur bond lengths and angles, we further propose structural optimization through solid‐solution formation and doping.

La2SiP4 (mP‐28, Z=4, Wyckoff sequence e7, space group P21/c (No. 14), a=10.8230(6) Å, b=7.5208(4) Å, c=7.9189(4) Å, and β=105.389(2)°) which crystallizes in the La2CuS4 structure type is reported. Instead of isolated CuS3 triangles bridged by disulfide anions, in the crystal structure of La2SiP4, one‐dimensional zig‐zag chains composed of SiP4 tetrahedra connected by P−P bonds are present. Lanthanum cations fill the voids between the chains and are coordinated by either 9P or 8P+Si atoms. La2SiP4 is a narrow bandgap semiconductor with calculated and measured optical bandgaps of 0.35 eV and 0.85(1) eV, respectively.

Centrosymmetric skutterudite RhP 3 was converted to a nonsymmorphic and chiral compound RhSi 0.3 P 2.7 (space group P2 1 2 1 2 1 ) by means of partial replacement of Si for P. The structure, determined by a combination of X-ray crystallography and solid state 31 P NMR, exhibits branched polyanionic P/Si chains that are unique among metal phosphides. A driving force to stabilize the locally noncentrosymmetric cis-RhSi 2 P 4 and fac-RhSi 3 P 3 fragments is πelectron back-donation between the Rh t 2g -type orbitals and the unoccupied antibonding Si/P orbitals, which is more effective for Si than for P. In situ studies and total energy calculations revealed the metastable nature of RhSi 0.3 P 2.7 . Electronic structure calculations predicted centrosymmetric cubic RhP 3 to be metallic which was confirmed by transport properties measurements. In contrast, the electronic structure for chiral orthorhombic RhSi 0.3 P 2.7 contained a bandgap, and this compound was shown to be a narrow gap semiconductor.

A facile and universal route for synthesizing transition metal borides has been developed by a reaction of boron triiodide (BI3) with elemental transition metals. This method employs relatively low synthesis...