Inorganic Chemistry

In this work, we illustrated the design and development of a metal-coordinated porous organic polymer ( POP ) namely VO@TPA-POP via a post-synthetic metalation strategy to incorporate oxo-vanadium sites in a pristine polymer ( TPA-POP ) having acetylacetonate (acac) as anchoring moiety. The as-synthesized VO@TPA-POP exhibited highly robust and porous framework, which has been utilized for thioanisole (TA) oxidation to its corresponding sulfoxide. The catalyst demonstrated notable stability and recyclability by maintaining its catalytic activity over multiple reaction cycles without any significant loss in activity...

Exploring materials that balance the second harmonic generation (SHG) effect and laser-induced damage threshold (LIDT) is the frontier of nonlinear optical (NLO) crystal research at present. In this work, the NLO property of anhydrous aluminum iodate is extensively explored and discussed first. It exhibits a strong SHG intensity of 18.3 × KH2 PO4 (KDP) and a high-powder LIDT of 1.4 × KDP at 1064 nm. Combining experimental and theoretical studies at the atomic level and electronic levels, it is found that the cations in the structure are replaced by cations with small radius and high valence, enabling the production of materials with large SHG responses...

Four kinds of polyoxometalate (POM)-viologen compounds were synthesized by hydrothermal method, namely (1-cby)2 ·[H2 (SiMo12 O40 )]·2H2 O ( 1 ), (1-cby)2 ·[H2 (SiW12 O40 )]·2H2 O ( 2 ), (1-cby)2 ·(1,1'-bcby)2 ·{H4 [Co4 (H2 O)2 (PW9 O34 )2 ]}·12H2 O ( 3 ), (1-cby)·(1,1'-bcby)·[H(α-PW11 O39 )CoII (1-cby)]·8H2 O ( 4 ) (1-cby·Br = 1-Cyclopropylmethyl-[4,4']bipyridinyl-1-ium bromide, 1,1'-bcby·Br = 1,1'-Bis-cyclopropylmethyl-[4,4']bipyridinyl-1-ium bromide)...

Developing highly efficient, cost-effective, non-noble-metal-based electrocatalysts with superior performance and stability for oxygen evolution reactions is of immense challenge as well as great importance for the upcoming sustainable and green energy conversion technologies. The multivariate metal-organic frameworks with hierarchical porous structures and unsaturated coordination modes are considered to be promising emerging energy materials. In this work, a series of multimetallic MOFs were directly grown on nickel foam (NF) through the solvothermal method...

In the last 5 years, low-dimensional chiral metal-halide semiconductors have attracted great interest in the generation of chiroptical activity. Among this new family of materials, one-dimensional (1D) networks have appeared as the best candidates for strong circular dichroism (CD) and circularly polarized luminescence (CPL). Here, we present a new family of 1D chiral lead-bromide materials prepared from organic S / R / rac -1-hydroxypropyl-2-ammonium ( S / R / rac -HP2A) cations. The presence or absence of polarity in the crystal structure as well as the perovskite or nonperovskite nature of the inorganic network depends on the initial stoichiometry of metal-halide salt and chiral amine during the crystallization...

Metathesis reactions, including alkane, alkene, and alkyne metatheses, have their origins in the fundamental understanding of chemical reactions and the development of specialized catalysts. These reactions stand as transformative pillars in organic chemistry, providing efficient rearrangement of carbon-carbon bonds and enabling synthetic access to diverse and complex compounds. Their impact spans industries such as petrochemicals, pharmaceuticals, and materials science. In this work, we present a detailed mechanistic study of the Re(V) catalyzed alkyne metathesis through density functional theory calculations...

The synthesis, luminescence, and electrochemical properties of the Ce(III) compound, [(C5 Me5 )2 (2,6-i Pr2 C6 H3 O)Ce(THF)], 1 , were investigated. Based on the electrochemical data, treatment of 1 with CuX (X = Cl, Br, I) results in the formation of the corresponding Ce(IV) complexes, [(C5 Me5 )2 (2,6-i Pr2 C6 H3 O)Ce(X)]. Each complex has been characterized using NMR, IR, and UV-vis spectroscopy as well as structurally determined using X-ray crystallography. Additionally, the treatment of [(C5 Me5 )2 (2,6-i Pr2 C6 H3 O)Ce(Br)] with AgF results in the formation of the putative [(C5 Me5 )2 (2,6-i Pr2 C6 H3 O)Ce(F)]...

The exploration of new rare-earth (RE)-based triangular-lattice materials plays a significant role in motivating the discovery of exotic magnetic states. Herein, we report a family of hexagonal perovskite compounds Ba6 RE2 Ti4 O17 (RE = Nd, Sm, Gd, Dy-Yb) with a space group of P 63 / mmc , where magnetic RE3+ ions are distributed on the parallel triangular-lattice layers within the ab -plane and stacked in an 'AA'-type fashion along the c -axis. The low-temperature magnetic characterizations indicate that all synthesized Ba6 RE2 Ti4 O17 compounds exhibit dominant antiferromagnetic (AFM) interactions and the absence of magnetic order down to 1...

Chiral organic-inorganic metal halides (OIMHs) are attractive for their potential applications in chiral optoelectronics and spintronics, such as circular polarized light emitters, detectors, and chiral-induced spin selectivity. Here, we report three pairs of chiral OIMHs with great water stability constructed from chiral viologens. These OIMHs contain either 1D or 0D structures, however, with small band gaps around 2 eV. Circular dichroism (CD) spectroscopy on transparent thin films of two OIMH pairs showed a wide CD response covering most of the visible light range...

The addition of 2 equiv of the phosphaylide H2 C═PPh3 to the dimethyl uranium metallocene Cp*2 UMe2 (Cp* = η5 -C5 Me5 ) in toluene with gentle heating at 40 °C generates the phosphorano-stabilized bis(carbene) Cp*2 U[C(H)PPh3 ]2 ( 1 ) in good yield. Characterization of 1 by X-ray crystallographic analysis reveals two short uranium-carbon bonds, ranging from 2.301(5) to 2.322(5) Å, consistent with the presence of U═C carbene-type bonds. Monitoring the reaction by NMR spectroscopy suggests that it proceeds through the intermediate formation of the methyl carbene complex Cp*2 U[C(H)PPh3 ](Me) ( 1 Int ); however, prolonged heating of these solutions leads to the ortho -cyclometalated carbene species Cp*2 U{κ2 -[C(H)PPh2 (C6 H4 )]} ( 2 ) via intramolecular C-H activation...

Ruddlesden-Popper oxyfluorides La2 Ni1- x Cu x O3 F2 (0 ≤ x ≤ 1) were obtained by topochemical reaction of oxide precursors La2 Ni1- x Cu x O4 , prepared by citrate-based soft chemistry synthesis, with polyvinylidene fluoride (PVDF) as the fluorine source. Systematic changes of the crystal structure in the oxide as well as the oxyfluoride substitution series were investigated. For 0.2 ≤ x ≤ 0.9, the oxyfluorides adopt the monoclinic ( C 2/ c ) structural distortion previously solved for the x = 0...

The core expansion of metallic or metalloid clusters by the addition of further homo- or heteronuclear vertices is pivotal to the nucleation and growth of particles. The exohedral grafting of a low-valent functionality followed by endohedral incorporation have been identified as key steps. Following previous work on the Si6 series, we now report the synthesis and full characterization of the amidinatotetrylene-functionalized seven-vertex siliconoids Si7 R5 [E(N t Bu)2 CPh] (E = Si, Ge, Sn). In the case of the silylene derivative, the solid-state structure was determined by single crystal X-ray diffraction...

Alkali-metal rare-earth carbonates (ARECs) find great potential in nonlinear optical applications. As the most common method, the hydrothermal reaction is widely used in synthesizing ARECs. The black-box nature of the hydrothermal reaction makes it difficult for understanding the formation processes and therefore may slow down the pace of structural discovery. Here, by simply soaking the rare-earth carbonates in Na2 CO3 solutions, we successfully obtain a series of noncentrosymmetric Na3 RE(CO3 )3 ·6H2 O (RE = Tb 1 , Sm 2 , Eu 3 , Gd 4 , Dy 5 , Ho 6 , and Er 7 ) compounds without using the high-temperature hydrothermal method...

Air-stable dinuclear complexes [(bmsab)NiII (tmsab)NiII (bmsab)]3- and [(bmsab)ZnII (tmsab)ZnII (bmsab)]3- (bmsab = bis(methanesulfoneamido)benzene, tmsab = tetra(methanesulfonamido)benzene) were prepared via a synthetic route based on heteroleptic precursor complexes. The new complexes combine a distorted tetrahedral coordination environment with an open-shell bridging ligand. The ZnII species was subjected to a detailed investigation of the (spectro-)electrochemical processes. The NiII species is a rare example of a complex that combines strong exchange coupling ( J > 440 cm-1 ) with pronounced positive zero-field splitting ( D = +72 cm-1 )...

Laves phases AB 2 form the most abundant group of intermetallic compounds, consisting of combinations of larger electropositive metals A with smaller metals B . Many practical applications of Laves phases depend on the ability to tune their physical properties through appropriate substitution of either the A or B component. Although simple geometrical and electronic factors have long been thought to control the formation of Laves phases, no single factor alone can make predictions accurately. Several machine learning models have been developed to discover new Laves phases, including variations caused by solid solubility, using elemental properties solely on the basis of chemical composition...

In recent years, organometallic complexes have attracted much attention as anticancer therapeutics aiming at overcoming the limitations of platinum drugs that are currently marketed. Still, the development of half-sandwich organometallic cobalt complexes remains scarcely explored. Four new cobalt(III)-cyclopentadienyl complexes containing N,N-heteroaromatic bidentate, and phosphane ligands were synthesized and fully characterized by elemental analysis, spectroscopic techniques, and DFT methods. The cytotoxicity of all complexes was determined in vitro by the MTS assay in colorectal (HCT116), ovarian (A2780), and breast (MDA-MB-231 and MCF-7) human cancer cell lines and in a healthy human cell line (fibroblasts)...

Photoluminescence (PL) spectra arising from 4f-4f dipole transitions of Eu3+ doped at both the A and B sites of perovskite-type alkaline earth zirconates obtained at various excitation wavelengths were evaluated. Changes in the excitation wavelength caused obvious differences in the PL intensity ratio of the induced electric dipole (ED) 5 D0 → 7 F2 transition to the magnetic dipole (MD) 5 D0 → 7 F1 transition for Eu3+ -doped SrZrO3 and CaZrO3 , in which only the B site had a center of symmetry...

The factors affecting the formation and crystal structures of unusual 6d1 Th(III) square planar aryloxide complexes, as exemplified by [Th(OArMe )4 ]1- (OArMe = OC6 H2 t Bu2 -2,6-Me-4), were explored by synthetic and reduction studies of a series of related Th(IV) tetrakis(aryloxide) complexes, Th(OArR )4 (OArR = OC6 H2 t Bu2 -2,6-R-4). Specifically, electronic, steric, and countercation effects were explored by varying the aryloxide ligand, the alkali metal reducing agent, and the alkali metal chelating agent...

In this study, a chiral [Cu(l-proline)2 ] complex-modified Fe3 O4 @SiO2 @UiO-66-NH2 (Zr) metal-organic framework [Fe3 O4 @SiO2 @UiO-66-NH-Cu(l-proline)2 ] via multifunctionalization strategies was designed and synthesized. One simple approach to chiralize an achiral MOF-structure that cannot be directly chiralized using a chiral secondary agent like 4-hydroxy-l-proline. Therefore, this chiral catalyst was synthesized with a simple and multistep method. Accordingly, Fe3 O4 @SiO2 @UiO-66-NH2 has been synthesized via Fe3 O4 modification with tetraethyl orthosilicate and subsequently with ZrCl4 and 2-aminoterephthalic acid...

We report the synthesis and structural characterization of a 2D metal-organic framework with AB-packing layers, [Co2 (pybz)2 (CH3 COO)2 ]·DMF ( Co2 , pybz= 4-(4-pyridyl)benzoate), containing a stable (4,4)-grid network fabricated by paddle-wheel nodes, ditopic pybz, and acetate ligands. After removal of the guest, the layer structure is retained but reorganized into an ABCD packing mode in the activated phase ( Co2a ). Consequently, the intralayer square windows (7.2 × 5.0 Å2 ) close, while the interlayer separation is decreased slightly from 3...