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Lone-Pair-Induced Structural Ordering in the Mixed-Valent 0D Metal-Halides Rb₂₃Bi^III _x Sb^III _7-x Sb^V ₂Cl₅₄ (0 ≤ x ≤ 7).

ABSTRACT: Mixed-valent metal-halides containing ns² lone pairs may exhibit intense visible absorption, while zero-dimensional (0D) ns²-based metal-chlorides are generally colorless but have demonstrated promising optoelectronic properties suitable for thermometry and radiation detection. Here, we report solvothermally synthesized mixed-valent 0D metal-halides Rb₂₃Bi^III _x Sb^III _7-x Sb^V ₂Cl₅₄ (0 ≤ x ≤ 7). Rb₂₃Sb^III ₇Sb^V ₂Cl₅₄ crystallizes in an orthorhombic space group (Cmcm) with a unique, layered 0D structure driven by the arrangement of the 5s² lone pairs of the Sb^IIICl₆ octahedra. This red material is likely the true structure of a previously reported monoclinic "Rb_2.67SbCl₆" phase, the structure of which was not determined. Partially or fully substituting Sb^III with isoelectronic Bi^III yields the series Rb₂₃Bi^III _x Sb^III _7-x Sb^V ₂Cl₅₄ (0 < x ≤ 7), which exhibits a similar layered 0D structure but with additional disorder that yields a trigonal crystal system with an enantiomorphic space group (R32). Second harmonic generation of 532 nm light from a 1064 nm laser using Rb₂₃Bi^III ₇Sb^V ₂Cl₅₄ powder confirms the noncentrosymmetry of this space group. As with the prototypical mixed-valent pnictogen halides, the visible absorption bands of the Rb₂₃Bi^III _x Sb^III _7-x Sb^V ₂Cl₅₄ family are the result of intervalent Sb^III-Sb^V and mixed-valent Bi^III-Sb^V charge transfer bands (CTB), with a blueshift of the absorption edge as Bi^III substitution increases. No PL is observed from this family of semiconductors, but a crystal of Rb₂₃Bi^III ₇Sb^V ₂Cl₅₄ exhibits a high resistivity of 1.0 × 10¹⁰ Ω·cm and X-ray photoconductivity with a promising μτ product of 8.0 × 10^-5 cm² s^-1 V^-1. The unique 0D layered structures of the Rb₂₃Bi^III _x Sb^III _7-x Sb^V ₂Cl₅₄ family highlight the versatility of the ns² lone pair in semiconducting metal-halides, pointing the way toward new functional 0D metal-halide compounds.

SUBMITTER: Benin BM

PROVIDER: S-EPMC8043103 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Project description:Studies on molecular co-crystal type materials are important in the design and preparation of easy-to-absorb drugs, non-centrosymmetric, and chiral crystals for optical performance, liquid crystals, or plastic phases. From a fundamental point of view, such studies also provide useful information on various supramolecular synthons and molecular ordering, including metric parameters, molecular matching, energetical hierarchy, and combinatorial potential, appealing to the rational design of functional materials through structure-properties-application schemes. Co-crystal salts involving anionic d-metallate coordination complexes are moderately explored (compared to the generality of co-crystals), and in this context, we present a new series of isomorphous co-crystalline salts (PPh4)3[M(CN)6](H3PG)2·2MeCN (M = Cr, 1; Fe, 2; Co 3; H3PG = phloroglucinol, 1,3,5-trihydroxobenzene). In this study, 1-3 were characterized experimentally using SC XRD, Hirshfeld analysis, ESI-MS spectrometry, vibrational IR and Raman, 57Fe Mössbauer, electronic absorption UV-Vis-NIR, and photoluminescence spectroscopies, and theoretically with density functional theory calculations. The two-dimensional square grid-like hydrogen-bond {[M(CN)6]3-;(H3PG)2}∞ network features original {[M(CN)6]3-;(H3PG)4} supramolecular cis-bis(chelate) motifs involving: (i) two double cyclic hydrogen bond synthons M(-CN⋅⋅⋅HO-)2Ar, {[M(CN)6]3-;H2PGH}, between cis-oriented cyanido ligands of [M(CN)6]3- and resorcinol-like face of H3PG, and (ii) two single hydrogen bonds M-CN⋅⋅⋅HO-Ar, {[M(CN)6]3-;HPGH2}, involving the remaining two cyanide ligands. The occurrence of the above tectonic motif is discussed with regard to the relevant data existing in the CCDC database, including the multisite H-bond binding of [M(CN)6]3- by organic species, mononuclear coordination complexes, and polynuclear complexes. The physicochemical and computational characterization discloses notable spectral modifications under the regime of an extended hydrogen bond network.

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Lone-Pair-Induced Structural Ordering in the Mixed-Valent 0D Metal-Halides Rb₂₃Bi^III _x Sb^III _7-x Sb^V ₂Cl₅₄ (0 ≤ x ≤ 7).

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Lone-Pair-Induced Structural Ordering in the Mixed-Valent 0D Metal-Halides Rb₂₃Bi^III _x Sb^III _7-x Sb^V ₂Cl₅₄ (0 ≤ x ≤ 7).