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Bis(triphenylsulfonium) tetrachloridozinc(II), (C18H15S)2[ZnCl4] (I), bis(triphenylsulfonium) tetrachloridocadmium(II), (C18H15S)2[CdCl4] (II), and bis(triphenylsulfonium) tetrachloridomercury(II) methanol monosolvate, (C18H15S)2[HgCl4]·CH3OH (III), each crystallize in the monoclinic space groupP21/n. In all three structures, there are two crystallographically independent triphenylsulfonium (TPS) cations per asymmetric unit, each adopting a distorted trigonal–pyramidal geometry about the S atom (S—C bond lengths in the 1.77–1.80 Å range and C—S—C angles of 100–107°). The [MCl4]2–anions (M= Zn2+, Cd2+, Hg2+) are tetrahedral; their M—Cl bond lengths systematically increase from Zn2+to Hg2+, consistent with the larger ionic radius of the heavier metal. Hirshfeld surface analyses show that H...H and H...C contacts dominate the TPS cation environments, whereas H...Cl and S...Minteractions anchor each [MCl4]2–anion to two surrounding TPS cations. Weak C—H...Cl hydrogen bonds, as well as inversion-centered π–π stacking, generate layers in (I) and (II) and dimeric [(TPS)2–HgCl4]2assemblies in (III).
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Eu(II)‐Based Quaternary Chalcogenides with Noncentrosymmetric Structures Stabilized by Site Disorder of d10 Metal Cations
Quaternary metal‐chalcogenides combining rare‐earth cations with late transition metal cations are attracting growing attention for their optical properties, such as for solar energy conversion or second harmonic generation. Synthetic explorations of theII3‐I2‐IV2‐Ch8family (II = Eu;I = Cu or Ag;IV = Si, Ch = S or Se) have yielded Eu3Ag2Si2S8(1) and Eu3Cu1.08(1)Si2.42(1)Se8(2). Their structures have been characterized by X‐ray diffraction to form in the noncentrosymmetric space groupI3dand to exhibit two distinct types of mixed‐site occupancies, for the Ag(I) cations in1and mixed Cu(I)/Si(IV) cations in2. In both, the cation disorder occurs to achieve charge balancing with the chalcogenide anions. A high yield of1can be achievedwith optical measurements showing indirect and direct band transitions of ≈2.2(1) and ≈2.4(1) eV, respectively. Its second harmonic generation response is found to be relatively strong, approximately 0.9 × AgGaS2, confirming its noncentrosymmetric structure. Band structure calculations reveal the valence and conduction band edges stem predominantly from the filled Ag(I)/Cu(I)‐based states and empty Si(IV)‐based states, respectively, with additional contributions from the chalcogenide anions. Calculation results also show that cation disorder facilitates a reduction in the antibonding interactions between the Ag(I)/Cu(I)d‐based and chalcogenidep‐based states.
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- Award ID(s):
- 2516105
- PAR ID:
- 10615894
- Publisher / Repository:
- Wiley-VCH
- Date Published:
- Journal Name:
- Zeitschrift für anorganische und allgemeine Chemie
- Volume:
- 651
- Issue:
- 9
- ISSN:
- 0044-2313
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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