Ortho‐Chalcogenostannates as Ligands: Syntheses, Crystal Structures, Electronic Properties, and Magnetism of Novel Compounds Containing Ternary Anionic Substructures [M₄(μ₄‐Se)(SnSe₄)₄]¹⁰⁻ (M=Mn, Zn, Cd, Hg), ${{{\hfill 3\atop \hfill \infty }}}${[Hg₄(μ₄‐Se)(SnSe₄)₃]⁶⁻}, or ${{{\hfill 1\atop \hfill \infty }}}${[HgSnSe₄]²⁻}

Abstract

By reaction of K4[SnSe4].1.5 MeOH with CdCl2 or Hg(OAc)2 in water/methanol it was possible to prepare single crystals of four novel compounds that contain ternary anionic coordination oligomers and polymers: [K10(H2O)16(MeOH)(0.5)][M4(mu4-Se)(SnSe4)4] (4: M=Cd, 5: M=Hg), [K6(H2O)3][Hg4(mu4-Se)(SnSe4)3].MeOH (6), and K2[HgSnSe4] (7), which were structurally characterized by single-crystal X-ray diffraction. The optical absorption properties of the isostructural compounds 4 and 5, as well as those of the recently reported Zn (2) and Mn (3) analogues, were studied by UV-visible spectroscopy. These investigations showed the quaternary phases to have relatively small optical gaps for their molecular size (2.2-2.6 eV), which are similar to the excitation energies that were observed for mesostructured solids of the respective combination of elements. According to DFT investigations on the ternary anions, an experimentally observed difference between the absorption behavior of the d10 compounds 2, 4, and 5 and the open-shell d(5) compound 3 is in line with different characters of the frontier orbitals in the two cases. Both the calculations and a magnetic measurement on 3 demonstrated antiferromagnetic coupling between the mu(4)-Se-bridged Mn centers.

Solvothermal syntheses of three new one-dimensional ternary selenidostannates: [DBNH][M1/2Sn1/2Se2] (M=Mn, Zn, Hg)

“…In contrast to a great progress have been made in synthesizing 1D binary chalcogenides based on group 13 and 14 metals, 1D heterometallic chalcogenides deserve to pay more attentions due to their potentials in achieving colourful structures [53,54]. Divalent transition metal cations (Mn 2+ , Zn 2+ , Cd 2+ , Hg 2+ ) are usually used to enrich the structures of 1D chain by directly engaging in the construction of inorganic chain [31,[55][56][57][58][59][60][61][62], or chelating with multidentate amines to generate unsaturated transition-metal complexes, which may coordinate with chalcogen atoms of inorganic chain [6,[63][64][65]. On the other hand, hybridize transition metals with group 13 and 14 metals may regulate the chemical and physical properties of 1D chain.…”

Syntheses, Structures, and Comprehensive NMR Spectroscopic Investigations of Hetero‐Chalcogenidometallates: The Right Mix toward Multinary Complexes

“…Many publications describe the influence of elemental substitutions on the optoelectronics of metal chalcogenide clusters or nanoparticles. [5] To perfect the fine-tuning of E g for compounds with P1-type cluster anions, that is, to fill the energetic increment between selenide and telluride compounds, we successfully reacted mixtures of [ 4À (E 1 , E 2 = S, Se, Te) have been generated following different routes that all lead to equilibria of all possible permutations of binary and ternary anions. This has been rationalized by means of NMR studies that can be explained by calculations using density functional theory (DFT) methods.…”

{Sn[Zn4Sn4S17]}6−: A Robust Open Framework Based on Metal‐Linked Penta‐Supertetrahedral [Zn4Sn4S17]10− Clusters with Ion‐Exchange Properties

“…Other frameworks are based on different units that range from simple tetrahedra to so‐called penta‐supertetrahedral clusters denoted as P n 1a. 2a,2b Recently the family of compounds featuring A 10 [M 4 ${{\rm M}{{\prime \hfill \atop 4\hfill}}}$ S 17 ] (A=K, Cs; M=Zn, Cd, Fe, Co; M′=Sn, Ge)4 and A′[Sn 4 ${{\rm M}{{{\rm II}\hfill \atop 4\hfill}}}$ Se 17 ] (A′=[K 10 (H 2 O) 16 (CH 3 OH) 0.5 ], [K 22 (H 2 O) 7 (CH 3 OH) 18 ](SnSe 4 ) 3 ; [K 36 Cl(H 2 O) 11 (CH 3 OH) 32 ]; [K 6 (H 2 O) 3 ]; M II =Co, Zn, Mn, Cd, Hg)5, 6b was shown to have discrete supertetrahedral clusters that belong to the penta‐supertetrahedral series P n 1a. 2a,2b This cluster type is an assembly of four {MQ 4 } (T1) and one {QM 4 } (anti‐T1) structural units, in which M is the metal ion and Q is the chalcogen atom (see Figure 1 a).…”