1D and 3D Polymeric Manganese(II) Thiolato Complexes: Synthesis, Structure, and Properties of    _∞³[Mn₄(SPh)₈] and _∞¹[Mn(SMes)₂]

Abstract

Reactions of [Mn{N(SiMe)}] with 2.1 equiv of RSH, R = Ph or Mes = CH-2,4,6-(CH), yield compounds of the formal composition "Mn(SR)". Single-crystal X-ray diffraction reveals that [Mn(SMes)] forms one-dimensional chains in the crystal via μ-SMes bridges, whereas [Mn(SPh)] comprises a three-dimensional network in which adamantanoid cages composed of four Mn atoms and six μ-bridging SPh ligands are connected in three dimensions by doubly bridging SPh ligands. Thermogravimetric analysis and powder diffractometry indicate an reversible uptake of solvent molecules (tetrahydrofuran) into the channels of [Mn(SMes)]. Magnetic measurements reveal antiferromagnetic coupling for both compounds with J = -8.2 cm ([Mn(SMes)]) and -10.0 cm ([Mn(SPh)]), respectively. Their optical absorption and photoluminescence (PL) excitation spectra display characteristic d-d bands of Mn ions in the visible spectral region. Both compounds emit bright phosphorescence at ∼800 nm at low temperatures (<100 K). However, only [Mn(SMes)] retains a moderately intense emission at ambient temperature (with a quantum yield of 1.2%). Similar PL properties are also found for the related selenolate complexes [Mn(SeR)] (R = Ph, Mes).

1‐D Polymeric Iron(II) Thiolato Complexes: Synthesis, Structure, and Properties of ∞1[Fe(SR)2] (R = Ph, Mes), ∞1[Fe(NH3)(SPh)(µ‐SPh)] and ∞1[(µ‐SPh)Fe(NH3)2(µ‐SPh)2Fe(µ‐SPh)]

“…Complex 2 displays a broad maximum in the temperature dependence of χ centered around 75 K which is characteristic for strong antiferromagnetic exchange in the chain. A similar behavior has been recently observed for the related chain compounds ∞ 1 [M(SMes) 2 ] (M = Mn,Co) and ∞ 1 [M(SeMes) 2 ] (M = Mn, Fe). The curve has been fitted for the data between 50 and 300 K by both the classical approximation used by Fisher (eqn S1, SI) which is expected to be good for large moments, and the approach of Bonner and Fisher, expanded by Weng,, (eqn S2, SI) which should be more appropriate for smaller, quantum spin systems.…”

“…At temperatures below 70 K the experimental curve deviates from the model in two characteristic ways which have been also observed for the above mentioned related complexes of general formula ∞ 1 [M(EMes) 2 ] (M = Mn, Fe, Co; E = S, Se) , , , . The decrease of χ is more rapid (steep) and there is a second increase of χ at low temperatures.…”

“…Fe–S distances range from 232.91(11) to 234.22(13) pm and the non‐bonding Fe ··· Fe distance was found to be 285.01(3) pm which is smaller than the one found in the folded Fe 2 S 2 units in the ring molecule [{Fe(SEt) 2 } 6 ] ((Fe–S–Fe: 82.55–84.18°, Fe ··· Fe: 290.32–293.55 pm). It should be noted that with respect to the neighboring 3d elements we found that “Mn(SPh) 2 ” instead forms a 3D structure in ∞ 3 [Mn 4 (SPh) 8 ] whereas for “Co(SPh) 2 ” a crystal structure could not be determined so far …”

“…The limited knowledge of the structures of these uncharged polymeric metal chalcogenolates is, in part, due to the relative insolubility of these compounds in inert solvents and the consequent problem of obtaining crystals of diffraction quality . 3D adamantoid network structures have been found some time ago for group 12 metal ions in ∞ 3 [Zn 4 (SPh) 8 CH 3 OH], ∞ 3 [Cd 4 (SR) 8 ] (R = Ph, 4‐CH 3 ‐C 6 H 4 ) and ∞ 3 [Cd 4 (SePh) 8 ] and recently also for manganese in ∞ 3 [Mn 4 (SPh) 8 ] …”

A Novel Manganese Complex with Mixed Ligands: Preparation, Structure, Photoluminescent and Semiconductive Properties

“…[27][28][29][30] Moreover, a great deal of investigations on the photoluminescence of manganese compounds has thus far been performed. [31][32][33] Therefore, to uncover potential photoluminescent behaviour, we conducted photoluminescence measurement of complex 1 with a solid-state sample at room temperature. The results of the photoluminescence experiments are shown in Fig.…”