Metal Chalcogenide Materials: Chalcogenolato complexes as “single‐source” precursors

Abstract

Modern inorganic materials are required to fulfill a range of demands for quality and performance in an increasing number of applications. Single‐source precursor molecules can satisfy many of these requirements. In this review article ligand design (leading, for example, to the dimer shown in the Figure) to address problems associated with gas phase pre‐reactions, thermal stability, ease of handling, toxicity, and purity for II‐VI deposition are discussed.

Influence of the Morphology of Lithiated Copper(I) Sulfides with the Formal Composition “Li2Cu4S3” on Their Stability in Electrochemical Cycling

“…The formation of SR 2 and metal sulfides is a well-established decomposition pathway for group 12 metal thiolates M(SR) 2 (M = Zn, Cd). [20] Under N 2 , thioanisol CH 3 SPh could be identified as an additional side product in the spectra of the cleavage products of both compounds (two times more for 3) and an additional not yet identified aryl compound ( Figures S4 and S5). The formation of thioanisol can only be explained by assuming that dealkylation reactions of the ether molecules occur, which indicates that more complex reactions than suggested by Scheme 2 occur and are also responsible for the formation of residual carbon.…”

Synthesis, Structure and Magnetic Behaviour of Manganese(II) Selenolate Complexes ∞1[Mn(SePh)2], [Mn(SePh)2(bipy)2] and [Mn(SePh)2(phen)2] (bipy = bipyridyl, phen = phenanthroline)

“…Metal chalcogenolato complexes have attracted interest because of their rich structural chemistry, [1][2][3] their potential use as precursors for M/Se materials [4,5] and their relevance as models for active sites of chalcogen-containing metalloproteins. [6,7] Manganese, for example, plays a role as a dopant for 12-16 semiconductor films and nanocrystals, referred to as dilute magnetic semiconductors (DMS), [8,9] as well as in some manganese-oxido cluster complexes such as [Mn 12 O 12 (O 2 CCH 3 ) 16 ] [10] and [Mn 84 O 72 (O 2 CMe) 78 -(OMe) 24 (MeOH) 12 (H 2 O) 42 (OH) 6 ], [11] which are known as single-molecule magnets (SMMs).…”

Trinuclear Early/Late‐Transition‐Metal Thiolate Complexes

“…We decided to use the spin-only value g = 2.00 because the 3 T 1 manifold expected for an ideal tetrahedron is strongly split by the ligand field of 3 into three 3 A 1 states in C 1 symmetry (Tables S17 and S18 in the Supporting Information). For 1, the simulated curves from three-and one-centre spin Hamiltonians with the ab initio calculated parameters are in qualitative agreement with the experimental data.…”

“…The mixed titanium(IV)/copper(I) trinuclear thiolate complexes [Li (15-crown-5) 2 ] were found to display absorption onsets in the near-infrared region at approximately 1350 and 1050 nm, respectively, originated by charge-transfer transitions from copper-based orbitals into titanium-based ones. Heterometallic thiolato complexes that contain vanadium in combination with another transition metal are limited to the trinuclear complexes [V III {M(aet) 3 } 2 ] 3+ (M = Rh III , Ir III ; aet = 2-aminoethanethiolate, en = ethylenediamine), which are bridged by bidentate 2-aminoethanethiolate ligands. [8] In contrast, no examples of heterometallic vanadium/cobalt or vanadium/nickel thiolato complexes were found in the literature.…”

“…In recent years metal-thiolato complexes have attracted interest owing to their rich structural chemistry, [1,2] their potential use as precursors for metal sulfide materials [3] and their relevance as models for active sites of sulfur-containing metalloproteins. [4,5] The combination of an electron-deficient and an electron-rich metal in heterobimetallic complexes offers the possibility of observing new and interesting properties relative to the homometallic complexes.…”