Molecular Chalcogenide Complexes of Aluminium, Indium and Antimony and their Conversion into Nanostructured Metal Chalcogenides

This PhD thesis describes the synthesis of novel molecular chalcogenide complexes of Al, In and Sb and their subsequent conversion into binary metal chalcogenides via chemical vapor deposition or microwave assisted synthesis. Firstly, two novel aluminum hydrido enaminonate complexes were synthesized through the reaction of AlH3 with an enaminone ligand in varying molar ratios to produce mono- and di-hydrido-aluminum enaminonates. The monohydride [Al(H)(TFB-TBA)2] displayed a monomeric 5-coordinated Al(III) center with two chelating enaminone units and a terminal hydride ligand. On the other hand, the dihydrido compound underwent rapid C-H bond activation and C-C bond formation, resulting in the formation of [Al(H)(TFB-TBA)]2. Secondly, N-Methyldiethanthiolamine ligand [(HSC2H4)2MeN] was employed to synthesize aluminium thiolate hydride [Al(H){(SC2H4)2MeN)}(THF)]. Moreover, three new heteroleptic indium aminothiolates [InCl({SC2H4}2NMe)]3, [In(PhS)({SC2H4}2NMe)]2 and [In({SC2H4}2NMe)(PyCHC(CF3)O)] were synthesized by in situ salt metathesis reaction involving indium trichloride, [(HSC2H4)2MeN] and H-PyCH=COCF3 ligands. The chemical vapor deposition of [In({SC2H4}2NMe)(PyCHC(CF3)O)] as precursor was conducted on FTO substrate to produce singular-phase In2S3 deposits. Furthermore, the electronic structure of [In({SC2H4}2NMe)(PyCHC(CF3)O)] was investigated through DFT calculations. As a result, MoS2 was deposited onto the In2S3 layer using MoO3 and S as precursors in a hot wall CVD process and was confirmed by X-ray diffraction and Raman spectroscopy results. However, MoS2@In2S3 heterostructures underwent noticeable conversion to MoO3 as indicated by Raman studies. Finally, new antimony thiolates [SbCl({SC2H4}2NMe)] and [Sb(PhS)({SC2H4}2NMe)] were synthesized. Their structural elucidation revealed their monomeric structure, unlike the indium thiolates. The subsequent transformation of [Sb(PhS)({SC2H4}2NMe)] into Sb2S3 by microwave assisted process was also confirmed.