% IMPORTANT: The following is UTF-8 encoded. This means that in the presence % of non-ASCII characters, it will not work with BibTeX 0.99 or older. % Instead, you should use an up-to-date BibTeX implementation like “bibtex8” or % “biber”. @ARTICLE{Klemeyer:622040, author = {Klemeyer, Lars and Gröne, Tjark L. R. and Zito, Cecilia de Almeida and Vasylieva, Olga and Gumus Akcaalan, Melike and Harouna-Mayer, Sani Y. and Caddeo, Francesco and Steenbock, Torben and Hussak, Sarah-Alexandra and Kesavan, Jagadesh Kopula and Dippel, Ann-Christin and Sun, Xiao and Köppen, Andrea and Saveleva, Viktoriia A. and Kumar, Surender and Bester, Gabriel and Glatzel, Pieter and Koziej, Dorota}, title = {{U}tilizing {H}igh {X}-ray {E}nergy {P}hoton-{I}n {P}hoton-{O}ut {S}pectroscopies and {X}-ray {S}cattering to {E}xperimentally {A}ssess the {E}mergence of {E}lectronic and {A}tomic {S}tructure of {Z}n{S} {N}anorods}, journal = {Journal of the American Chemical Society}, volume = {146}, number = {49}, issn = {0002-7863}, address = {Washington, DC}, publisher = {ACS Publications}, reportid = {PUBDB-2025-00152}, pages = {33475-33484}, year = {2024}, abstract = {The key to controlling the fabrication process of transition metal sulfide nanocrystals is to understand the reaction mechanism, especially the coordination of ligands and solvents during their synthesis. We utilize in situ high-energy resolution fluorescence detected X-ray absorption spectroscopy (HERFD-XAS) as well as in situ valence-to-core X-ray emission spectroscopy (vtc-XES) combined with density functional theory (DFT) calculations to identify the formation of a tetrahedral [Zn(OA)$_4$]$^{2+}$ and an octahedral [Zn(OA)$_6$]$^{2+}$ complex, and the ligand exchange to a tetrahedral [Zn(SOA)$_4$]$^{2+}$ complex (OA = oleylamine, OAS = oleylthioamide), during the synthesis of ZnS nanorods in oleylamine. We observe in situ the transition of the electronic structure of [Zn(SOA)$_4$]$^{2+}$ with a HOMO/LUMO gap of 5.0 eV toward an electronic band gap of 4.3 and 3.8 eV for 1.9 nm large ZnS wurtzite nanospheres and 2 × 7 nm sphalerite nanorods, respectively. Thus, we demonstrate how in situ multimodal X-ray spectroscopy and scattering studies can not only resolve structure, size, and shape during the growth and synthesis of NPs in organic solvents and at high temperature but also give direct information about their electronic structure, which is not readily accessible through other techniques.}, cin = {DOOR ; HAS-User / FS-PETRA-D}, ddc = {540}, cid = {I:(DE-H253)HAS-User-20120731 / I:(DE-H253)FS-PETRA-D-20210408}, pnm = {632 - Materials – Quantum, Complex and Functional Materials (POF4-632) / 6G3 - PETRA III (DESY) (POF4-6G3) / DFG project G:(GEPRIS)390715994 - EXC 2056: CUI: Advanced Imaging of Matter (390715994) / GRK 2536 - GRK 2536: Hybridstrukturen auf der Nanometerskala: Chemische Konzepte zur Herstellung heterogener Nanostrukturen mit anisotropen Materialeigenschaften (NANOHYBRID) (408076438) / LINCHPIN - A platform to LINk between CHemistry and PhysIcs of colloidal Nanomaterials (818941)}, pid = {G:(DE-HGF)POF4-632 / G:(DE-HGF)POF4-6G3 / G:(GEPRIS)390715994 / G:(GEPRIS)408076438 / G:(EU-Grant)818941}, experiment = {EXP:(DE-H253)P-P07-20150101 / EXP:(DE-H253)P-P21.1-20150101 / EXP:(DE-H253)P-P62-20221101}, typ = {PUB:(DE-HGF)16}, pubmed = {pmid:39585247}, UT = {WOS:001362819700001}, doi = {10.1021/jacs.4c10257}, url = {https://bib-pubdb1.desy.de/record/622040}, }