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How Does Substitutional Doping Affect Visible Light Absorption in a Series of Homodisperse Ti 11 Polyoxotitanate Nanoparticles?
Author(s) -
Chen Yang,
Jarzembska Katarzy.,
Trzop Elżbieta,
Zhang Lei,
Coppens Philip
Publication year - 2015
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201500961
Subject(s) - doping , affect (linguistics) , nanoparticle , absorption (acoustics) , materials science , series (stratigraphy) , visible spectrum , optics , nanotechnology , analytical chemistry (journal) , optoelectronics , chemistry , physics , psychology , environmental chemistry , composite material , geology , paleontology , communication
Homodisperse doped polyoxotitanate nanoclusters with formulae Ti 11 (MX)O 14 (O i Pr) 17 (M=Mn, Fe or Co; X=Cl, Br or I, O i Pr=isopropoxide) display strongly dopant‐dependent properties. Spectroscopic solution and reflectance measurements backed up by density of states and time‐dependent DFT calculations based on the determined structures, show the prominent effect of FeX substitution by decreasing the HOMO–LUMO gap of the particles. The effect is attributed to the presence of an occupied Fe β orbital halfway up the bandgap, leading to long‐wavelength absorption with electron transfer to the titanium atoms of the cluster. Whereas the light absorption varies significantly with variation of the transition metal dopant, its dependency on the nature of the halogen atom or the change in dipole moment across the series is minor.