TY - JOUR
T1 - Substitution Effect on the Charge Transfer Processes in Organo-Imido Lindqvist-Polyoxomolybdate
AU - Hermosilla-Ibáñez, Patricio
AU - Wrighton-Araneda, Kerry
AU - Cañón-Mancisidor, Walter
AU - Gutiérrez-Cutiño, Marlen
AU - Paredes-García, Verónica
AU - Venegas-Yazigi, Diego
N1 - Funding Information:
The authors thank ACT-1404 (IPMaG), FONDECYT 1161255 and Financiamiento Basal FB0807 (CEDENNA). Powered@NLHPC: This research was partially supported by the super-computing infrastructure of the National Laboratory for High Performance Computing, NLHPC (ECM-02), CMM, U de Chile. The authors thank CONICYT FONDEQUIP/UHPLC MS/MS EQM 120065. This work was done under the LIA-M3 1027 CNRS Collaborative Program. WCM and DVY thank DICYT, Universidad de Santiago de Chile (USACH) POSTDOC_DICYT, 021640VY_POSTDOC, Vicerrectoria de Investigación, Desarrollo e Innovación.
Publisher Copyright:
© 2018 by the authors. Licensee MDPI, Basel, Switzerland.
PY - 2018/12/22
Y1 - 2018/12/22
N2 - Two new aromatic organo-imido polyoxometalates with an electron donor triazole group ([n-Bu₄N]₂[Mo₆O18NC₆H₄N₃C₂H₂]) (1) and a highly conjugated fluorene ([n-Bu₄N]₂[Mo₆O18NC13H₉]) (2) have been obtained. The electrochemical and spectroscopic properties of several organo-imido systems were studied. These properties were analysed by the theoretical study of the redox potentials and by means of the excitation analysis, in order to understand the effect on the substitution of the organo-imido fragment and the effect of the interaction to a metal centre. Our results show a bathochromic shift related to the charge transfer processes induced by the increase of the conjugated character of the organic fragment. The cathodic shift obtained from the electrochemical studies reflects that the electronic communication and conjugation between the organic and inorganic fragments is the main reason of this phenomenon.
AB - Two new aromatic organo-imido polyoxometalates with an electron donor triazole group ([n-Bu₄N]₂[Mo₆O18NC₆H₄N₃C₂H₂]) (1) and a highly conjugated fluorene ([n-Bu₄N]₂[Mo₆O18NC13H₉]) (2) have been obtained. The electrochemical and spectroscopic properties of several organo-imido systems were studied. These properties were analysed by the theoretical study of the redox potentials and by means of the excitation analysis, in order to understand the effect on the substitution of the organo-imido fragment and the effect of the interaction to a metal centre. Our results show a bathochromic shift related to the charge transfer processes induced by the increase of the conjugated character of the organic fragment. The cathodic shift obtained from the electrochemical studies reflects that the electronic communication and conjugation between the organic and inorganic fragments is the main reason of this phenomenon.
KW - charge transfer
KW - electronic properties
KW - organoimido
KW - polyoxometalate
KW - Rhenium
KW - TD-DFT
UR - http://www.scopus.com/inward/record.url?scp=85058914242&partnerID=8YFLogxK
U2 - 10.3390/molecules24010044
DO - 10.3390/molecules24010044
M3 - Article
C2 - 30583556
AN - SCOPUS:85058914242
SN - 1420-3049
VL - 24
JO - Molecules (Basel, Switzerland)
JF - Molecules (Basel, Switzerland)
IS - 1
M1 - 24010044
ER -