Deconvoluting the atom‐specific electron density within polynuclear systems remains a challenge. A multiple‐wavelength anomalous diffraction study on four clusters that share the same [Co 6 Se 8 ] core was performed. Two cluster types were designed, one having a symmetric ligand sphere and the other having an asymmetric ligand sphere. It was found that in the neutral, asymmetric, CO‐bound cluster, the Co−CO site is more highly oxidized than the other five Co atoms; when an electron is removed, the hole is distributed among the Se atoms. In the neutral, symmetric cluster, the Co atoms divide by electron population into two sets of three, each set being meridional; upon removal of an electron, the hole is distributed among all the Co atoms. This ligand‐dependent tuning of the electron/hole distribution relates directly to the performance of clusters in biological and synthetic systems.
Hernández Sánchez, Raúl, Champsaur, Anouck M., Choi, Bonnie, Wang, Suyin Grass, Bu, Wei, Roy, Xavier, Chen, Yu‐Sheng, Steigerwald, Michael L., Nuckolls, Colin, & Paley, Daniel W. (2018). Electron Cartography in Clusters. Angewandte Chemie (International Edition), 57(42). https://doi.org/10.1002/anie.201806426
@article{osti_1472173,
author = {Hernández Sánchez, Raúl and Champsaur, Anouck M. and Choi, Bonnie and Wang, Suyin Grass and Bu, Wei and Roy, Xavier and Chen, Yu‐Sheng and Steigerwald, Michael L. and Nuckolls, Colin and Paley, Daniel W.},
title = {Electron Cartography in Clusters},
annote = {Abstract Deconvoluting the atom‐specific electron density within polynuclear systems remains a challenge. A multiple‐wavelength anomalous diffraction study on four clusters that share the same [Co 6 Se 8 ] core was performed. Two cluster types were designed, one having a symmetric ligand sphere and the other having an asymmetric ligand sphere. It was found that in the neutral, asymmetric, CO‐bound cluster, the Co−CO site is more highly oxidized than the other five Co atoms; when an electron is removed, the hole is distributed among the Se atoms. In the neutral, symmetric cluster, the Co atoms divide by electron population into two sets of three, each set being meridional; upon removal of an electron, the hole is distributed among all the Co atoms. This ligand‐dependent tuning of the electron/hole distribution relates directly to the performance of clusters in biological and synthetic systems. },
doi = {10.1002/anie.201806426},
url = {https://www.osti.gov/biblio/1472173},
journal = {Angewandte Chemie (International Edition)},
issn = {ISSN 1433-7851},
number = {42},
volume = {57},
place = {Germany},
publisher = {Wiley Blackwell (John Wiley & Sons)},
year = {2018},
month = {09}}
Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 366, Issue 1862https://doi.org/10.1098/rsta.2007.2135