Binding modes of carboxylate- and acetylacetonate-linked chromophores to homodisperse polyoxotitanate nanoclusters.
The binding of carboxylate- and acetylacetonate-linked chromophores to homodisperse polyoxotitanate nanoclusters with 17 Ti atoms or more are surveyed and found to be limited to chelate-bidentate and the bridging modes, the former being dominant for the acetylacetonate-linked chromophores, the latter for the carboxylate linkers. Chromophores with acetylacetonate linking groups invariably bind in the chelate mode, whereas carboxylic acid terminated chromophores more frequently are observed to have the bridging mode, with the exception of three cases in which a strong electron-donating substituent is present on two different sensitizers. The calculations for isonicotinateand nitrophenylacetylacetonate functionalized Ti17 clusters show the observed binding modes to correspond to the lower energy functionalized clusters, but do not predict the difference between the cinnamic acid and dimethylaminocinnamic acid binding to Ti17, which are bridging and chelate respectively. Both binding modes were never observed to occur for a single chromophore, even when synthetic conditions were varied. Density of state calculations show broadening and splitting of the chromophore LUMO on complexation due to interaction with the cluster's conduction band, as well as frequent penetration of sensitizer orbitals into the bandgap of the functionalized nanoparticle.
Chemistry Department, University at Buffalo, SUNY, Buffalo, New York 14260-3000, USA.
Jesse D
JD
Sokolow
Elzbieta
E
Trzop
Yang
Y
Chen
Jiji
J
Tang
Laura J
LJ
Allen
Robert H
RH
Crabtree
Jason B
JB
Benedict
Philip
P
Coppens