Negative Ion Photoelectron Spectroscopy Reveals Remarkable Noninnocence of Ligands in Nickel Bis(dithiolene) Complexes [Ni(dddt)2](-) and [Ni(edo)2](-).
[Ni(dddt)2](-) (dddt = 5,6-dihydro-1,4-dithiine-2,3-dithiolate) and [Ni(edo)2](-) (edo = 5,6-dihydro-1,4-dioxine-2,3-dithiolate) are two donor-type nickel bis(dithiolene) complexes, with the tendency of donating low binding energy electrons. These two structurally similar complexes differ only with respect to the outer atoms in the ligand framework where the former has four S atoms while the latter has four O atoms. Herein, we report a negative ion photoelectron spectroscopy (NIPES) study on these two complexes to probe the electronic structures of the anions and their corresponding neutrals. The NIPE spectra exhibit the adiabatic electron detachment energy (ADE) or, equivalently, the electron affinity (EA) of the neutral [Ni(L)2](0) to be relatively low for this type of complexes, 2.780 and 2.375 eV for L = dddt and edo, respectively. The 0.4 eV difference in ADEs shows a significant substitution effect for sulfur in dddt by oxygen in edo, i.e., noninnocence of the ligands, which has decreased the electronic stability of [Ni(edo)2](-) by lowering its electron binding energy by ∼0.4 eV. The observed substitution effect on gas-phase EA values correlates well with the measured redox potentials for [Ni(dddt)2](-/0) and [Ni(edo)2](-/0) in solutions. The singlet-triplet splitting (ΔEST) of [Ni(dddt)2](0) and [Ni(edo)2](0) is also determined from the spectra to be 0.57 and 0.53 eV, respectively. Accompanying DFT calculations and molecular orbital (MO) composition analyses show significant ligand contributions to the redox MOs and allow the components of the orbitals involved in each electronic transition and spectral assignments to be identified.
College of Chemistry and Chemical Engineering, Southwest University , Chongqing 400715, China.|Department of Chemistry, Tongji University , Shanghai 200092, China.
Xing
X
Liu
Physical Sciences Division, Pacific Northwest National Laboratory , P.O. Box 999, MS K8-88, Richland, Washington 99352, United States.
Gao-Lei
GL
Hou
Department of Chemistry, Tongji University , Shanghai 200092, China.
Xuefeng
X
Wang
Physical Sciences Division, Pacific Northwest National Laboratory , P.O. Box 999, MS K8-88, Richland, Washington 99352, United States.
Xue-Bin
XB
Wang