%0 Generic
%A Nawn, Graeme
%A McDonald, Robert
%A Hicks, Robin G.
%D 2016
%T Synthesis
and Characterization of Heterobimetallic (Pd/B) Nindigo Complexes
and Comparisons to Their Homobimetallic (Pd2, B2) Analogues
%U https://acs.figshare.com/articles/dataset/Synthesis_and_Characterization_of_Heterobimetallic_Pd_B_Nindigo_Complexes_and_Comparisons_to_Their_Homobimetallic_Pd_sub_2_sub_B_sub_2_sub_Analogues/2369149
%R 10.1021/ic400911k.s002
%2 https://acs.figshare.com/ndownloader/files/4008646
%K BF
%K LUMO
%K IR
%K cyclic voltammetry experiments
%K Pd 2 complexes
%K Nindigo ligand
%K HOMO
%X Reactions of Nindigo-BF2 complexes with Pd(hfac)2 produced mixed complexes with
Nindigo binding to both a BF2 and a Pd(hfac) unit. These
complexes are the first in which the Nindigo ligand binds two different
substrates, and provide a conceptual link between previously reported
bis(BF2) and bis(Pd(hfac)) complexes. The new Pd/B complexes
have intense near IR absorption near 820 nm, and they undergo multiple
reversible oxidations and reductions as probed by cyclic voltammetry
experiments. The spectral, redox, and structural properties of these
complexes are compared against those of the corresponding B2 and Pd2 complexes with the aid of time-dependent density
functional calculations. In all cases the low-energy electronic transitions
are ligand-centered π–π* transitions, but the highest
occupied molecular orbital (HOMO) and lowest unoccupied molecular
orbital (LUMO) energiesand hence the absorption wavelength
as well as the oxidation and reduction potentialsare significantly
modulated by the moieties bound to the Nindigo ligand.
%I ACS Publications