Halide-to-metal charge transfer

In practice linear relationships between with a not far from unity very frequently emerge in diverse systems. Below we illustrate some particularly instructive ones, particularly concerning halide to metal charge-transfer (Imct) which has received less attention, and discuss why this fortunate situation prevails. 

Halide to metal charge transfer (hmet) transitions tend to dominate the uvMsible spectrum in these complexes.. The manifolds are complex at first sight but generally well understood, and historically thay have contributed greatly to our understsnding of bonding in tsuch complexes. One of the themes of this paper is the beauty and informative power of hmet transitions in varied systems. 

In-Plane Halide to Metal Charge Transfer Transitions... 

It is interesting to note that in the Os -n(NH3)n family (X = Cl, Br, 1- n = 2,3,4), where the measured change in the Os couple is of the same order (0.33 V/X-), the halide to metal charge-transfer bands do not shift appreciably as the stoichiometry alters. Clearly, this is well accomodated by our model. Thus, in addition to the familiar effects of the ligands on the metal center, a "ligand field theory for ligands" is required. The present analysis is an early step in the quantification of these terms. 

Molecules in the second coordination sphere, that is, solvent or partners of an ion pair, can transfer charge to the metal ion of a coordination complex in an optically induced electronic transition. The excited states are, respectively, known as solvent to metal charge transfer (SMCT) and ion pair charge transfer (IPCT) excited states. A typical example are the ion pairs, [Cora(NH3)6]3 +, X-, formed between [Coln(NH3)6]3 + and halide and pseudohalide ions X. The UV-Vis spectrum of ion... 

The same coordination geometry was also inferred from the analysis of the lowest energy LMCT bands (see Ligand-to-Metal Charge Transfer) in the far-UV absorption spectra of Zu7- and Cd7-MT, and those of corresponding tetrahedral halide complexes (see Cadmium Inorganic Coordination Chemistry see Zinc Inorganic Coordination Chemistry) Further support came from... 

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