Metal dithiolene complexes for all‐optical switching devices

Abstract

Optical data storage, transmission, and handling will require a means to carry out all‐optical switching of information if semiconductor‐based electronics are not to become a serious bottle‐neck for the technology. The various materials which aree being examined wiith a view of this application are reviewed are some recent progress made with metal dithiolene complexes (see figure) described.

Neutral d8 metal bis-dithiolene complexes: Synthesis, electronic properties and applications

“…-Previous investigations of the nonlinear optical properties of these complexes have focused on third-order susceptibilities at 1.06 m for applications in all-optical signal processing [26][27][28][29]. For a few complexes, the two-photon absorption at 1.06 m has been measured, since nonlinear absorption is detrimental to alloptical signal processing; low 2PA coefficients were observed [30,31].…”

The Electronic Structure and Spectroscopy of Metallo‐Dithiolene Complexes

“…The electronic structure studies on the [MoO(bdt) 2 ] 1À ion provide a basis for the spectral interpretation of other oxo-molybdenum-bis(dithiolenes), particularly those possessing more elaborated, or highly redox-active dithiolene ligands. The latter dithiolene ligand systems are of particular interest, since the synergistic interactions that can occur between transition metal ions and their redox-active ligands form the basis for a myriad of complex phenomena including facile redox behavior (16,82,281,396), enzymatic catalysis (397,398), novel optical properties (248,399), and valence tautomerism (400)(401)(402)(403)(404). The judicious choice of metal and ligand allows for the occurrence of accessible low-lying electronic states possessing considerable CT character.…”

“…Extensive electronic structure and spectroscopic studies of metallo-bis(dithiolenes) have been undertaken as a result of their potential involvement in electrically conducting (115,116,142,145,146,201,202,270,359,(361)(362)(363) and optoelectronic device technologies (113,119,160,248,(364)(365)(366)(367)(368)(369)(370)(371)(372)(373)(374), as well as their presence in the active sites of certain pyranopterin Mo and pyranopterin W enzymes (11, 13, 17, 19, 27, 28, 36, 45- There have been a considerable number of MO calculations performed on four-coordinate square-planar metallo-bis(dithiolene) complexes at various levels of theory (283,327,328,(379)(380)(381)(382)(383)(384). The most important differences in the results of these various calculations rests in the energy level ordering of the valence MOs as well as the degree of metal-sulfur covalency.…”

A Series of Novel Derivatives with Giant Second Hyperpolarizabilities, Based on Radiaannulenes, Tetrathiafulvalene, Nickel Dithiolene, and Their Lithiated Analogues

“…Previous studies of our group have shown that substitution of the central CC of TTF by Ni has a large effect on the L and NLO properties. , The resulting bis­(ethylene-1,2-dithiolato)­nickel (NiBDT) has many interesting properties (e.g., photochemical and thermal stability, tunable properties), due to which it is considered to be a very promising material. − Several theoretical studies have also shown that lithiation may lead to a significant increase of the second hyperpolarizability. − …”