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

Bonneval, Bénédicte Garreau-de; Ching, Kathleen Moineau-Chane; Alary, Fabienne; Bui, Thanh‐Tuân; Valade, Lydie

doi:10.1016/j.ccr.2010.02.019

Cited by 147 publications

(81 citation statements)

References 106 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…There is a monotonic increase of γ zzzz (for brevity γ), that is, γ(8) Ͼ γ (7)...γ(1) (Figure 8). This trend is shown by both the gas-phase hyperpolarizability results and those produced by the PCM (solvent: CS 2 ).…”

Section: F First and Second Hyperpolarizabilitiesmentioning

confidence: 99%

See 1 more Smart Citation

Ni Dithiolenes – A Theoretical Study on Structure–Property Relationships

et al. 2013

View full text Add to dashboard Cite

The linear and nonlinear optical (L&NLO) properties, the energy difference between the highest occupied molecular orbital and the lowest unoccupied molecular orbital (HOMO-LUMO gap), the first excitation energy (E exc ), and four indices for the evaluation of the diradical character (DC) of a series of Ni dithiolene derivatives have been computed by employing density functional theory (DFT). The selected DFT functionals provide reliable results for several properties [e.g., excitation energies and (hyper)polarizabilities]. An Atoms in Molecules analysis has been performed and several related properties have been reported (e.g., the average de-[a] Institute

show abstract

Section: F First and Second Hyperpolarizabilitiesmentioning

confidence: 99%

“…[3] Tanaka et al [4] synthesized a three dimensional metallic crystal composed of a single component, Ni(tmdt) 2 (tmdt = trimethylenetetrathiafulvalenedithiolate). [7] Their long ex-localization index, charge density, and its Laplacian). [5] Dithiolene complexes can be used for energy conversion [6] and the development of photodetectors.…”

Section: Introductionmentioning

confidence: 99%

Ni Dithiolenes – A Theoretical Study on Structure–Property Relationships

et al. 2013

View full text Add to dashboard Cite

show abstract

“…1,2‐Dithiolene complexes are of interest for scientists in fields ranging from material science to biochemistry,2, 3 while their physico–chemical properties render them ideal subjects for theoretical investigations 4. As regards linear and nonlinear optical (NLO) properties, as well as magnetism and electrical conductivity, attention has been focused mainly on bis(1,2‐dithiolene) complexes of d 8 metal ions,5 the ligands of which can be considered as being derived from ethylene‐1,2‐dithiolate (H 2 ‐edt 2− ) by replacement of the hydrogen atoms with alkyl or aryl groups. These complexes show a common square‐planar coordination at the metal center,6 peculiar spectroscopic and electrochemical features, such as intense electrochromic visible–near infrared (NIR) absorption,7 and the ability to exist in several well‐defined oxidation states,8 which are generally reversibly accessible by chemical or electrochemical means 9.…”

Section: Introductionmentioning

confidence: 99%

Gold(III) Complexes of Asymmetrically Aryl‐Substituted 1,2‐Dithiolene Ligands Featuring Potential‐Controlled Spectroscopic Properties: An Insight into the Electronic Properties of bis(Pyren‐1‐yl‐ethylene‐1,2‐dithiolato)Gold(III)

Aragoni

Arca

Devillanova

et al. 2010

Chemistry An Asian Journal

View full text Add to dashboard Cite

The electrochemical, UV/Vis-NIR absorption, and emission-spectroscopic features of (TBA(+))(1(-)) and the corresponding neutral complex 1 were investigated (TBA(+)=tetrabutylammonium; 1(-)=[Au(III)(Pyr,H-edt)(2)](-); Pyr,H-edt(2-)=pyren-1-yl-ethylene-1,2-dithiolato). The intense electrochromic NIR absorption (λ(max)=1432 nm; ε=13000 M(-1) cm(-1) in CH(2)Cl(2)) and the potential-controlled visible emission in the range 400-500 nm, the energy of which depends on the charge of the complex, were interpreted on the grounds of time-dependent DFT calculations carried out on the cis and trans isomers of 1, 1(-), and 1(2-). In addition, to evaluate the nonlinear optical properties of 1(x-) (x=0, 1), first static hyperpolarizability values β(tot) were calculated (β(tot)=78×10(-30) and 212×10(-30) esu for the cis isomer of 1(-) and 1, respectively) and compared to those of differently substituted [Au(Ar,H-edt)(2)](x-) gold dithiolenes [Ar=naphth-2-yl (2), phenyl (3); x=0, 1].

show abstract

“…2,11 While both molybdenum and tungsten enzymes contain the dithiolene unit, 2,5 transition metal–bis-dithiolenes, possessing unique optical, conductive, and magnetic properties, have shown promise in the development of optoelectronic devices. 4,7,10 …”

mentioning

confidence: 99%

A Stable Anionic Dithiolene Radical

et al. 2017

View full text Add to dashboard Cite

Sulfurization of anionic N-heterocyclic dicarbene, [:C{[N(2,6-Pri2C6H3)]2CHCLi}]n (2), with elemental sulfur (in a 1:2 ratio) in Et2O at low temperature gives 3 by inserting two sulfur atoms into the Li–C (i.e., C2 and C4) bonds in polymeric 2. Further reaction of 3 with 2 equiv of elemental sulfur in THF affords 4• via unexpected C–H bond activation, which represents the first anionic dithiolene radical to be structurally characterized in the solid state. Alternatively, 4• may also be synthesized directly by reaction of 1 with sulfur (in a 1:4 ratio) in THF. Reaction of 4• with GeCl2·dioxane gives an anionic germanium(IV)–bis(dithiolene) complex (5). The nature of the bonding in 4• and 5 was probed by experimental and theoretical methods.

show abstract

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

Cited by 147 publications

References 106 publications

Ni Dithiolenes – A Theoretical Study on Structure–Property Relationships

Ni Dithiolenes – A Theoretical Study on Structure–Property Relationships

Gold(III) Complexes of Asymmetrically Aryl‐Substituted 1,2‐Dithiolene Ligands Featuring Potential‐Controlled Spectroscopic Properties: An Insight into the Electronic Properties of bis(Pyren‐1‐yl‐ethylene‐1,2‐dithiolato)Gold(III)

A Stable Anionic Dithiolene Radical

Contact Info

Product

Resources

About