Role played by the organometallic fragment on the first hyperpolarizability of iron–acetylide complexes: A TD-DFT study

Mendes, Paulo J.; Carvalho, A.J. Palace; Ramalho, J. P. Prates

doi:10.1016/j.theochem.2008.12.037

Cited by 19 publications

(17 citation statements)

References 40 publications

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“…The total static (i.e., under zero frequency) 108 second-order (quadratic) hyperpolarizability (the first hyperpolarizability) 109 β tot was calculated as previously described. 110 …”

Section: Methodsmentioning

confidence: 99%

“…The total static (i.e., under zero frequency) 108 second-order (quadratic) hyperpolarizability (the first hyperpolarizability) 109 β tot was calculated as previously described. 110 Throughout all this work, molecules in their optimized standard orientation were rotated in order to align the main symmetry axis (bisecting C−C 1,2-dithiolene bonds and passing through the central metal ion) with the z axis and lie on the yz plane. Molden 6.2 111 and GaussView 6.0.16 112 were used to analyze Kohn−Sham (KS) molecular orbital (MO) compositions and energies.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

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Diradical Character of Neutral Heteroleptic Bis(1,2-dithiolene) Metal Complexes: Case Study of [Pd(Me₂timdt)(mnt)] (Me₂timdt = 1,3-Dimethyl-2,4,5-trithioxoimidazolidine; mnt^2– = 1,2-Dicyano-1,2-ethylenedithiolate)

et al. 2020

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The reaction of the bis(1,2-dithiolene) complex [Pd(Me2timdt)2] (1; Me2timdt•– = monoreduced 1,3-dimethyl-2,4,5-trithioxoimidazolidine) with Br2 yielded the complex [Pd(Me2timdt)Br2] (2), which was reacted with Na2mnt (mnt2– = 1,2-dicyano-1,2-ethylenedithiolate) to give the neutral mixed-ligand complex [Pd(Me2timdt)(mnt)] (3). Complex 3 shows an intense solvatochromic near-infrared (NIR) absorption band falling between 955 nm in DMF and 1060 nm in CHCl3 (ε = 10700 M–1 cm–1 in CHCl3). DFT calculations were used to elucidate the electronic structure of complex 3 and to compare it with those of the corresponding homoleptic complexes 1 and [Pd(mnt)2] (4). An in-depth comparison of calculated and experimental structural and vis–NIR spectroscopic properties, supported by IEF-PCM TD-DFT and NBO calculations, clearly points to a description of 3 as a dithione-dithiolato complex. For the first time, a broken-symmetry (BS) procedure for the evaluation of the singlet diradical character (DC) of heteroleptic bis(1,2-dithiolene) complexes has been developed and applied to complex 3. The DC, predominant for 1 (n D C = 55.4%), provides a remarkable contribution to the electronic structures of the ground states of both 3 and 4, showing a diradicaloid nature (n D C = 24.9% and 27.5%, respectively). The computational approach developed here clearly shows that a rational design of the DC of bis(1,2-ditiolene) metal complexes, and hence their linear and nonlinear optical properties, can be achieved by a proper choice of the 1,2-dithiolene ligands based on their electronic structure.

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“…The total static (i.e., under zero frequency) 108 second-order (quadratic) hyperpolarizability (the first hyperpolarizability) 109 β tot was calculated as previously described. 110 …”

Section: Methodsmentioning

confidence: 99%

Section: ■ Experimental Sectionmentioning

confidence: 99%

Diradical Character of Neutral Heteroleptic Bis(1,2-dithiolene) Metal Complexes: Case Study of [Pd(Me₂timdt)(mnt)] (Me₂timdt = 1,3-Dimethyl-2,4,5-trithioxoimidazolidine; mnt^2– = 1,2-Dicyano-1,2-ethylenedithiolate)

et al. 2020

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“…In recent years, with the rapid growth of computer power as well as efficient algorithms, NLO calculations have been performed using ab initio methods coupled with derivative methods (discussed later), in particular density functional theory (DFT) [81][82][83][84][85][86]. A detailed discussion of quantum chemical NLO calculations with reference to the metal alkynyl complexes is given in a later section.…”

Section: Sum-over-states (Sos) Methodsmentioning

confidence: 99%

Computational studies of the nonlinear optical properties of organometallic complexes

Kodikara

Stranger

Humphrey

2018

Coordination Chemistry Reviews

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“…In order to determine the influence of the solvent on the properties of the complexes, solvation calculations were also carried out in dmso, implicitly taken into account by means of the polarizable continuum model (PCM) in its integral equation formalism variant (IEF‐PCM) 62. The total static second‐order (quadratic) hyperpolarizability (the first hyperpolarizability)63 β tot was calculated as described previously 31,64. The programs GaussView 5.0.8,65 and Molden 5.466 were used to investigate the charge distributions and molecular orbital shapes.…”

Section: Methodsmentioning

confidence: 99%

On the Role of Chalcogen Donor Atoms in Diimine‐Dichalcogenolate Pt^II SONLO Chromophores: Is It Worth Replacing Sulfur with Selenium?

et al. 2015

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Two new diimine‐diselenolate PtII chromophores [Pt(bipy)(Me‐dset)] (1) and [Pt(phen)(Me‐dset)] (2) (Me‐dset2– = N‐methyl‐2‐thioxothiazoline‐4,5‐diselenolate) were synthesized and characterized. The effect of replacing sulfur with selenium was investigated by comparing the UV/Vis spectroscopic and electrochemical properties of 1 and 2 with those of the corresponding sulfur analogues, [Pt(bipy)(Me‐dmet)] (3) and [Pt(phen)(Me‐dmet)] (4), with a particular focus on their linear and nonlinear optical properties.

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Role played by the organometallic fragment on the first hyperpolarizability of iron–acetylide complexes: A TD-DFT study

Cited by 19 publications

References 40 publications

Diradical Character of Neutral Heteroleptic Bis(1,2-dithiolene) Metal Complexes: Case Study of [Pd(Me₂timdt)(mnt)] (Me₂timdt = 1,3-Dimethyl-2,4,5-trithioxoimidazolidine; mnt^2– = 1,2-Dicyano-1,2-ethylenedithiolate)

Diradical Character of Neutral Heteroleptic Bis(1,2-dithiolene) Metal Complexes: Case Study of [Pd(Me₂timdt)(mnt)] (Me₂timdt = 1,3-Dimethyl-2,4,5-trithioxoimidazolidine; mnt^2– = 1,2-Dicyano-1,2-ethylenedithiolate)

Computational studies of the nonlinear optical properties of organometallic complexes

On the Role of Chalcogen Donor Atoms in Diimine‐Dichalcogenolate Pt^II SONLO Chromophores: Is It Worth Replacing Sulfur with Selenium?

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Role played by the organometallic fragment on the first hyperpolarizability of iron–acetylide complexes: A TD-DFT study

Cited by 19 publications

References 40 publications

Diradical Character of Neutral Heteroleptic Bis(1,2-dithiolene) Metal Complexes: Case Study of [Pd(Me2timdt)(mnt)] (Me2timdt = 1,3-Dimethyl-2,4,5-trithioxoimidazolidine; mnt2– = 1,2-Dicyano-1,2-ethylenedithiolate)

Diradical Character of Neutral Heteroleptic Bis(1,2-dithiolene) Metal Complexes: Case Study of [Pd(Me2timdt)(mnt)] (Me2timdt = 1,3-Dimethyl-2,4,5-trithioxoimidazolidine; mnt2– = 1,2-Dicyano-1,2-ethylenedithiolate)

Computational studies of the nonlinear optical properties of organometallic complexes

On the Role of Chalcogen Donor Atoms in Diimine‐Dichalcogenolate PtII SONLO Chromophores: Is It Worth Replacing Sulfur with Selenium?

Contact Info

Product

Resources

About

Diradical Character of Neutral Heteroleptic Bis(1,2-dithiolene) Metal Complexes: Case Study of [Pd(Me₂timdt)(mnt)] (Me₂timdt = 1,3-Dimethyl-2,4,5-trithioxoimidazolidine; mnt^2– = 1,2-Dicyano-1,2-ethylenedithiolate)

Diradical Character of Neutral Heteroleptic Bis(1,2-dithiolene) Metal Complexes: Case Study of [Pd(Me₂timdt)(mnt)] (Me₂timdt = 1,3-Dimethyl-2,4,5-trithioxoimidazolidine; mnt^2– = 1,2-Dicyano-1,2-ethylenedithiolate)

On the Role of Chalcogen Donor Atoms in Diimine‐Dichalcogenolate Pt^II SONLO Chromophores: Is It Worth Replacing Sulfur with Selenium?