Non symmetric dithiolenes and dithiolates

Cerrada, Elena; Dı́az, Cristina; Laguna, Mariano; Romeo, Inocencio; Teruel, Helena; Urzay, N.

doi:10.1016/s0379-6779(00)01111-5

Cited by 6 publications

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“…We also intended to use -CN (an electron withdrawing group) as one of the substituents because of their importance of the derivatives as optoelectronic materials. 15 The significance of cyano-substituted dithiolene complexes are evidenced by the fact that a platinum dithiolene complex with cyano substituents gives a χ (3) () third order non linearity) value of 4.2 × 10 -12 esu compared to 1.4 × 10 -13 esu exhibited by a CF 3 analogue. 14 In this context, the synthesis of heteroleptic Ni(II) and Pd(II)dithiolenes with asymmetrically substituted cyanide group has recently been reported.…”

Section: Resultsmentioning

confidence: 99%

“…As shown in Scheme , we have succeeded in preparing a number of dithiolene derivatives with a range of substituents, X = H( 1 ), NO 2 ( 2 ), F( 3 ), Cl( 4 ), and Br( 5 ), leading to compounds 1 − 5 , respectively. We also intended to use −CN (an electron withdrawing group) as one of the substituents because of their importance of the derivatives as optoelectronic materials . The significance of cyano-substituted dithiolene complexes are evidenced by the fact that a platinum dithiolene complex with cyano substituents gives a χ (3) (= third order non linearity) value of 4.2 × 10 −12 esu compared to 1.4 × 10 −13 esu exhibited by a CF 3 analogue .…”

Section: Resultsmentioning

confidence: 99%

“…This can result in a decrease in the width of the absorption band . Laguna and co-workers have chosen an asymmetrically substituted phenyl group on dithiolene-transition metal complexes, in which the phenyl group contains the −CN group as substituent, and studied the resulting optoelectronic properties . Drexhage and co-workers discovered that transition metal dithiolene complexes, especially those of Nickel, are particularly suitable for Q-switching lasers-dyes for Nd:YAG lasers operating at 1064 nm. , The NIR absorption maxima, observed in nickel dithiolenes system, is a function of both extensive electron delocalization within the dithiolene ring system, and the interaction of this delocalized system with available d-orbitals on the central metal .…”

Section: Introductionmentioning

confidence: 99%

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New Series of Asymmetrically Substituted Bis(1,2-dithiolato)-Nickel(III) Complexes Exhibiting Near IR Absorption and Structural Diversity

Madhu

Das

2008

Inorg. Chem.

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The synthesis, structural characterization, and properties of a new series of asymmetrically substituted bis(dithiolene) nickel(III) compounds [Bu4N][Ni(Phdt)2] (1) (Phdt = 2-Phenyl-1,2-dithiolate), [Bu4N][Ni(NO2Phdt)2] (2) (NO2Phdt = 2-( p-nitrophenyl)-1,2-dithiolate), [Bu4N][Ni(FPhdt)2] (3) (FPhdt = 2-( p-fluorophenyl)-1,2-dithiolate), [Bu4N][Ni(ClPhdt)2] (4) (ClPhdt = 2-( p-chlorophenyl)-1,2-dithiolate), and [Bu4N][Ni(BrPhdt)2] (5) (BrPhdt = 2-( p-bromophenyl)-1,2-dithiolate) have been described. All complexes 1- 5 exhibit absorptions in the near-infrared region; the shift of these absorption bands can be tuned by the choice of the substituents on the relevant dithiolene moieties. The substituents on the dithiolene moiety are also responsible for their structural diversities. The nature of the substituents on the dithiolene moiety play an important role in tuning the redox potentials along this series. The nitro derivative (compound 2) exhibits several redox couples in its cyclic voltammogram in contrast to the other compounds in this series. The synthesis and characterization of two asymmetrically halogen substituted tetrathiafulvalene (TTF) derivatives 4,4'-bis(4-chlorophenyl)-tetrathiafulvalene ClPhTTF (6) and 4,4'-bis(4-bromophenyl)-tetrathiafulvalene (BrPhTTF) (7) have been described. One of these compounds has been structurally characterized. Iodine treatment of the monoanionic Ni(III) compound [Bu4N][Ni(ClPhdt)2] (4) results in the formation of a neutral Ni(IV) complex [Ni(ClPhdt)2] (8). All monoanionic compounds 1- 5 are Ni(III) complexes, as evidenced by electron spin resonance spectroscopy. Interestingly, strong Cl...Cl interactions are observed in the solid state structures of the chlorinated compounds 6 and 8. Finally, the structural features of compound [Ni(ClPhdt)2] (8) and the TTF derivative ClPhTTF (6) are compared based on their enormous structural similarities, and the neutral compound [Ni(ClPhdt)2] (8) is classed as the "an inorganic counterpart of TTF".

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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New Series of Asymmetrically Substituted Bis(1,2-dithiolato)-Nickel(III) Complexes Exhibiting Near IR Absorption and Structural Diversity

Madhu

Das

2008

Inorg. Chem.

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“…Impelled by the low‐energy electronic NIR absorption of neutral gold complexes15–17 and by the capability of asymmetrically substituted 1,2‐dithiolene ligands to form noncentrosymmetric complexes capable to exhibit second‐order nonlinear optical (NLO) properties,18–20 we turned to investigate the possibility of attaching a single fluorogenic substituent to each 1,2‐dithiolene ligand so as to include in a single molecular compound the peculiar properties of the luminescent substituents along with the linear and NLO properties of the dithiolene core. In this paper, we report on the synthesis of bis(1,2‐dithiolene) complexes that belong to the general class [Au(Ar,H‐edt) 2 ] x − (Ar,H‐edt 2 − =arylethylene‐1,2‐dithiolato; x =0, 1, 2) and feature phenyl, 2‐naphtyl, and 1‐pyrenyl luminescent substituents (Ar=Ph ( 1 x − ), Naph ( 2 x − ), and Pyr ( 3 x − ), respectively; Scheme ).…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Characterization of Novel Gold(III) Complexes of Asymmetrically Aryl‐Substituted 1,2‐Dithiolene Ligands Featuring Potential‐Controlled Spectroscopic Properties

Ambrosio

Aragoni

Arca

et al. 2010

Chemistry An Asian Journal

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The tetrabutylammonium (TBA(+)) salts of square-planar monoanionic gold complexes of the unsymmetrically substituted Ar,H-edt(2-) 1,2-dithiolene ligands (Ar,H-edt(2-)=arylethylene-1,2-dithiolato; Ar=phenyl (1(-)), 2-naphthyl (2(-)), and 1-pyrenyl (3(-))) were synthesized and characterized by spectroscopic and electrochemical methods and the corresponding neutral species (1, 2, and 3, respectively) were obtained in CH(2)Cl(2) solution at room temperature by diiodine oxidation. The single-crystal X-ray diffraction structural data collected for (TBA(+))(2(-)), supported by DFT theoretical calculations, are consistent with the ene-1,2-dithiolate form of the ligand and the Au(III) oxidation state. All complexes feature intense near-IR absorptions (at about 1.5 microm) in their neutral states and Vis-emitting properties in the 400-550 nm range, the energy of which is controlled by the charge of the complex in the case of the 3(-)/3 couple. The spectroscopic and electrochemical features of 1(x-) and 2(x-) (x=0, 1), both in their cis and trans conformations, were investigated by means of DFT and time-dependent (TD) DFT calculations.

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“…These materials are successfully used in various applications, like catalysis [20], various types of sensors [21,22], electrochromism [23,24], electric [25], and optoelectronic [26] applications. Owing to the high prospective of the porous nickel and cobalt oxides, we tried to prepare them sonochemically, from alkoxide precursors [27].…”

Section: Introductionmentioning

confidence: 99%

Preparation of stable porous nickel and cobalt oxides using simple inorganic precursor, instead of alkoxides, by a sonochemical technique

Srivastava

Pol

Palchik

et al. 2005

Ultrasonics Sonochemistry

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Porous nickel and cobalt oxides were prepared using NiSO4.6H2O and anhydrous Co(CH3COO)2, a precursor other than alkoxides and cetyltrimethylammonium bromide as organic surfactant. The sonication method has been used for such synthesis. The surfactants were removed by calcination, as well as by solvent extraction and it is extent was examined by IR spectroscopy. The trend of removal of surfactant was followed by TGA studies and the change in phases by DSC. The products were identified by XRD. Peak in low angle XRD indicates the porous nature of the oxides. The morphology of the pores was studied by transmission electron microscopy. The pores were found less ordered, having an average size of 4-6 nm. The Brunauer-Emmet-Teller surface areas of the as-prepared, as well as the treated samples are reported having H2 and H4 type hysteresis for Ni and Co, respectively.

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Non symmetric dithiolenes and dithiolates

Cited by 6 publications

References 0 publications

New Series of Asymmetrically Substituted Bis(1,2-dithiolato)-Nickel(III) Complexes Exhibiting Near IR Absorption and Structural Diversity

New Series of Asymmetrically Substituted Bis(1,2-dithiolato)-Nickel(III) Complexes Exhibiting Near IR Absorption and Structural Diversity

Synthesis and Characterization of Novel Gold(III) Complexes of Asymmetrically Aryl‐Substituted 1,2‐Dithiolene Ligands Featuring Potential‐Controlled Spectroscopic Properties

Preparation of stable porous nickel and cobalt oxides using simple inorganic precursor, instead of alkoxides, by a sonochemical technique

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