Hg(II) sensing properties of (diphosphine)Pt(dmit) complexes (dmit: C3S52−: 1,3-dithiole-2-thione-4,5-dithiolate)

Jeon, Hyokyung; Suh, Wooyoung; Noh, Dong-Youn

doi:10.1016/j.inoche.2012.07.004

Cited by 15 publications

(10 citation statements)

References 22 publications

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“…Synthesis of (dppe)Pt(dmit). The (dppe)Pt(dmit) complex was prepared using (dppe)PtCl 2 and Na 2 (dmit) according to a previously reported procedure, and its spectroscopic data were in good agreement with the reported values [13].…”

Section: Synthesissupporting

confidence: 69%

“…In supramolecular chemistry, the fluorescent chemosensor is one of the most significant designs because of the possibility of straightforward manipulation of photophysical processes that enables sensitive and selective signaling of targeted ion components [10]. Previously, we have reported a series of studies regarding (diphosphine)Pt(dmit) complexes (dmit: 1,3-dithiole-2-thione-4,5-dithiolate) as cation chemosensors that can be converted to operate via a ratiometric internal charge transfer, especially for Hg 2+ detection [11][12][13]. These complexes created a large pseudo-Stokes shift between the analyte-free and analyte-bound emissive states.…”

Section: Introductionmentioning

confidence: 99%

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Heteroleptic Pt(II)-dithiolene-based Colorimetric Chemosensors: Selectivity Control for Hg(II) Ion Sensing

et al. 2020

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Hg 2+ ions can accumulate in the natural environment and in organisms, where they cause damage to the central nervous system. Therefore, the detection of Hg 2+ ions is essential for monitoring environmental contamination and human health. Herein, we demonstrate a simple method for tuning chemosensor signal ratios that significantly increased chemosensor selectivity for Hg 2+ detection. Selectivity tuning was accomplished for chemosensors of the type (diphosphine)Pt(dmit), bearing the two different terminal groups 1,2-bis(diphenylphosphino)ethane (dppe) and 1,2-bis[bis(pentafluorophenyl)phosphino]ethane) (dfppe) due to the modulation of specific intermolecular interactions between the dmit ligand and Hg 2+ ion. The structure exhibited a large pseudo-Stokes shift, which was advantageous for the internal reference signal and for eliminating potential artifacts. Straightforward chain-end manipulation enabled the tuning of chemosensor properties without additional chemical alterations. Based on these findings, we propose a new platform for improving the selectivity and sensitivity of colorimetric cation sensors. The results of this study will facilitate the designing of organic materials whose certain properties can be enhanced through precise control of the materials' chemical hybridization by simple functional end-group manipulation.

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Section: Synthesissupporting

confidence: 69%

Section: Introductionmentioning

confidence: 99%

Heteroleptic Pt(II)-dithiolene-based Colorimetric Chemosensors: Selectivity Control for Hg(II) Ion Sensing

et al. 2020

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“…Previous published procedure showed the reaction between RN (PPh 2 ) 2 NiCl 2 and in situ formed Na 2 dmit from CH 3 ONa and (PhCO) 2 dmit in absolute methanol and under nitrogen atmosphere [46] only produced low yields of dmit nickel complexes. This study adopted a modified procedure by Jeon et al [49] ;…”

Section: General Featuresmentioning

confidence: 99%

“…[41] In recent years, a considerable amount of interest has been placed on this dmit complexes [41][42][43][44][45][46] and their applications in organic conductors, [41,47,48] chemical sensors, [49,50] magnetic materials, [42,43] and nonlinear optical materials. [44,49,[51][52][53] As an analogous to dmit, the maleonitriledithiolate (mnt 2− ) complexes also attracted some attentions for the prominent biomimetic and redox properties. [54] A homoleptic complex (n-Bu 4 N) [Co (mnt) 2 ] was first reported to have excellent photoand electrocatalytic activities for the reduction of protons to hydrogen.…”

Section: Introductionmentioning

confidence: 99%

Heteroleptic dmit nickel complexes with bis(diphenylphosphanyl)amine ligands as robust molecular electrocatalysts for hydrogen evolution

Xie

Cao

et al. 2020

Applied Organom Chemis

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Four new neutral heteroleptic dmit nickel complexes bearing bis(diphenylphosphanyl)amine ligands, [RN (PPh 2) 2 Ni(dmit)] (where dmit 2− = 1,-3-dithiole-2-thione-4,5-dithiolate; R = (CH 2) 4 CH 3 [1], (CH 2) 3 OCH 3 [2], (CH 2) 2 CH (CH 3) 2 [3], and CHPhCH 3 [4]), have been synthesized in moderated yields by the reactions between (n-Bu) 2 Sn(dmit) and RN (PPh 2) 2 NiCl 2 at room temperature. The complexes were fully characterized by elemental analysis, spectroscopy (Fourier transform infrared [FTIR], ultraviolet-visible [UV-vis], 1 H, 13 C{ 1 H}, and 31 P{ 1 H} nuclear magnetic resonance [NMR]), thermogravimetric analysis, and single crystal X-ray diffraction. In the crystal structures of 1-3 and 4Á2CH 2 Cl 2 , every nickel atom adopts a slightly distorted square-planar coordination by two phosphorus atoms of the RN (PPh 2) 2 ligand and two sulfur atoms of the dmit ligand. Furthermore, the electrochemical behaviors and electrocatalytic activities of 1-4 for hydrogen evolution have also been investigated by the cyclic voltammetry using trifluoroacetic acid (TFA) as the proton source. With the addition of 120-mM trifluoroacetic acid to 0.5-mM 1-4 in MeCN, the turnover frequency values of these catalysts were estimated to be 2827-5149 s −1 , and the relevant overpotentials were 0.72-0.79 V. Density functional theory (DFT) calculations and electrochemical investigations suggest that H 2 production proceeds via a key hydride intermediate [NiH (SH)] with an adjacent protonated sulfur atom of the dmit ligand in which the chelating sulfur atoms serve as proton relays. These findings demonstrate that these heteroleptic dmit nickel complexes could serve as robust and effective molecular electrocatalysts for hydrogen evolution.

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“…[ 7 ] In this regard, the soft S ‐donor containing thione ligands have been proved as excellent soft Lewis bases due to the presence of π‐electrons of the C–S bond and lone‐pair electrons residing on the sulfur center, which in turn makes them an electron‐rich moiety. [ 8 ] This high Hg–S affinity, which is well known as thiophilicity, has been extensively explored to synthesize targeted coordination complexes comprising sulfur donor ligands and their application in various fields, namely, medicine, [ 9 ] waste remediation, [ 10 ] and sensor design. [ 11 ] Unfortunately, the thiophilicity of mercury(II) compounds for sulfur containing amino acid cysteine residues in biosystems lead to the inherent toxicity with mercury(II) and methylmercury(II) cations.…”

Section: Introductionmentioning

confidence: 99%

New mercury(II) halide complexes with neutral ferrocene functionalized thiazolidine‐2‐thiones: Crystallographic and computational analyses

Singh

Kociok‐Köhn

et al. 2021

Applied Organom Chemis

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Three new Hg(II) complexes with general formula [Hg(L)X2]2 (X = Cl (Hg 1), Br (Hg 2), and I (Hg 3)) have been synthesized using the novel ferrocenyl functionalized ligand 3‐ferrocenyl methyl‐thiazolidine‐2‐thione (L). The ligand (L) and the complexes have been characterized by Fourier transform infrared (FTIR), multinuclear nuclear magnetic resonance (NMR), electronic absorption, photoluminescence spectroscopies, and single crystal X‐ray diffraction. The single crystal X‐ray diffraction studies indicated that Hg 1 and Hg 2 are centrosymmetric dimers with distorted tetrahedral geometry around the Hg(II) centers generated by the two bridging halides, a terminal halide, and an exocyclic sulfur of ligand. Hg 3 possess two monomers with trigonal planar geometries around Hg(II), which are further held by weak Hg⋯I interactions. Variation in geometrical parameters have been attributed to differences in the nature of the halide donors attached to the Hg(II). The cyclic voltammetry experiments for all the compounds suggested their quasi‐reversible redox properties. Also, the photoluminescent investigation for Hg 1 and Hg 2 indicated medium strong photoluminescence emission at ~500 nm arising due to metal‐to‐ligand charge‐transfer (MLCT) transitions of the ferrocenyl moiety. The solid‐state structure of complexes are stabilized by varied interactions, namely, C–H⋯C and bifurcated H⋯Cl⋯H interactions in Hg 1, C–H⋯C, C–H⋯S, S⋯C (Cp), and C–H⋯Br interactions in Hg 2 and C–H⋯C, C–H⋯S, and C⋯S interactions in Hg 3. The nature and percentage contribution of all these interactions have been studied by the Hirshfeld surface analyses. The interaction energies for the dimers of all four compounds have been assessed with the help of density functional theory (DFT) and quantum theory of atoms in molecules (QTAIM).

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Hg(II) sensing properties of (diphosphine)Pt(dmit) complexes (dmit: C3S52−: 1,3-dithiole-2-thione-4,5-dithiolate)

Cited by 15 publications

References 22 publications

Heteroleptic Pt(II)-dithiolene-based Colorimetric Chemosensors: Selectivity Control for Hg(II) Ion Sensing

Heteroleptic Pt(II)-dithiolene-based Colorimetric Chemosensors: Selectivity Control for Hg(II) Ion Sensing

Heteroleptic dmit nickel complexes with bis(diphenylphosphanyl)amine ligands as robust molecular electrocatalysts for hydrogen evolution

New mercury(II) halide complexes with neutral ferrocene functionalized thiazolidine‐2‐thiones: Crystallographic and computational analyses

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