Janus Microspheres for Visual Assessment of Molecular Interconnects

Fliedel, Christophe; Faramarzi, Vina; Rosa, Vítor; Doudin, B.; Braunstein, Pierre

doi:10.1002/chem.201303626

Cited by 17 publications

(34 citation statements)

References 26 publications

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“…For example, the presence of the additional thioether group in the N-substituent could result in (i) intermolecular interactions of interest for electronic communication between metal centers, (ii) the stabilization of catalytically active, electron-deficient species, including through hemilability, 19 and/or in favorable interactions with a cocatalyst, (iii) controlled anchoring of molecules on metal surfaces. 5,20 In this study, we detail the synthesis and characterization of complexes obtained by reaction of ligands 1 and 2 with FeCl 2 and show that, while the structures of the ligands are very similar, their complexes, 3 and 4, respectively, exhibit considerable differences. Although in both cases an unsymmetrical coordination of the phosphorus atoms led to pseudochelation of their respective ligands, 3 is a coordination polymer, whereas 4 is a dinuclear complex.…”

Section: ■ Introductionmentioning

confidence: 99%

Unsymmetrical Chelation of N-Thioether-Functionalized Bis(diphenylphosphino)amine-Type Ligands and Substituent Effects on the Nuclearity of Iron(II) Complexes: Structures, Magnetism, and Bonding

et al. 2015

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Starting from the short-bite ligands N-thioether-functionalized bis(diphenylphosphino)amine-type (Ph2P)2N(CH2)3SMe (1) and (Ph2P)2N(p-C6H4)SMe (2), the Fe(II) complexes [FeCl2(1)]n (3), [FeCl2(2)]2 (4), [Fe(OAc)(1)2]PF6 (5), and [Fe(OAc)(2)2]PF6 (6) were synthesized and characterized by Fourier transform IR, mass spectrometry, elemental analysis, and also by X-ray diffraction for 3, 4, and 6. Complex 3 is a coordination polymer in which 1 acts as a P,P-pseudochelate and a (P,P),S-bridge, whereas 4 has a chlorido-bridged dinuclear structure in which 2 acts only as a P,P-pseudochelate. Since these complexes were obtained under strictly similar synthetic and crystallization conditions, these unexpected differences were ascribed to the different spacer between the nitrogen atom and the −SMe group. In both compounds, one Fe–P bond was found to be unusually long, and a theoretical analysis was performed to unravel the electronic or steric reasons for this difference. Density functional theory calculations were performed for a set of complexes of general formula [FeCl2(SR2){R21PN(R2)P′R23}] (R = H, Me; R1, R2, and R3 = H, Me, Ph), to understand the reasons for the significant deviation of the iron coordination sphere away from tetrahedral as well as from trigonal bipyramidal and the varying degree of unsymmetry of the two Fe–P bonds involving pseudochelating PN(R)P ligands. Electronic factors nicely explain the observed structures, and steric reasons were further ruled out by the structural analysis in the solid-state of the bis-chelated complex 6, which displays usual and equivalent Fe–P bond lengths. Magnetic susceptibility studies were performed to examine how the structural differences between 3 and 4 would affect the interactions between the iron centers, and it was concluded that 3 behaves as an isolated high-spin Fe(II) mononuclear complex, while significant intra- and intermolecular ferromagnetic interactions were evidenced for 4 at low temperatures. Complexes 3 and 4 were also tested in catalytic ethylene oligomerization but did not exhibit any significant activity under the studied conditions.

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Section: ■ Introductionmentioning

confidence: 99%

Unsymmetrical Chelation of N-Thioether-Functionalized Bis(diphenylphosphino)amine-Type Ligands and Substituent Effects on the Nuclearity of Iron(II) Complexes: Structures, Magnetism, and Bonding

et al. 2015

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“…state, 31,32,33,34,35 with a spin-only Landé factor g = 2.147(2), significantly larger than the free-electron value. The latter and the high TIP values are expected because of the mixing of the ground state with the low-lying 4 T 2 state issued from the same 4 F atomic term. 36 For compound 8 (Figure 12), even with a strong TIP contribution of 600⋅10 − 6 cm 3 ⋅mol − 1 , as observed in other salts containing a tetrahedral CoCl 4 2 − anion, 30,36 the χ M T value still increases at high temperatures.…”

Section: Magnetic Measurementsmentioning

confidence: 93%

“…1 The versatility of DPPA-type ligands can be amplified by the introduction of various N-substituents and empowers an extensive number of applications, such as the formation of mono-or polynuclear complexes, 2 or the anchoring of coordination compounds into mesoporous materials 3 or on metallic surfaces. 4 Metal complexes with such short-bite ligands are involved in various catalytic reactions, 5 and their Ni and Cr derivatives have been successfully applied to the catalytic oligo-or polymerization of ethylene. 6,7 The study of the electronic structure of first-row transition metal ions in relation with their stereochemistry is a very relevant field in coordination and biological chemistry and it is essential to analyze how stereochemistry, electronic structure and magnetic properties correlate.…”

Section: Introductionmentioning

confidence: 99%

“…Previous studies have shown i.a. that (i) bis-chelated dicationic Pd(II) complexes with ligands 1 and 2 could be used to assess molecular anchoring on Au(111) surfaces (Janus microspheres), 4 (ii) the N-functionalization influences the behavior of Ni(II) complexes containing such tritopic P,P,S ligands in catalytic ethylene oligomerization, 6a and (iii) that a combination of dicationic Ni(II) complexes containing two chelating ligands 1 or 2, and Zn metal allows the activation of both C sp3 −Cl bonds of CH 2 Cl 2 under mild conditions and affords mixed phosphine, phosphonium ylide species. 10 Further indications that subtle changes in ligand design can strongly affect the nature of the resulting coordination complexes were also provided by the reactions between FeCl 2 and ligand 1 or 2 (1:1 molar ratio) since they led, under strictly similar reaction conditions, to an infinite coordination polymer or a dinuclear complex, respectively.…”

Section: Introductionmentioning

confidence: 99%

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Zwitterionic Cobalt Complexes with Bis(diphenylphosphino)(N-thioether)amine Assembling Ligands: Structural, EPR, Magnetic, and Computational Studies

Fliedel¹,

Rosa²,

Vileno

et al. 2016

Inorg. Chem.

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The coordination of two heterofunctional P,P,S ligands of the N-functionalized DPPA-type bearing an alkylthioether or arylthioether N-substituent, (Ph2P)2N(CH2)3SMe (1) and (Ph2P)2N(p-C6H4)SMe (2), respectively, toward cobalt dichloride was investigated to examine the influence of the linker between the PNP nitrogen and the S atoms. The complexes [CoCl2(1)]2 (3) and [CoCl2(2)]2 (4) have been isolated, and 3 was shown by X-ray diffraction to be a unique dinuclear, zwitterion containing one CoCl moiety bis-chelated by two ligands 1 and one CoCl3 fragment coordinated by the S atom of a thioether function. The FT-IR, UV-vis, and EPR spectroscopic features of 3 were analyzed as the superposition of those of constitutive fragments identified by a retrosynthetic-type analysis. A similar approach provided insight into the nature of 4 for which no X-ray diffraction data could be obtained. A comparison between the spectroscopic features of 4 and of its constitutive fragments, [CoCl(2)2]PF6 (7) and [H2']2[CoCl4] (8) (2' = NH2(p-C6H4)SMe), and between those of 4 and 3 suggested that 4 could either have a zwitterionic structure, similar to that of 3, or contain a tetrahedral dicationic bis-chelated Co center associated with a CoCl4 dianion. Magnetic and EPR studies and theoretical calculations were performed. Doublet spin states were found for the pentacoordinated complexes [CoCl(1)2]PF6 (5) and 7 and anisotropic quadruplet spin states for the tetrahedral complexes [CoCl3(H1')] (6) (1' = NH2(CH2)3SMe) and 8. A very similar behavior was observed for 3 and 4, consisting in the juxtaposition of noninteracting doublet and quadruplet spin states. Antiferromagnetic interactions explain the formation of dimers for 6 and of layers for 8. The EPR signatures of 3 and 4 correspond to the superposition of low-spin nuclei in 5 and 7 and high-spin nuclei in 6 and 8, respectively. From DFT calculations, the solid-state structure of 4 appears best described as zwitterionic, with a low-spin state for the Co1 atom.

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“…The role of thio functionalities in coordination chemistry and its interplay with materials and surface science continues to receive much attention. In particular, ligands augmented with structurally exposed thio substituents are used to generate metal complexes of interest for example catalysis and molecular electronics and spintronics .…”

Section: Introductionmentioning

confidence: 99%

Ion‐Directed Coordinative Polymerization of Copper(II) Pyridyl‐Alcohol Complexes Through Thiane Functionalities

Schmitz

Izarova

Besson

et al. 2019

Zeitschrift anorg allge chemie

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A mononuclear complex [Cu(HL·S)2(NO3)2] (1) and a one‐ dimensional coordination polymer [Cu(HL·S)Cl2]n (2) [HL·S = 4‐(pyridin‐2‐ylmethyl)tetrahydro‐2H‐thiopyran‐4‐ol] showcase the structure‐directing role of the counterions in their formation reaction: monodentate ligation of NO3– and Cl– induces an octahedral (with two HL·S per Cu in 1) or trigonal‐bipyramidal (with one HL·S per Cu in 2) CuII coordination environment. In contrast to 1 exhibiting no coordinative metal–sulfur bonds in the crystal lattice (space group P21/c), 2 (P21/c) features intermolecular Cu–S contacts of 2.3188(7) Å. The coordination compounds are thermally stable up to ca. 160 °C. Whereas 1 demonstrates the spin‐like behavior of an isolated central CuII ion, compound 2 exhibits weak antiferromagnetic intra‐chain coupling with J ≈ –2.1 cm–1 between neighboring CuII ions.

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Janus Microspheres for Visual Assessment of Molecular Interconnects

Cited by 17 publications

References 26 publications

Unsymmetrical Chelation of N-Thioether-Functionalized Bis(diphenylphosphino)amine-Type Ligands and Substituent Effects on the Nuclearity of Iron(II) Complexes: Structures, Magnetism, and Bonding

Unsymmetrical Chelation of N-Thioether-Functionalized Bis(diphenylphosphino)amine-Type Ligands and Substituent Effects on the Nuclearity of Iron(II) Complexes: Structures, Magnetism, and Bonding

Zwitterionic Cobalt Complexes with Bis(diphenylphosphino)(N-thioether)amine Assembling Ligands: Structural, EPR, Magnetic, and Computational Studies

Ion‐Directed Coordinative Polymerization of Copper(II) Pyridyl‐Alcohol Complexes Through Thiane Functionalities

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