Non-innocent behaviour in mononuclear and polynuclear complexes: consequences for redox and electronic spectroscopic properties

Ward, Michael D.; McCleverty, Jon A.

doi:10.1039/b110131p

Cited by 403 publications

(297 citation statements)

References 61 publications

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“…Figure 2). The spin-density in trans-[1] Figure 4) is evenly distributed over the molecular backbone with both the bridging ligand (C≡C / C 6 H 4 / C≡C 19 % / 18 % / 19 %) and the metal centers, Ru(dppe)Cp*, (21 % / 21 %) contributing significantly (the large involvement of the bridge atoms in carrying the spin-density supports redox non-innocent description of this ligand in such delocalized arrangements [48,49] ). This solution corresponds to lowest-energy states calculated previously for [1] + and analogues.…”

Section: Analysis Of [1]mentioning

confidence: 99%

Mixed‐Valence Ruthenium Complexes Rotating through a Conformational Robin–Day Continuum

Parthey

Gluyas

Fox

et al. 2014

Chemistry A European J

107

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Section: Analysis Of [1]mentioning

confidence: 99%

Mixed‐Valence Ruthenium Complexes Rotating through a Conformational Robin–Day Continuum

Parthey

Gluyas

Fox

et al. 2014

Chemistry A European J

107

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“…Anilates in fact are very challenging building blocks because of: (i) their interesting redox properties [70]; (ii) their ability to mediate magnetic superexchange interactions when the ligand coordinates two metals ions in the 1,2-bis-bidentate coordination mode; (iii) the possibility of modulating the strength of this magnetic superexchange interaction by varying the substituents (X) on the 3,6 position of the anilato-ring [71]; moreover the presence of different It is noteworthy that among the described coordination modes, I and II are the most common, whereas III, IV and V have been only rarely observed.…”

Section: Substituentmentioning

confidence: 99%

“…Anilates in fact are very challenging building blocks because of: (i) their interesting redox properties [70]; (ii) their ability to mediate magnetic superexchange interactions when the ligand coordinates two metals ions in the 1,2-bis-bidentate coordination mode; (iii) the possibility of modulating the strength of this magnetic superexchange interaction by varying the substituents (X) on the 3,6 position of the anilato-ring [71]; moreover the presence of different substituents in the anilato moiety give rise to intermolecular interactions such as H-Bonding, Halogen-Bonding, π-π stacking and dipolar interactions which may influence the physical properties of the resulting material. Therefore, these features provide an effective tool for engineering a great variety of new materials with unique physical properties.…”

Section: Substituentmentioning

confidence: 99%

Recent Advances on Anilato-Based Molecular Materials with Magnetic and/or Conducting Properties

et al. 2017

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Abstract:The aim of the present work is to highlight the unique role of anilato-ligands, derivatives of the 2,5-dioxy-1,4-benzoquinone framework containing various substituents at the 3 and 6 positions (X = H, Cl, Br, I, CN, etc.), in engineering a great variety of new materials showing peculiar magnetic and/or conducting properties. Homoleptic anilato-based molecular building blocks and related materials will be discussed. Selected examples of such materials, spanning from graphene-related layered magnetic materials to intercalated supramolecular arrays, ferromagnetic 3D monometallic lanthanoid assemblies, multifunctional materials with coexistence of magnetic/conducting properties and/or chirality and multifunctional metal-organic frameworks (MOFs) will be discussed herein. The influence of (i) the electronic nature of the X substituents and (ii) intermolecular interactions i.e., H-Bonding, Halogen-Bonding, π-π stacking and dipolar interactions, on the physical properties of the resulting material will be also highlighted. A combined structural/physical properties analysis will be reported to provide an effective tool for designing novel anilate-based supramolecular architectures showing improved and/or novel physical properties. The role of the molecular approach in this context is pointed out as well, since it enables the chemical design of the molecular building blocks being suitable for self-assembly to form supramolecular structures with the desired interactions and physical properties.Keywords: benzoquinone derivatives; molecular magnetism; multifunctional molecular materials; spin-crossover materials; metal-organic frameworks General IntroductionThe aim of the present work is to highlight the key role of anilates in engineering new materials with new or improved magnetic and/or conducting properties and new technological applications. Only homoleptic anilato-based molecular building blocks and related materials will be discussed. Selected examples of para-/ferri-/ferro-magnetic, spin-crossover and conducting/magnetic multifunctional materials and MOFs based on transition metal complexes of anilato-derivatives, on varying the substituents at the 3,6 positions of the anilato moiety, will be discussed herein, whose structural features or physical properties are peculiar and/or unusual with respect to analogous compounds reported in the literature up to now. Their most appealing technological applications will be also reported.

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“…[2][3][4][5][6][7][8][9][10] While materials are considered to be electrochromic when marked visible color changes are shown under illumination, recent interest in electrochromic devices (ECD's) for multispectral energy modulation by reflectance and absorbance has extended the definition. 11 Chemical species are now being studied for modulation of radiation in the near infra-red (NIR), 10,12 thermal infra-red, 13 and microwave regions, and 'color' can mean response of detectors to these electromagnetic regions, not just the human eye. 11 …”

Section: Introductionmentioning

confidence: 99%

Electrochromic organic and polymeric materials for display applications

2006

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An electrochromic material is one where a reversible color change takes place upon reduction (gain of electrons) or oxidation (loss of electrons), on passage of electrical current after the application of an appropriate electrode potential. In this review the general field of electrochromism is introduced, with coverage of the types, applications, and chemical classes of electrochromic materials and the experimental methods that are used in their study. The main classes of electrochromic organic and polymeric materials are then surveyed, with descriptions of representative examples based on transition metal coordination complexes, viologen systems, and conducting polymers. Examples of the application of such organic and polymeric electrochromic materials in electrochromic displays are given.

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Non-innocent behaviour in mononuclear and polynuclear complexes: consequences for redox and electronic spectroscopic properties

Cited by 403 publications

References 61 publications

Mixed‐Valence Ruthenium Complexes Rotating through a Conformational Robin–Day Continuum

Mixed‐Valence Ruthenium Complexes Rotating through a Conformational Robin–Day Continuum

Recent Advances on Anilato-Based Molecular Materials with Magnetic and/or Conducting Properties

Electrochromic organic and polymeric materials for display applications

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