Current trends and future challenges in the experimental, theoretical and computational analysis of intervalence charge transfer (IVCT) transitions

D’Alessandro, Deanna M.; Keene, F. Richard

doi:10.1039/b514590m

Cited by 222 publications

(366 citation statements)

References 45 publications

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“…This behavior is typically observed for intervalence charge-transfer (IVCT) excitations. [72,73] The observed spectra can be deconvoluted into two Gaussian-shaped bands, which are assumed to represent the IVCT transition and a ligand-to-metal charge-transfer (LMCT) transition. [41] The sum of these two Gaussian functions allows an almost exact overlay with the experimental spectra.…”

Section: J(mentioning

confidence: 99%

Electron‐Transfer Studies of trans‐Platinum Bis(acetylide) Complexes

et al. 2014

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Section: J(mentioning

confidence: 99%

Electron‐Transfer Studies of trans‐Platinum Bis(acetylide) Complexes

et al. 2014

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“…This intense absorption features are attributed to ligand-based IVCT. Notably, a solid-state UV-vis-NIR spectrum of a molecular Fe III semiquinone-catecholate compound shows a similar, though narrower, IVCT band at νmax = 5200 cm −1 [192]. Since all the iron centers are trivalent as confirmed by Mossbauer spectroscopy, the origin of the IVCT must be the organic dhbq 2−/3− moieties.…”

Section: Anilato-based Multifunctional Organic Framework (Mofs)mentioning

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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“…[36][37]50 Indeed, these absorptions fall into the spectral range in which intervalence absorptions of bis(triarylamine) radical cations are commonly observed. 16,20,[34][35][51][52][53][54][55][56][57][58][59][60][61] An important difference to the intervalence absorptions of coordination compounds 40,[62][63][64][65] are the comparatively large extinction coefficients of these bands, but this is a (favorable) peculiarity of organic mixed-valence compounds which has been noted many times before. Table 2.…”

Section: -49mentioning

confidence: 99%

Charge Delocalization in a Homologous Series of α,α′-Bis(dianisylamino)-Substituted Thiophene Monocations

et al. 2012

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A homologous series of three molecules containing thiophene, bithiophene and terthiophene bridges between two redox-active tertiary amino-groups was synthesized and explored. Charge-delocalization in the one-electron oxidized forms of these molecules was investigated by a combination of cyclic voltammetry, near-infrared optical absorption spectroscopy, and EPR spectroscopy. All three cation radicals can be described as organic mixed-valence species, and for all of them the experimental data is consistent with strong delocalization of the unpaired electron. Depending on what model is used for 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 2 analysis of the optical absorption data, estimates for the electronic coupling matrix element (H AB ) range from ∼5000 cm -1 to ∼7000 cm -1 for the shortest member of the homologous series. According to optical absorption and EPR spectroscopy even the terthiophene radical appears to belong either to Robin-Day class III or to a category of radicals commonly denominated as borderline class II / class III systems. The finding of such a large extent of charge delocalization over up to three adjacent thiophene units is remarkable.

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Current trends and future challenges in the experimental, theoretical and computational analysis of intervalence charge transfer (IVCT) transitions

Cited by 222 publications

References 45 publications

Electron‐Transfer Studies of trans‐Platinum Bis(acetylide) Complexes

Electron‐Transfer Studies of trans‐Platinum Bis(acetylide) Complexes

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

Charge Delocalization in a Homologous Series of α,α′-Bis(dianisylamino)-Substituted Thiophene Monocations

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