Design and Synthesis of a Thermally Stable Organic Electride

Redko, Mikhail Y.; Jackson, James E.; Huang, Rui; Dye, James

doi:10.1021/ja053216f

Cited by 124 publications

(145 citation statements)

References 40 publications

(52 reference statements)

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“…[12] The geometric parameters of the anion are almost identical for both complexes. The anion has a nearly planar trigonal arrangement, with the La atom 0.019 or 0.016 out of the plane determined by the centroids of the three Cp'' ligands (M1, M2, and M3) for 1 and 2, respectively.…”

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confidence: 92%

“…And if the extra electrons were trapped in the cavities formed by closely packed encapsulated K + cations and neutral [LaCp'' 3 ] molecules in a manner similar to electrides, narrow signals with the free-electron g value would be observed. [12] The paramagnetic properties were confirmed by temperature-dependent susceptibility measurements by the SQUID technique. The magnetic behavior of 2 (Figure 2 (0.216 g, 0.28 mmol) in THF (10 mL) was added to an ampoule containing a K mirror (0.010 g, 0.26 mmol) and a glass-coated magnetic stirring bar.…”

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confidence: 96%

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Lanthanum Does Form Stable Molecular Compounds in the +2 Oxidation State

et al. 2008

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Dedicated to Professor William J. Evans on the occasion of his 60th birthdayThe continuing quest for molecular complexes of lowoxidation-state lanthanides (other than the well-known samarium(II), europium(II), and ytterbium(II)) has produced significant achievements.[1] The majority of such compounds are derivatives of neodymium, dysprosium, and thulium, [2] obtained from the corresponding molecular iodides (often prepared in situ): [NdI 2 (thf) [2c,d] or by the reduction of an appropriate Ln III derivative. [2e,f] The present state of lanthanum, cerium, praseodymium, and gadolinium redox chemistry was described by S. A. Cotton: "None of these metals exhibits a stable + 2 state in any of its compounds and … they are unlikely to form stable compounds in this state." [3] Thus, the isolation of room-temperature-stable solid La II compounds is a very unexpected and significant breakthrough in the chemistry of lanthanides.Related to the subject of this study is a large group of inorganic materials: reduced or metal-rich rare-earth-metal halides, [4] including LaI 2 (featuring an extended structure with La 5d1 electrons delocalized on a conduction band), in which a lanthanum atom can be considered as being in the + 2 oxidation state.[4b] These compounds are better treated in a materials science context, where the metal valence [5,6] rather than the oxidation state is of primary importance.Previously [8] The latter featured redox ambiguity, which was also found in cerocene [9] and bis(pentalene)-cerium, [10] in which a metal-bound ligand had readily accessible adjacent oxidation states. For the binuclear arenebridged complexes, three different metal-ligand formal charge distributions are possible: Ln 2+

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Lanthanum Does Form Stable Molecular Compounds in the +2 Oxidation State

et al. 2008

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“…[13,14] Electrides are ionic compounds in which the cations are complexed by complexants and the anionic sites are occupied by trapped excess electrons. Since some electrides were synthesized by Dye's group, [15][16][17] electrides have attracted widespread attention of other researchers due to their broad potential applications in catalysis, nanodevices, and functional materials. [18,19] Doping (super)alkali atoms is one of the most effective ways to design a system with excess electron.…”

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confidence: 99%

Investigation on the electronic structures and nonlinear optical properties of alkali metal atom doped all‐cis 1,2,3,4,5,6‐hexafluorocyclohexane

Hou

Wang

et al. 2018

Int J of Quantum Chemistry

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On the basis of stable all‐cis 1,2,3,4,5,6‐hexafluorocyclohexane, a series of alkali metal atom doped MF6C6H6 (M = Li, Na, and K) compounds were theoretically constructed and studied by using ab initio quantum chemistry method. The calculated results show that the HOMO–LUMO gap of the MF6C6H6 conspicuously narrowed from 10.41 eV of pure F6C6H6 to about 2.00 eV of MF6C6H6. The electride characteristics of MF6C6H6 are verified by their electronic structures, HOMOs, and small VIE values. As expected, these electrides possess considerable static first hyperpolarizabilities (β0). Among the studied electrides, the largest β0 of the LiF6C6H6 is 7.00 × 105 au, which is about 3030 times larger than pure F6C6H6. TD‐M06‐2X calculations show that these larger β0 values are attributed to lower transition energies for the crucial excited states of MF6C6H6 systems. Further, the vibrational contributions to the static first hyperpolarizabilities of these molecules are also estimated. Moreover, Li atom doped dimer and trimer of F6C6H6 also present unusual electride's features and exhibit dramatically large β0. Thus, the F6C6H6 interacting with the alkali metal atoms may be a potential promising NLO nanomaterial.

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“…[9][10][11][12][13][14] To date, fifteen(seven inorganic and eight organic)s olide lectrides have been reported, eight of which are stable at room temperature. [13,[15][16][17][18][19] In some other cases,t he electride character is revealed only at high pressure. [20][21][22][23][24][25][26][27] Molecular electrides [28] are another type of electrides that have an electron( or as ignificant portion of an electron) that cannotb ea ssigned to any nucleus of the molecule, yet is relativelywell localisedin the molecular space.…”

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confidence: 99%

Metal Cluster Electrides: A New Type of Molecular Electride with Delocalised Polyattractor Character

Bakouri

Postils

Garcia‐Borràs

et al. 2018

Chemistry A European J

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Electrides are ionic substances containing isolated electrons. These confined electrons are topologically characterised by a quasi-atom, that is, a non-nuclear attractor (NNA) of the electron density. The electronic structure of the octahedral A Li and A Be species shows that these species have a large number of NNAs. These NNAs have highly delocalised electron densities and, as a result, the chemical bonding pattern of these systems is reminiscent of that in solid metals, in which metal cations are surrounded by a "sea" of delocalised valence electrons. We propose the term metal cluster electrides to refer to this new class of compounds. In this study, we establish a computational protocol to identify, characterize, and design metal cluster electrides and we elucidate the intricate bonding patterns of this particular type of species.

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Design and Synthesis of a Thermally Stable Organic Electride

Cited by 124 publications

References 40 publications

Lanthanum Does Form Stable Molecular Compounds in the +2 Oxidation State

Lanthanum Does Form Stable Molecular Compounds in the +2 Oxidation State

Investigation on the electronic structures and nonlinear optical properties of alkali metal atom doped all‐cis 1,2,3,4,5,6‐hexafluorocyclohexane

Metal Cluster Electrides: A New Type of Molecular Electride with Delocalised Polyattractor Character

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