Estimation of the Thermochemical Radii and Ionic Volumes of Complex Ions

Simoes, Marcus C.; Hughes, Kevin J.; Ingham, D.B.; Ma, Lin; Pourkashanian, Mohamed

doi:10.1021/acs.inorgchem.7b01205

Cited by 82 publications

(64 citation statements)

References 20 publications

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“…[36] to the above ICT-induced polar solvent relaxation (Scheme 3A). [36] to the above ICT-induced polar solvent relaxation (Scheme 3A).…”

Section: Resultsmentioning

confidence: 92%

“…Figure 7shows the time constant of the initial decay component of the F 1 band versus the anion Xradius for salts 2[X] in toluene.The decay time increases systematically with the growth of the thermochemical radius of the counter anions [36] (see also Tables 1and S5, and Figure S15). Figure 7shows the time constant of the initial decay component of the F 1 band versus the anion Xradius for salts 2[X] in toluene.The decay time increases systematically with the growth of the thermochemical radius of the counter anions [36] (see also Tables 1and S5, and Figure S15).…”

Section: Angewandte Chemiementioning

confidence: 92%

“…Secondly,a ssuming that the given ionic species would primarily exist in aform of nondissociated ion pairs in toluene and other nonpolar solvents,i ti sr easonable to expect asignificant influence of the counterions on the excited-state dynamics of ionic chromophores if the mechanism of ICTinduced counterion migration is operative. Figure 7shows the time constant of the initial decay component of the F 1 band versus the anion Xradius for salts 2[X] in toluene.The decay time increases systematically with the growth of the thermochemical radius of the counter anions [36] (see also Tables 1and S5, and Figure S15).…”

Section: Angewandte Chemiementioning

confidence: 92%

“…This indicates that the higher energy barrier in the anion migration process arises from the higher viscosity of 1,4-dioxane,w hich supports our conjecture.A dditionally,e mission spectra of 2[OTf] measured at different temperatures ( Figure S21) show an increase in the relative intensity of the F 2 band upon heating from À15 8 8Cto+ 65 8 8Cinboth toluene and 1,4-dioxane.The results in toluene as afunction of the thermochemical radius of the counter anions. [36] can be rationalized by ad ecrease in viscosity at elevated temperature,which facilitates the anion migration process.…”

Section: Angewandte Chemiementioning

confidence: 99%

“…[b] Calculated thermochemical radii of the anions. [36] Angewandte Chemie Forschungsartikel to the above ICT-induced polar solvent relaxation (Scheme 3A). Scheme 3Bdepicts the general concept using salt 2 as an example.I nalow polarity medium, the ion pairs of 2 have appreciable electrostatic interaction but poor dipole interaction with the solvation sphere.E xcitation conceivably produces the S 1 state with CT character,i nw hich -+ PR 3 (acceptor) and -NPh 2 (donor) become more neutral and positively charged, respectively,a ssuming complete charge transfer (see also Figure S5, which shows the difference in the electron density for the S 0 !S 1 transition).…”

Section: Angewandte Chemiementioning

confidence: 99%

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“…[36] to the above ICT-induced polar solvent relaxation (Scheme 3A). [36] to the above ICT-induced polar solvent relaxation (Scheme 3A).…”

Section: Resultsmentioning

confidence: 92%

Section: Angewandte Chemiementioning

confidence: 92%

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confidence: 92%

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confidence: 99%

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Toward Design Rules for Multilayer Ferroelectric Energy Storage Capacitors – A Study Based on Lead‐Free and Relaxor‐Ferroelectric/Paraelectric Multilayer Devices

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Future pulsed‐power electronic systems based on dielectric capacitors require the use of environment‐friendly materials with high energy‐storage performance that can operate efficiently and reliably in harsh environments. Here, we present a study of multilayer structures, combining paraelectric‐like Ba0.6Sr0.4TiO3 (BST) with relaxor‐ferroelectric BaZr0.4Ti0.6O3 (BZT) layers on SrTiO3‐buffered Si substrates, with the goal to optimize the high energy‐storage performance. The energy‐storage properties of various stackings are investigated and an extremely large maximum recoverable energy storage density of about 165.6 J cm−3 (energy efficiency ≈ 93%) is achieved for unipolar charging‐discharging of a 25‐nm‐BZT/20‐nm‐BST/910‐nm‐BZT/20‐nm‐BST/25‐nm‐BZT multilayer structure, due to the extremely large breakdown field of 7.5 MV cm−1 and the lack of polarization saturation at high fields in this device. We find strong indications that the breakdown field of the devices is determined by the outer layers of the multilayer stack and can be increased by improving the quality of these layers. We are also able to deduce design optimization rules for this material combination, which we can to a large extend justify by structural analysis. These rules are expected also to be useful for optimizing other multilayer systems and are therefore very relevant for further increasing the energy storage density of capacitors.This article is protected by copyright. All rights reserved

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Chemical Doping of Conjugated Polymers with the Strong Oxidant Magic Blue

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et al. 2020

Adv Elect Materials

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The opto-electronic as well as the mechanical properties of semiconducting polymers depend strongly on the charge-carrier density, which can be tuned chemically or electrochemically, a process which is referred to as doping. Hence, doping is a powerful tool to optimize the performance of organic electronic devices, such as transistors, solar cells and organic light-emitting diodes (OLEDs), [1,5] as well as of organic thermoelectric materials. [6][7][8] Further, in case of electrochemical transistors and light-emitting electrochemical cells, modulation of the charge-carrier density is essential to the operation of these devices. [9,10] One way to introduce charges is via redox doping, also referred to as molecular doping, which involves an electron transfer between the semiconducting polymer and a small molecule, the socalled redox dopant. In case of p-doping a positive energetic offset between the electron affinity (EA) of the small-molecular dopant and the ionization energy (IE) of the semiconducting polymer is advantageous, i.e., EA dopant > IE polymer . Depending on the relative position of the energy levels one or even two electrons can be transferred from the polymer backbone to a dopant molecule. [11] A broad variety of p-and n-type polymer-dopant couples have been studied. The most common p-type redox dopant is 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ), [12,13] which shows an electron affinity of EA ≈ 5.2 eV and readily oxidizes polymers such as poly(3-hexylthiophene) (P3HT; IE ≈ 5.1 eV) [14][15][16][17][18][19] and thiophene-thienothiophene copolymers (PBTTT; IE ≈ 5.2 eV). [20,21] Many other conjugated polymers such as, for example, high-mobility donor-acceptor polymers have an IE of more than 5.3 eV and can therefore not be doped with F4TCNQ. At the same time, doping of high mobility polymers is of special interest in the field of organic thermoelectrics, because the use of such polymers may allow to increase the thermoelectric power factor, which scales with the electrical conductivity and hence charge-carrier mobility. [22,23] There are only few examples of dopants with a high electron affinity including 1,3,4,5,7,8-hexafluoro-tetracyano-naphthoquinodimethane (F6TCNNQ) (EA ≈ 5.3 eV), [11,24] hexacyano-trimethylene-cyclopropane (EA ≈ 5.9 eV) [24] and its derivatives, [25] and molybdenum dithiolene complexes such as Mo(tfd-COCF 3 ) 3 Molecular doping of organic semiconductors is a powerful tool for the optimization of organic electronic devices and organic thermoelectric materials. However, there are few redox dopants that have a sufficiently high electron affinity to allow the doping of conjugated polymers with an ionization energy of more than 5.3 eV. Here, p-doping of a broad palette of conjugated polymers with high ionization energies is achieved by using the strong oxidant tris(4bromophenyl)ammoniumyl hexachloroantimonate (Magic Blue). In particular diketopyrrolopyrrole (DPP)-based copolymers reach a conductivity of up to 100 S cm −1 and a thermoelectric power factor of 10 µW m −...

show abstract

Estimation of the Thermochemical Radii and Ionic Volumes of Complex Ions

Cited by 82 publications

References 20 publications

A Facile Molecular Machine: Optically Triggered Counterion Migration by Charge Transfer of Linear Donor‐π‐Acceptor Phosphonium Fluorophores

A Facile Molecular Machine: Optically Triggered Counterion Migration by Charge Transfer of Linear Donor‐π‐Acceptor Phosphonium Fluorophores

Toward Design Rules for Multilayer Ferroelectric Energy Storage Capacitors – A Study Based on Lead‐Free and Relaxor‐Ferroelectric/Paraelectric Multilayer Devices

Chemical Doping of Conjugated Polymers with the Strong Oxidant Magic Blue

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