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Breuning, Esther; Rüben, Mario; Lehn, Jean‐Maríe; Renz, Franz; Garcia, Yann; Ksenofontov, Vadim; Gütlich, Philipp; Wegelius, Elina

doi:10.1002/1521-3773(20000717)39:14<2377::aid-anie2377>3.0.co;2-s

Cited by 46 publications

(66 citation statements)

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“…Custom-designed compounds with an extraordinary level of sophistication such as the supramolecular chain of rotaxanes [91] or molecules containing coupled structural and electronic switches [100] have already been synthesized. Beyond molecular design, efforts are increasingly devoted also to rationalization and control over supramolecular organization, something which may be key to device integration [101]. The potential to graft molecular switches onto polymeric chains [31], inorganic nanoparticles [102] and surfaces [103], or even on macromolecules of biological interest [78] is certainly a huge advantage over other actuating materials.…”

Section: Discussionmentioning

confidence: 99%

Switchable molecule-based materials for micro- and nanoscale actuating applications: Achievements and prospects

Manrique-Juárez

Rat

Salmon

et al. 2016

Coordination Chemistry Reviews

230

202

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Section: Discussionmentioning

confidence: 99%

Switchable molecule-based materials for micro- and nanoscale actuating applications: Achievements and prospects

Manrique-Juárez

Rat

Salmon

et al. 2016

Coordination Chemistry Reviews

230

202

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“…10). Thus, 2×2 Co II 4 (Ruben et al, 2003a) and Fe II 4 (Breuning et al, 2000;Ruben et al, 2003b) grid complexes present, respectively, multiple electronic levels and triggered spin-transition processes that may be of interest for supramolecular electronics and spintronics. Addressing such entities may become possible via surface deposition (Semenov et al, 1999).…”

Section: Self-organization In Supramolecular Nanoscience and Nanotechmentioning

confidence: 99%

Supramolecular Chemistry: From Molecular Information toward Self-Organization and Complex Matter

Lehn¹

2012

Albert Einstein Memorial Lectures

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“…[12,13]. In the heptanuclear complex [{Fe II (CN) 6 }{Fe III L 5 } 6 ]Cl 2 , the central ferrocyanide unit is magnetically silent although the peripheral Fe(III) centers alter the spin state [14].…”

Section: Figmentioning

confidence: 99%

Interplay between spin crossover and exchange interaction in iron(III) complexes

Boča

Němec

Šalitroš

et al. 2009

Pure and Applied Chemistry

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In the dinuclear and polynuclear metal complexes exhibiting the low-spin (LS) to high-spin (HS) transition, the spin-crossover phenomenon interferes with the magnetic exchange interaction. The latter manifests itself in forming spin-multiplets, which causes a possible overlap of the band originating in different reference spin states (LL, LH, HL, and HH). A series of dinuclear Fe(III) complexes has been prepared; the iron centers are linked by a bidentate bridge (CN -, and diamagnetic metallacyanates {Fe(CN) 5 (NO)}, {Ni(CN) 4 }, {Pt(CN) 4 }, and {Ag(CN) 2 }). Magnetic measurements confirm that the spin crossover proceeds on the thermal propagation. This information has been completed also by the Mössbauer spectral (MS) data. A theoretical model has been developed that allows a simultaneous fitting of all available experimental data (magnetic susceptibility, magnetization, HS mole fraction) on a common set of parameters.The explicit inclusion of the interelectron repulsion means that atomic terms |α,L,S,M L ,M S 〉 are accounted for in the orbital-spin basis set and in the language of the crystal-field (CF) theory, the CF terms |α,Γ,γ,S,M S 〉 (like 2 T 2g , 6 A 1g ). On including the spin-orbit interaction, we arrive at the CF multiplets |α,Γ ',γ'〉 which are classified in terms of irreducible representations of the respective double group (Γ 1 through Γ 8 for O'). The splitting of the isolated 2 T 2g (×6) CF term into Γ 8 = U 3/2 (×4) and Γ 7 = E 5/2 (×2) multiplets equals (3/2)λ = (3/2)ξ = 690 cm -1 for Fe(III), and thus it is rather high, whereas no splitting of the term 6 A 1g → (Γ 8 , Γ 7 ) occurs in the first order for an octahedral system.A theoretical modeling based upon the generalized CF theory has been done, where the electron repulsion (Racah parameters B = 1122 cm -1 , and C = 4.2 B), CF strength (F 4 -poles of individual ligands), spin-orbit interaction (coupling constant ξ = 460 cm -1 ), orbital-Zeeman, and spin-Zeeman interactions are explicitly included [3]. The calculated Zeeman levels enter the partition function from which the magnetization and magnetic susceptibility are evaluated by using apparatus of the statistical thermodynamics. Calculated temperature dependence of the effective magnetic moment is displayed in Fig. 2, and one can see that the spin crossover occurs only in a very narrow interval of the CF strength. With F 4 = 17 700 cm -1 , the ground CF term is 6 A 1g (HS), whereas with F 4 = 18 200 cm -1 , it is 2 T 2g (LS). In the intermediate CF strength, a delicate situation occurs. With F 4 = 18 000 cm -1 , the ground CF term is 6 A 1g , preventing the spin crossover since it is already HS. However, the spin-orbit splitting of the excited 2 T 2g term (690 cm -1 ) is greater than the inter-term gap (425 cm -1 ) so that the ground CF multiplet is Γ 7 (×2) ← 2 T 2g . Therefore, the condition for the spin crossover ΔS > 0 is fulfilled, and it proceeds according to the bold curve shown in Fig. 2. (Because of the calculations in the complete 252-member basis set spanned by d 5 functions, th...

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Cited by 46 publications

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Switchable molecule-based materials for micro- and nanoscale actuating applications: Achievements and prospects

Switchable molecule-based materials for micro- and nanoscale actuating applications: Achievements and prospects

Supramolecular Chemistry: From Molecular Information toward Self-Organization and Complex Matter

Interplay between spin crossover and exchange interaction in iron(III) complexes

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