Ein molekularer, multifunktioneller Schalter auf der Basis des Redoxverhaltens eines Ferrocenyl‐Polychlortriphenylmethyl‐Radikals

Sporer, Christian; Ratera, Imma; Ruiz‐Molina, Daniel; Zhao, Yanyun; Vidal-Gancedo, José; Wurst, Klaus; Jaitner, Peter; Clays, Koen; Persoons, André; Rovira, Concepció; Veciana, Jaume

doi:10.1002/ange.200454150

Cited by 31 publications

(20 citation statements)

References 26 publications

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“…[1] For ex-ample, all-optical computers may arise from exploiting NLO effects that allow data transmission and processing, solely through laser light beams. [3] NLO chromophores most often have simple dipolar electronic structures. Metal complexes permit greatly expanded structural diversity and vast scope for realising multifunctional optical materials, [2] featuring, for example, redox-switchable NLO responses.…”

Section: Introductionmentioning

confidence: 99%

Heptametallic, Octupolar Nonlinear Optical Chromophores with Six Ferrocenyl Substituents

Coe

Foxon

Helliwell

et al. 2013

Chemistry A European J

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New complexes with six ferrocenyl (Fc) groups connected to ZnII or CdII tris(2,2′‐bipyridyl) cores are described. A thorough characterisation of their BPh4− salts includes two single‐crystal X‐ray structures, highly unusual for such species with multiple, extended substituents. Intense, visible d(FeII)→π* metal‐to‐ligand charge‐transfer (MLCT) bands accompany the π→π* intraligand charge‐transfer absorptions in the near UV region. Each complex shows a single, fully reversible FeIII/II wave when probed electrochemically. Molecular quadratic nonlinear optical (NLO) responses are determined by using hyper‐Rayleigh scattering and Stark spectroscopy. The latter gives static first hyperpolarisabilities β0 reaching as high as approximately 10−27 esu and generally increasing with π‐conjugation extension. Z‐scan cubic NLO measurements reveal high two‐photon absorption cross‐sections σ2 of up to 5400 GM in one case. DFT calculations reproduce the π‐conjugation dependence of β0, and TD‐DFT predicts three transitions close in energy contributing to the MLCT bands. The lowest energy transition has octupolar character, whereas the other two are degenerate and dipolar in nature.

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Section: Introductionmentioning

confidence: 99%

Heptametallic, Octupolar Nonlinear Optical Chromophores with Six Ferrocenyl Substituents

Coe

Foxon

Helliwell

et al. 2013

Chemistry A European J

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“…[19] Another family of persistent organic radicals is the perchlorinated triphenylmethyl (trityl) radicals (PTMs). [20] These molecules have been investigated because of their paramagnetism, [21] electroactivity, [22] and/or optical properties. [23,24] Recently, we have developed a strategy based on the use of these radicals as paramagnetic bridging ligands.…”

Section: Introductionmentioning

confidence: 99%

Three‐Dimensional Porous Metal–Radical Frameworks Based on Triphenylmethyl Radicals

Datcu

Roques

Jubera

et al. 2011

Chemistry A European J

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Lanthanide coordination polymers {[Ln(PTMTC)(EtOH)(2)H(2)O]·x H(2)O, y EtOH} [Ln=Tb (1), Gd (2), and Eu (3)] and {[Ln(αH-PTMTC)(EtOH)(2)H(2)O]·x H(2)O, y EtOH} [Ln=Tb (1'), Gd (2'), and Eu (3')] have been prepared by reacting Ln(III) ions with tricarboxylate-perchlorotriphenylmethyl/methane ligands that have a radical (PTMTC(3-)) or closed-shell (αH-PTMTC(3-)) character, respectively. X-ray diffraction analyses reveal 3D architectures that combine helical 1D channels and a fairly rare (6,3) connectivity described with the (4(2).8)·(4(4).6(2).8(5).10(4)) Schäfli symbol. Such 3D architectures make these polymers porous solids upon departure of the non-coordinated guest-solvent molecules as confirmed by the XRD structure of the guest-free [Tb(PTMTC)(EtOH)(2)H(2)O] and [Tb(αH-PTMTC)(EtOH)(2)H(2)O] materials. Accessible voids represent 40% of the cell volume. Metal-centered luminescence was observed in Tb(III) and Eu(III) coordination polymers 1' and 3', although the Ln(III)-ion luminescence was quenched when radical ligands were involved. The magnetic properties of all these compounds were investigated, and the nature of the {Ln-radical} (in 1 and 2) and the {radical-radical} exchange interactions (in 3) were assessed by comparing the behaviors for the radical-based coordination polymers 1-3 with those of the compounds with the diamagnetic ligand set. Whilst antiferromagnetic {radical-radical} interactions were found in 3, ferromagnetic {Ln-radical} interactions propagated in the 3D architectures of 1 and 2.

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“…[1] An appreciable number of photochromic families have been reported to date; [2] however, those based on an electron-transfer (redox) chemical process, especially for metal-organic compounds, are rare. [3] We present herein a hydrothermally synthesized 3D complex [Cd 2 (ic)(mc) (4,4'-bipy) 3 ] n ·4n H 2 O (1Y; ic= itaconate, mc = mesaconate) which exhibits reversible radicalbased redox photochromic behavior. This compound also merits attention for its unusual five-connected Archimedeantype topological structure and unexpected "capture" of isomeric ic and mc ligands that are generated in situ from trans-propene-1,2,3-tricarboxylic acid (H 3 L, Scheme 1).…”

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“…Both ic and mc ligands in 1Y serve as two-connecting ligands by linking Cd1 atoms to yield an arch-bridge-like 1D chain along the [1 10] (4,4'-bipy) 3 (NO 3 ) 4 ] n ·4n H 2 O. [8] Furthermore, these bilayers are cross-bridged by 4,4'-bipy ligands through the N41 and N42 atoms to generate a 3D Archimedean-type network with a 4 2 6 6 8 2 topology built upon five-connected Cd II metal centers (Figure 2 c,d).…”

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Photochromism of a 3D Cd^II Complex with Two Captured Ligand Isomers Generated In Situ from the Same Precursor

et al. 2008

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Photochromic compounds have gained intense interest owing to their novel photochemical and photophysical reactions as well as their various potential applications such as in sunglasses and optical memories.[1] An appreciable number of photochromic families have been reported to date; [2] however, those based on an electron-transfer (redox) chemical process, especially for metal-organic compounds, are rare.[3] We present herein a hydrothermally synthesized 3D complex [Cd 2 (ic)(mc)(4,4'-bipy) 3 ] n ·4n H 2 O (1Y; ic= itaconate, mc = mesaconate) which exhibits reversible radicalbased redox photochromic behavior. This compound also merits attention for its unusual five-connected Archimedeantype topological structure and unexpected "capture" of isomeric ic and mc ligands that are generated in situ from trans-propene-1,2,3-tricarboxylic acid (H 3 L, Scheme 1).Yellow prismatic crystals of 1Y accompanied by a few colorless block crystals of [Cd 3 L 2 (H 2 O) 6 ] n (2; Figure S1 in the Supporting Information) were obtained by the hydrothermal reaction of CdCO 3 , 4,4'-bipy, H 3 L, and deionized water in a molar ratio of 1:1:1:1111 at 120 8C for 12 h. Powder X-ray diffraction (PXRD) verified the purity of a mechanically separated sample of 1Y ( Figure S2 in the Supporting Information). Thermal analysis and PXRD data show that compound 1Y still keeps its metal-organic framework at 200 8C after the elimination of lattice water molecules ( Figure S2 and S3 in the Supporting Information).A single-crystal X-ray diffraction study of 1Y revealed a 3D structure based on a network of seven-coordinated Cd II centers linked by three kinds of bridging ligands. As shown in Figure 1, the central Cd1 atom is located in a pentagonalbipyramidal coordination environment with N41 and N42 atoms of crystallographically independent 4,4'-bipy ligands acting as the two pyramidal apexes. An important feature of 1Y is the simultaneous "capture" of isomeric ic and mc ligands that originate from the in situ pyrolysis of H 3 L. [4]

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Ein molekularer, multifunktioneller Schalter auf der Basis des Redoxverhaltens eines Ferrocenyl‐Polychlortriphenylmethyl‐Radikals

Cited by 31 publications

References 26 publications

Heptametallic, Octupolar Nonlinear Optical Chromophores with Six Ferrocenyl Substituents

Heptametallic, Octupolar Nonlinear Optical Chromophores with Six Ferrocenyl Substituents

Three‐Dimensional Porous Metal–Radical Frameworks Based on Triphenylmethyl Radicals

Photochromism of a 3D Cd^II Complex with Two Captured Ligand Isomers Generated In Situ from the Same Precursor

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Ein molekularer, multifunktioneller Schalter auf der Basis des Redoxverhaltens eines Ferrocenyl‐Polychlortriphenylmethyl‐Radikals

Cited by 31 publications

References 26 publications

Heptametallic, Octupolar Nonlinear Optical Chromophores with Six Ferrocenyl Substituents

Heptametallic, Octupolar Nonlinear Optical Chromophores with Six Ferrocenyl Substituents

Three‐Dimensional Porous Metal–Radical Frameworks Based on Triphenylmethyl Radicals

Photochromism of a 3D CdII Complex with Two Captured Ligand Isomers Generated In Situ from the Same Precursor

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Photochromism of a 3D Cd^II Complex with Two Captured Ligand Isomers Generated In Situ from the Same Precursor