Molekulare magnetische Materialien

Molecule-based magnetic materials.

Organic Polyradicals as Redox Mediators: Effect of Intramolecular Radical Interactions on Their Efficiency

The spin–spin interactions between unpaired electrons in organic (poly)radicals, especially nitroxides, are largely investigated and are of crucial importance for their applications in areas such as organic magnetism, molecular charge transfer, or multiple spin labeling in structural biology. Recently, 2,2,6,6-tetramethylpiperidinyloxyl and polymers functionalized with nitroxides have been described as successful redox mediators in several electrochemical applications; however, the study of spin–spin interaction effect in such an area is absent. This communication reports the preparation of a novel family of discrete polynitroxide molecules, with the same number of radical units but differe…

Magnetic molecular metals based on the organic donor molecule BET (BET = Bis(ethylenethio)tetrathiafulvalene): The series BET2[MCI4] (M3⊕= Ga, Fe)

Impact of molecule-based magnetic materials: A critical outlook

Abstract A critical outlook of the field of molecular magnetic materials is presented. This article is inspired by an international symposium devoted to the “ Design, Characterization and Modelling of Molecule-Based Magnetic Materials (DCM4-II)” that took place at Strasbourg (France), from May 28th to June 1st, within the E-MRS 2007 Spring Meeting (Symposium R) organized by the European Materials Research Society in collaboration with the European Science Foundation . A series of papers linked to this symposium are published in this issue and in the previous issue (Volume 11, Issue 4) of Solid State Sciences.

Coexistence of ferro- and antiferromagnetic interactions in a metal-organic radical-based (6,3)-helical network with large channels.

A metal–organic open-framework with an unprecedented (6,3)-helical topology, large channels and mixed ferro- and antiferromagnetic interactions has been synthesized using a three-connecting tricarboxylic polychlorotriphenylmethyl radical and Co(II) ions. Lloret Pastor, Francisco, Francisco.Lloret@uv.es

A New Valence Tautomerism Example in an Electroactive Ferrocene Substituted Triphenylmethyl Radical

A new molecular system combining an open-shell organic radical that acts as an acceptor group, different from an o-quinone moiety, covalently linked to a ferrocene moiety, acting as the donor group, is shown to exhibit valence tautomerism.

Mechanistic studies of the ring opening reactions of [1,2,3]triazolo[1,5-a]pyridines

Abstract A mechanism with radical intervention is proposed for the opening of the triazole ring in [1,2,3] triazolo[1,5-a]pyridines which results in the production of 2- or 2,6-disubstituted pyridines.

Symmetry: Friend or foe?

While symmetry in molecules or supramolecular complexes is desirable from the design point of view and affords simpler NMR spectra, the study of symmetrical species by NMR is often subject to ambiguities resulting from signal degeneracy. In this paper we shall discuss different ways of breaking symmetry in order to obtain additional structural information by NMR.

Allocation of Ambipolar Charges on an Organic Diradical with a Vinylene-Phenylenediyne Bridge.

Two redox and magnetically active perchlorotriphenylmethyl (• PTM) radical units have been connected as end-capping groups to a bis(phenylene)diyne chain through vinylene linkers. Negative and positive charged species have been generated, and the influence of the bridge on their stabilization is discussed. Partial reduction of the electron-withdrawing • PTM radicals results in a class-II mixed-valence system with the negative charge located on the terminal PTM units, proving the efficiency of the conjugated chain for the electron transport between the two terminal sites. Counterintuitively, the oxidation process does not occur along the electron-rich bridge but on the vinylene units. The • …

Role of the Open-Shell Character on the Pressure-Induced Conductivity of an Organic Donor-Acceptor Radical Dyad

Single‐component conductors based on neutral organic radicals have received a lot of attention due to the possibility that the unpaired electron can serve as a charge carrier without the need of a previous doping process. Although most of these systems are based on delocalized planar radicals, we present here a nonplanar and spin localized radical based on a tetrathiafulvalene (TTF) moiety, linked to a perchlorotriphenylmethyl (PTM) radical by a conjugated bridge, which exhibits a semiconducting behavior upon application of high pressure. The synthesis, electronic properties, and crystal structure of this neutral radical TTF‐Ph‐PTM derivative (1) are reported and implications of its crystal…

Tetrathiafulvalene-Based Mixed-Valence Acceptor-Donor-Acceptor Triads: A Joint Theoretical and Experimental Approach

This work presents a joint theoretical and experimental characterisation of the structural and electronic properties of two tetrathiafulvalene (TTF)-based acceptor-donor-acceptor triads (BQ-TTF-BQ and BTCNQ-TTF - BTCNQ; BQ is naphthoquinone and BTCNQ is benzotetracyano-p-quinodimethane) in their neutral and reduced states. The study is performed with the use of electrochemical, electron paramagnetic resonance (EPR), and UV/Vis/NIR spectroelectrochemical techniques guided by quantum-chemical calculations. Emphasis is placed on the mixed-valence properties of both triads in their radical anion states. The electrochemical and EPR results reveal that both BQ-TTF-BQ and BTCNQ-TTF-BTCNQ triads in…

Structure Determination from Powder X-Ray Diffraction Data of a Hydrogen-Bonded Molecular Solid with Competing Ferromagnetic and Antiferromagnetic Interactions: The 2-(3,4-Dihydroxyphenyl)-α-Nitronyl Nitroxide Radical

Tetrathiafulvalene-Polychlorotriphenylmethyl Dyads: Influence of Bridge and Open-Shell Characteristics on Linear and Nonlinear Optical Properties

Three conjugated donor-π-acceptor radical systems (1 a–1 c) were prepared by bridging a tetrathiafulvalene (TTF) electron-donor unit to a polychlorotriphenylmethyl (PTM) electron-acceptor radical through vinylene units of different lengths. The dependence of the intramolecular charge transfer on the length of the conjugated bridge has been analyzed by different electrochemical and spectroscopic techniques. Linear optical properties and the second-order nonlinear optical (NLO) response of these derivatives have been computed by comparing systems 1 a–1 c with the non-radical analogues (2 a–2 c). Interestingly, an enhanced NLO response is predicted for dyads 1 a–1 c with PTM in the radical for…

Von den Pulver-Röntgenbeugungsdaten zur Struktur eines Molekülkristalls mit Wasserstoffbrückenbindungen und konkurrierenden ferromagnetischen und antiferromagnetischen Wechselwirkungen – das 2-(3,4-Dihydroxy-phenyl)-α-nitronylnitroxid-Radikal

Experimental and Theoretical Studies on Magnetic Exchange in Silole-Bridged Diradicals.

International audience; Five bis(tert-butylnitroxide) diradicals connected by a silole [2,5-R2-3,4-diphenylsilole; R = Me3CN(®O.bul.)Z; Z = p-C6H4 (7a), p-C6H4C6H4-p (7b), 1,4-naphthalenediyl (7c), m-C6H4 (7d)] or a thiophene [2,5-R2-thiophene; R = p-Me3CN(®O.bul.)C6H4 (12)] ring as a coupler were studied. Compd. 12 crystallizes in the orthorhombic space group Pna21 with a 20.752(5), b 5.826(5), and c 34.309(5) .ANG.. X-ray crystal structure detn., electronic spectroscopy, variable-temp. EPR spectroscopy, SQUID measurements and DFT computations (UB3LYP/6-31+G*) were used to study the mol. conformations and electronic spin coupling in this series of mols. Whereas compds. 7b, 7c, and 7d are q…

Dibenzocycloheptatriene as end-group of Thiele and tetrabenzo-Chichibabin hydrocarbons

The authors are grateful for the financial support from: MICIU/FEDER/AEI, Spain (PG2018-101181-B-I00, PGC2018-095808B-I00, MAT2016-80826-R, FIP-2018-HECTIC-PTM, Prometeo2019/076 and the "Severo Ochoa" Programme for Centres of Excellence in R & D; SEV-2015-0496), the European Research Council (ERC) (677023), DGR (Catalunya) (2017-SGR-918), and SNSF (Switzerland, TS., PZ00P2_174175). We thank the CSIRC-Alhambra and SciCore (Basel, Switzerland) for supercomputing facilities and the Servei de RMN, UAB, for instrument time.

Reversible switching of the Au(111) work function by near infrared irradiation with a bistable SAM based on a radical donor–acceptor dyad

We describe the modification of the work function (WF) of Au(111) upon deposition of self-assembled monolayers (SAMs) with two donor–acceptor (D–A) systems, one based on a ferrocene-polychlorotriphenylmethyl radical (Fc–PTM) dyad and another on its non-radical dyad analogue. Kelvin Probe Force Microscopy (KPFM) has been used to measure the changes in the Contact Potential Difference (CPD) between the tip and the SAM under application of a cycling sweep of direct current (DC) voltage bias. These measurements showed that both SAMs exhibit a hysteretic behaviour in their WF changes. Interestingly, the hysteresis loop of the radical SAM is notably reduced when irradiated with NIR light, which w…

CCDC 1817871: Experimental Crystal Structure Determination

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CCDC 1986124: Experimental Crystal Structure Determination

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CCDC 1817872: Experimental Crystal Structure Determination

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CCDC 2012097: Experimental Crystal Structure Determination

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CCDC 2012098: Experimental Crystal Structure Determination

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