We have investigated the magnetic properties of four recently synthesized stable TMM-type nitroxide diradicals. Four new diradicals are proposed by tailoring one of the species in such a way that both conjugation and planarity increase. As a remarkable consequence, the intramolecular ferromagnetic exchange interaction was found to be quite high in the proposed radicals. The calculated coupling constants were in the range of +102 to +140 cm-1. The MO and spin density analysis are provided to interpret the exchange interactions. We observed the existence of intramolecular pi-pi-interactions for the species 2. This slightly increased the J value by shortening the length of the spacer between the two spin sources.
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http://dx.doi.org/10.1021/jp073076r | DOI Listing |
J Comput Chem
January 2025
Manipal Centre for Natural Sciences, Manipal Academy of Higher Education, Manipal, Karnataka, India.
The magnetic nature of nonalternant hydrocarbon (Azulene) bridged nitronyl nitroxide (AzNN) and imino-nitroxide (AzIN) diradicals are investigated with 38 different DFT functionals to find out a correct functional to predict the magnetic nature of these diradicals. The effect of Hartree-Fock exchange (HFX) in the hybrid functionals are investigated for the prediction of magnetic nature of the nonalternant hydrocarbon bridged diradicals. The utility of Borden and Davidson's proposal of disjoint and nondisjoint SOMOs for the prediction of magnetic nature of alternant hydrocarbon bridged diradicals is assessed for the nonalternant hydrocarbon based diradicals.
View Article and Find Full Text PDFJ Org Chem
September 2024
Anhui Key Laboratory of Advanced Building Materials, School of Materials Science and Chemical Engineering, Anhui Jianzhu University, Hefei 230601, China.
To explore the distinctions in spin coupling between the molecular bridges of alternating and nonalternating π-systems, we synthesized a pair of isoelectronic compounds, namely, and , by utilizing naphthalene and azulene (naphthalene = Na and azulene = Az) as the bridges, respectively. Moreover, we conducted assessments to predict the coupling paths for nonalternating azulene. Variable-temperature EPR (VT-EPR) and SQUID results consistently reveal that both and exhibit antiferromagnetic coupling interactions, with coupling constants of = -22.
View Article and Find Full Text PDFRapid Commun Mass Spectrom
September 2024
Aix Marseille Université, CNRS, UMR7273, Institut de Chimie Radicalaire, Marseille, France.
Rationale: Optimizing the structure of digital polymers is an efficient strategy to ensure their tandem mass spectrometry (MS/MS) readability. In block-truncated poly(phosphodiester)s, homolysis of C-ON bonds in long chains permits the release of smaller blocks amenable to sequencing. Yet the dissociation behavior of diradical blocks was observed to strongly depend on their charge state.
View Article and Find Full Text PDFChemistry
July 2024
Institute of Nanotechnology (INT), Karlsruhe Institute of Technology (KIT), Hermann-von-Helmholtz-Platz 1, 76344, Eggenstein-Leopoldshafen, Germany.
A diradical with engineered g-asymmetry was synthesized by grafting a nitroxide radical onto the [Y(Pc)]⋅ radical platform. Various spectroscopic techniques and computational studies revealed that the electronic structures of the two spin systems remained minimally affected within the diradical system. Fluid-solution Electron Paramagnetic Resonance (EPR) experiments revealed a weak exchange coupling with |J| ~ 0.
View Article and Find Full Text PDFChemistry
May 2024
Departament de Ciència de Materials i Química Física & IQTCUB, Facultat de Química, Universitat de Barcelona, Martí i Franquès 1, E-08028, Barcelona.
Spin-polarized donor radicals based on tetrathiafulvalene (TTF) derivatives and nitronyl nitroxide (NN) radicals in which one-electron oxidation involves the HOMO instead of the SOMO are well known for exhibiting magnetoresistance. In particular, BTBN consists of one dibromo-TTF and one NN radical, which are linked by a phenyl coupler group. One of the key factors driving magnetoresistance is the presence of intramolecular ferromagnetic (FM) coupling between the oxidized π-donor (TTF⋅, D unit) and NN (R unit).
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