The 2:1 salt of a new donor molecule, EDT-DSDTFVSDS with FeBr4- ion, (EDT-DSDTFVSDS)2.FeBr4 showed an essentially metallic behavior despite a small upturn in the electrical resistance below ca. 30 K (electrical conductivities at 290 and 4.2 K are 200 and 170 S cm-1, respectively). The Fe(III) d spins of the FeBr4- ions in this salt were subject to antiferromagnetic ordering at 3.3 K by virtue of a strong pi-d interaction (Jpid) which is comparable to that in a molecular metallic conductor, lambda-(BETS)2.FeCl4, and of a very weak d-d interaction (Jdd). This strong pi-d interaction was evidenced by a large and negative magnetoresistance effect (ca. 20% at 5 T) as well as by the appearance of a large dip in the resistance at the magnetic field (ca. 2.0 T) parallel to the easy axis for the spin-flop transition of the Fe(III) d spins.
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http://dx.doi.org/10.1021/ja064307v | DOI Listing |
Biomaterials
April 2025
Department of Chemistry, Korea University, Seoul, 02841, South Korea. Electronic address:
Pyroptosis is considered as a new way to effectively boost the immune response of tumors and inhibit tumor growth. Effective strategies to induce pyroptosis mainly rely on chemotherapeutic drugs and phototherapy, but their potential biotoxicity and phototoxicity limit their application in biomedicine. Herein, we designed a NIR-II emitting pyroptosis biotuner, Rd-TTPA, which induced pyroptosis under ultrasound irradiation to achieve pyroptosis-enhanced sonodynamic therapy (SDT) and immunogenic cell death (ICD) for tumors.
View Article and Find Full Text PDFSpectrochim Acta A Mol Biomol Spectrosc
January 2025
Department of Physics, St. John's College of Arts and Science, M.S. University, Kanyakumari 629204, Tamil Nadu, India.
The nonlinear optical properties of push-pull chromophores, namely (E)-7-(4-bromophenyl)-2,5-bis(4-nitrophenyl)-3,4,5,6-tetrahydro-2H-1,2-diazepin-4-ol (A-π-D-π-A) and (E)-7-(4-bromophenyl)-5-(4-nitrophenyl)-2-phenyl-3,4,5,6-tetrahydro-2H-1,2-diazepin-4-ol (A-π-D-π-D), have been investigated using the z-scan technique. NMR, FT-IR, and UV-visible spectral analysis have been performed. The results were compared with density functional theory calculations employing the B3LYP/6-311++G (d, p) basis set.
View Article and Find Full Text PDFPhys Chem Chem Phys
June 2024
School of Energy and Power Engineering, Shandong University, Jinan, Shandong, 250061, China.
An study of the rovibronic spectra for the cyano radical (CN) based on a diabatic representation is presented. This work considers 17 electronic states, 59 dipole moment curves, 88 spin-orbit coupling curves, and 30 electronic angular momentum coupling curves, which are obtained using the internally contracted multireference configuration interaction method including the Davidson correction (icMRCI + Q) with the aug-cc-pwCV5Z-DK basis set. The diabatic transformations are performed based on a property-based diabatization method to remove the avoided crossings for the DΠ-HΠ and bΠ-2Π pairs.
View Article and Find Full Text PDFChemphyschem
September 2024
Departament de Química and Institut de Química Computacional i Catàlisi (IQCC), Universitat de Girona, Campus Montilivi s/n, 17071, Girona, Spain.
Metal-ligand interactions are at the heart of transition metal complexes. The Dewar-Chat-Duncanson model is often invoked, whereby the metal-ligand bonding is decomposed into the simultaneous ligand→metal electron donation and the metal→ligand back-donation. The separate quantification of both effects is not a trivial task, neither from experimental nor computational exercises.
View Article and Find Full Text PDFInorg Chem
June 2024
Institute of Organic Chemistry and Biochemistry, Czech Academy of Sciences, Prague 6 16610, Czech Republic.
Relativistic restricted active space (RAS) second-order multireference perturbation theory (MRPT2) methods, incorporating spin-orbit (SO) coupling perturbatively via state interaction (SO-MRPT2/RASSCF), were used to reproduce the absorption spectra of parent metalloporphyrins containing the Mg, Zn, Co, Ni, Cu, or FeCl ions in the 12,500-40,000 cm region. Particular attention was paid to the interaction between the porphyrin ring and the metal 3 electrons in states of different multiplicities (we used metal 3 and double -shell or 3' orbitals). For this class of compounds, the -electron valence state perturbation theory (NEVPT2) method is superior to the complete active space perturbation theory (CASPT2) and successfully reproduces the energies of all four characteristic transitions (, , , and ) of closed-shell metalloporphyrins.
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