Computational methods (DFT at the B3LYP, PBE0 and m06 levels, MO fragments decomposition, and the broken symmetry approach) have been used to evaluate the influence of the bridging ligand (BL) on the extent of electron delocalization in coordination polymers based on diruthenium tetracarboxylates. The efficiency of three different nitrogenated axial ligands, namely pyrazine (pz), phenazine (phz), and tetrazine (tz), to mediate electron coupling between Ru2(II,II) or Ru2(II,III) centers has been estimated through four different parameters: calculated Ru-N distances, HOMO-LUMO gaps, HOMO and LUMO compositions, and magnetic coupling constants J. All these parameters pointed toward a coordination polymer based on Ru2(II,II) centers axially linked by tetrazine being the best candidate for exhibiting electron delocalization through the Ru2-BL framework. Such a compound has been synthesized and characterized; its vis-NIR spectrum exhibited the predicted features, mainly an intense low-energy MLCT band, assigned to the expected Ru2(II,II) → tz process associated with electron delocalization.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1021/ct400179t | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Hydroxyl Radical-π Interaction in a Single Crystal.
JACS Au
January 2025
Department of Chemistry, Indian Institute of Technology Roorkee, Roorkee 247667, Uttarakhand, India.
Numerous attempts for organic radical stability mostly entail steric hindrance, spin-delocalization, supramolecular interaction with the host, π-π interactions, and hydrogen bonding. To date, there is no report of single crystals containing a hydroxyl radical (OH). In this work, we have stabilized OH in the crystal, which has been obtained from the filtrate after separating the precipitate of the chromenopyridine radical (DCP(2)) from the reaction mixture.
View Article and Find Full Text PDFProbing the structural transformation and bonding of metal-boride clusters MB (M = La, Ta, Re, Ir).
Phys Chem Chem Phys
January 2025
Department of Chemistry and Guangdong Provincial Key Laboratory of Catalytic Chemistry, Southern University of Science and Technology, Shenzhen 518055, China.
Theoretical investigations using density functional theory (DFT) and wavefunction theory (WFT) have been performed to understand the geometric and electronic structures, chemical bonding, and structural transformation of 5d6s-metal doped triboron clusters MB (M = La, Ta, Re, Ir; = 1, 3, 5, 7). Global-minimum structural searches find that early-metal doped MB (M = La, Ta) clusters adopt a two-dimensional (2D) planar structure, with σ- and π-type delocalized molecular orbitals (MOs) consisting of M-5d and B-2p atomic orbitals (AOs) identified by chemical bonding analysis. In contrast, late-metal doped MB (M = Re, Ir) clusters prefer three-dimensional (3D) structures of near-pyramidal and triangular pyramid geometries, respectively, which exhibit enhanced stability involving σ- and δ-type M(5d)-B(2p) interactions.
View Article and Find Full Text PDFCuS@Ag Heterostructure-based Surface Plasmonic Coupling Electrochemiluminescence Sensor for Glioma miRNA-124-3p Detection.
Biosens Bioelectron
January 2025
Department of Analytical Chemistry, College of Chemistry, Jilin University, Changchun, 130012, China. Electronic address:
As an emerging class of extended crystalline organic materials, covalent organic framework (COF)-based aggregation-induced emission luminogen (AIE-gen) exhibited encouraging emissive properties. In this work, 4',4'',4‴,4‴'-(1,1,2,2-Ethenetetrayl)tetra(4-biphenylcarbaldehyde) (ETBC) as AIEgen was used to prepare AIE-COF (ET-COF-COOH) luminescent nanoprobe. ETBC and 1,3,5-Tris(4-aminophenyl)benzene (TAPB) had an extended π electronic system that allowed electron delocalization and overlapping transport.
View Article and Find Full Text PDFHeteroatom sulfur-doping in single-atom FeNC catalysts for durable oxygen reduction performance in zinc-air batteries.
J Colloid Interface Sci
January 2025
Department of Chemistry & Institute for Sustainable Energy, College of Sciences, Shanghai University, Shanghai 200444, PR China. Electronic address:
Heteroatom doping into the transition metal-based catalysts is an effective strategy to improve the oxygen reduction reaction (ORR) kinetics. Herein, we proposed a one-step, soft template assisted, and green method for the synthesis of Sulfur (S) doped single atom FeNC catalyst. XAFS demonstrated that the Fe active sites in the FeNSC were more likely to possess the Fe-N configuration.
View Article and Find Full Text PDFActivating Redox Chemistry of Quinones for High Energy Density Aqueous Sodium-Ion Batteries.
J Am Chem Soc
January 2025
State Key Laboratory of Material Processing and Die & Mould Technology, School of Materials Science and Engineering, Huazhong University of Science and Technology, Wuhan 430074, P. R. China.
Anode materials with high capacity and suitable redox potential are crucial for improving the energy density of aqueous sodium-ion batteries (ASIBs). And organic anode materials play a promising role due to their tunable electrochemical performance. However, the insufficient electroactive sites lead to a low capacity, hindering the elevation of energy density.
View Article and Find Full Text PDFWant AI Summaries of new PubMed Abstracts delivered to your In-box?
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!