Bi3+ and Pb2+ uptake by a monolacunary Keggin-type [PW11O39]7- anion leads to the formation of [PW11O39Bi]4- and [PW11O39Pb]5- complexes with a stereochemically active lone pair at the incorporated heterometal. The two complexes were isolated as (TBA)4[PW11O39Bi] (1) and (TBA)5[PW11O39Pb] (2) and characterized by 31P and 183W NMR spectroscopy, high-resolution electrospray mass-spectrometry (HR-ESI-MS) and cyclic voltammetry (CV). EXAFS and XANES data confirm the unchanged oxidation state and ψ-square pyramidal geometry of Bi3+ and Pb2+ in 1 and 2. DFT calculations were used in order to (i) confirm the absence of ligands attached to the heterometal sites in both complexes and localize the lone pair, and (ii) assign all signals in the 183W NMR spectra. Complexes 1 and 2 demonstrate photoluminescence (PL). A reversible change in the PL spectra of both complexes in the presence of water vapor has been detected. On the contrary, PL data for sandwich-type ((CH3)4N)4K3[H4(PW11O39)2Bi]·25H2O (3) do not show sensitivity to water vapor.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1039/d1dt00499a | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
A coumarin and 1,8-napthyridine conjugated novel molecular hybrid: Synthesis, DFT insights and unveiling the selective fluorescent sensing of Hg ions with live-cell imaging application.
Spectrochim Acta A Mol Biomol Spectrosc
December 2024
Department of Chemistry, School of Sciences, National Institute of Technology Andhra Pradesh, Tadepalligudem 534101, Andhra Pradesh, India. Electronic address:
Herein, we have used a simple synthetic strategy to access a novel non-sulfur fluorescent molecular probe coumarin and 1,8-napthyridine conjugated probe DNCS. The developed probe has great selectivity and sensitivity for detecting Hg ions. Our photophysical properties evaluation for the synthesized probe with different metal ions (Ba, Al, Ca, Bi, Ce, Cd, Cu, Sr, Co, Fe, Cr, Fe, Mn, Hg, Zn, Pb, Ni, and Sn) unveiled the very selective and sensitive fluorescence sensing behavior with Hg ions in the energy window of near UV and visible light radiation in an organic aqueous solvent mixture (EtOH and water).
View Article and Find Full Text PDFDouble-Armed 18- and 21-Membered Macrocycles as Potential Chelators for Lead and Bismuth Radiopharmaceuticals.
Inorg Chem
November 2024
A. N. Nesmeyanov Institute of Organoelement Compounds of Russian Academy of Sciences, 119991 st. Vavilova, 28, GSP-1, Moscow 119991, Russian Federation.
With increasing clinical applications and interest in targeted alpha therapy, there is growing interest in developing alternative chelating agents for [Pb]Pb and [Bi]Bi that exhibit rapid radiolabeling kinetics and kinetic inertness. Herein we report the synthesis and detailed investigation of diacetate and dipicolinate 18- and 21-membered macrocyclic chelators BADA-18, BADA-21, BADPA-18, and BADPA-21 for the complexation of Pb and Bi ions with potential use in the preparation of radiopharmaceuticals. The formation of mononuclear complexes was established by using ESI-mass spectrometry, and their stability constants were determined by potentiometric titration.
View Article and Find Full Text PDFThe HSmacropa Series: Increasing the Chemical Softness of Hmacropa with Sulfur Atoms to Chelate Radiometals [Bi]Bi and [Pb]Pb for Radiopharmaceutical Applications.
Inorg Chem
November 2024
Department of Chemistry, Simon Fraser University, Burnaby, British Columbia V5A 1S6, Canada.
The effects of replacing nitrogen with sulfur atoms in the 18-membered macrocycle of the Hmacropa chelator on the binding affinity and stability of "intermediate" (radio)metal [Pb]Pb and [Bi]Bi complexes are investigated. The 1,4,10,13-tetraoxo-7,16-diazacyclooctadecane backbone was replaced with derivatives containing sulfur in the 1,4- or the 1,4,10,13-positions to yield the novel chelators HSmacropa (NOS) and HSmacropa (NOS), respectively. Trends on the Pb- and Bi-complex stability constants, coordination chemistry, radiolabeling, and kinetic inertness were assessed via potentiometric titrations, UV-vis spectroscopy, NMR spectroscopy, X-ray crystallography and density functional theory (DFT) calculations.
View Article and Find Full Text PDFOptical Basicity for Understanding the Lewis Basicity of Chloride Molten Salt Mixtures.
J Phys Chem Lett
May 2024
Chemical and Materials Engineering, University of Nevada, Reno, 1664 North Virginia Street, Reno, Nevada 89557-0388, United States.
Currently, there is a lack of reliable measurement techniques for understanding the basicity of molten chloride salts. Optical basicity, an ultraviolet-visible (UV-vis) spectroscopic method for measuring Lewis basicity, is explored for its applicability to molten chloride salts. Shifts in probe ion (Pb and Bi) electronic transitions are observed that show that cations in chloride salts follow the same basicity series as in oxide melts, and an increase in basicity is observed with increasing temperature.
View Article and Find Full Text PDFCOF-Topological Quantum Material Nano-heterostructure for CO to Syngas Production under Visible Light.
Angew Chem Int Ed Engl
April 2024
Chemistry and Physics of Materials Unit (CPMU), School of Advanced Materials (SAMat), International Centre for Materials Science (ICMS), Jawaharlal Nehru Centre for Advanced Scientific Research (JNCASR), 560064, Jakkur, Bangalore, India.
Efficient solar-driven syngas production (CO+H mixture) from CO and HO with a suitable photocatalyst and fundamental understanding of the reaction mechanism are the desired approach towards the carbon recycling process. Herein, we report the design and development of an unique COF-topological quantum material nano-heterostructure, COF@TI with a newly synthesized donor-acceptor based COF and two dimensional (2D) nanosheets of strong topological insulator (TI), PbBiTe. The intrinsic robust metallic surfaces of the TI act as electron reservoir, minimising the fast electron-hole recombination process, and the presence of 6s lone pairs in Pb and Bi in the TI helps for efficient CO binding, which are responsible for boosting overall catalytic activity.
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!