Detailed in the present investigation are results pertaining to the photoelectron spectroscopy of negatively charged atomic ions and their isoelectronic molecular counterparts. Experiments utilizing the photoelectron imaging technique are performed on the negative ions of the group 10 noble metal block (i.e. Ni-, Pd-, and Pt-) of the periodic table at a photon energy of 2.33 eV (532 nm). The accessible electronic transitions, term energies, and orbital angular momentum components of the bound electronic states in the atom are then compared with photoelectron images collected for isoelectronic early transition metal heterogeneous diatomic molecules, M-X- (M = Ti,Zr,W; X = O or C). A superposition principle connecting the spectroscopy between the atomic and molecular species is observed, wherein the electronic structure of the diatomic is observed to mimic that present in the isoelectronic atom. The molecular ions studied in this work, TiO-, ZrO-, and WC- can then be interpreted as possessing superatomic electronic structures reminiscent of the isoelectronic elements appearing on the periodic table, thereby quantifying the superatom concept.
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http://dx.doi.org/10.1073/pnas.0911240107 | DOI Listing |
Nature
March 2025
Key Laboratory of Advanced Display and System Applications of Ministry of Education, Shanghai University, Shanghai, People's Republic of China.
The electroluminescence performance of heavy-metal-free blue quantum dot (QD) light-emitting diodes (QLEDs) is much lower than that of state-of-the-art cadmium-based counterparts. Ecofriendly ZnSeTe QDs are an ideal alternative to cadmium-based blue QDs, but face issues with colour impurity and inferior stability caused by the aggregated tellurium (Te) that dominates compositional inhomogeneity. Here we developed an isoelectronic control strategy using congeneric sulfur coordinated with triphenyl phosphite (TPP-S) to construct homogeneous ZnSeTeS QDs with pure-blue emissions and near-unity photoluminescence quantum yield.
View Article and Find Full Text PDFJ Phys Chem Lett
February 2025
Department of Chemistry, Brown University, Providence, Rhode Island 02912, United States.
The closed-shell B, B, and B species are recognized recently to be electron-precise molecular wheels with three delocalized π-bonds reminiscent of benzene, giving rise to the concept of "borozene". The B borozene is especially stable because the B ring has the right size to host a central boron atom. Replacing a B atom by C yields a highly stable closed-shell CB, which is isoelectronic to B.
View Article and Find Full Text PDFJ Org Chem
February 2025
Faculty of Chemistry, Nicolaus Copernicus University, Gagarina Street 7, 87-100 Toruń, Poland.
The structural and photophysical properties in the halogen bonding environment were thoroughly studied for a newly synthesized series of fluorescent dyes and their model derivatives. The analysis revealed that the ground-state interactions among both series are likewise. The fluorescent dyes have push-pull topology, and there is a low-lying charge-transfer (CT) excited state in their electronic structure.
View Article and Find Full Text PDFJ Am Chem Soc
January 2025
Department of Chemistry and the Manitoba Institute for Materials, University of Manitoba, 144 Dysart Road, Winnipeg, Manitoba R3T 2N2, Canada.
The ability to manipulate excited-state decay cascades using molecular structure is essential to the application of abundant-metal photosensitizers and chromophores. Ligand design has yielded some spectacular results elongating charge-transfer excited state lifetimes of Fe(II) coordination complexes, but triplet metal-centered (MC) excited states─recently demonstrated to be critical to the photoactivity of isoelectronic Co(III) polypyridyls─have to date remained elusive, with temporally isolable examples limited to the picosecond regime. With this report, we show how strong-field donors and intramolecular π-stacking can conspire to stabilize a long-lived MC excited state for a remarkable 4.
View Article and Find Full Text PDFJ Am Chem Soc
November 2024
Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford, South Parks Road, Oxford, OX1 3QR, United Kingdom.
Molecular chains of two-coordinate carbon atoms (cumulenes) have long been targeted, due to interest in the electronic structure and applications of extended π-systems, and their relationship to the carbon allotrope, carbyne. While formal (isoelectronic) B═N for C═C substitution has been employed in two-dimensional (2-D) materials, unsaturated one-dimensional all-inorganic "molecular wires" are unknown. Here, we report high-yielding synthetic approaches to heterocumulenes containing a five-atom BNBNB chain, the geometric structure of which can be modified by choice of end group.
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