Unsupported non-bridged uranium–carbon double bonds have long been sought after in actinide chemistry as fundamental synthetic targets in the study of actinide-ligand multiple bonding. Here we report that, utilizing I_h(7)-C₈₀ fullerenes as nanocontainers, a diuranium carbide cluster, U=C=U, has been encapsulated and stabilized in the form of UCU@I_h(7)-C₈₀. This endohedral fullerene was prepared utilizing the Krätschmer–Huffman arc discharge method, and was then co-crystallized with nickel(II) octaethylporphyrin (Ni^II-OEP) to produce UCU@I_h(7)-C₈₀·[Ni^II-OEP] as single crystals. X-ray diffraction analysis reveals a cage-stabilized, carbide-bridged, bent UCU cluster with unexpectedly short uranium–carbon distances (2.03 Å) indicative of covalent U=C double-bond character. The quantum-chemical results suggest that both U atoms in the UCU unit have formal oxidation state of +5. The structural features of UCU@I_h(7)-C₈₀ and the covalent nature of the U(f¹)=C double bonds were further affirmed through various spectroscopic and theoretical analyses.

The concept of oxidation state (OS) is based on the concept of Lewis electron pairs, in which the bonding electrons are assigned to the more electronegative element. This approach is useful for keeping track of the electrons, predicting chemical trends, and guiding syntheses. Experimental and quantum‐chemical results reveal a limit near +8 for the highest OS in stable neutral chemical substances under ambient conditions. OS=+9 was observed for the isolated [IrO₄]⁺ cation in vacuum. The prediction of OS=+10 for isolated [PtO₄]²⁺ cations is confirmed computationally for low temperatures only, but hasn't yet been experimentally verified. For high OS species, oxidation of the ligands, for example, of O⁻² with formation of ^.O⁻¹ and O−O bonds, and partial reduction of the metal center may be favorable, possibly leading to non‐Lewis type structures.

The chemical elements are the “conserved principles” or “kernels” of chemistry that are retained when substances are altered. Comprehensive overviews of the chemistry of the elements and their compounds are needed in chemical science. To this end, a graphical display of the chemical properties of the elements, in the form of a Periodic Table, is the helpful tool. Such tables have been designed with the aim of either classifying real chemical substances or emphasizing formal and aesthetic concepts. Simplified, artistic, or economic tables are relevant to educational and cultural fields, while practicing chemists profit more from “chemical tables of chemical elements.” Such tables should incorporate four aspects:(i)typical valenceelectron configurations of bonded atomsin chemical compounds (instead of the common but chemically atypical ground states of free atoms in physical vacuum);(ii)at least three basic chemical properties (valence number, size, and energyof the valence shells), their joint variation across the elements showing principal and secondary periodicity;(iii)elements in which the (sp)⁸, (d)¹⁰, and (f)¹⁴valence shells become closed and inert under ambient chemical conditions, thereby determining the “fix-points” of chemical periodicity;(iv)peculiar elements at the top and at the bottomof the Periodic Table. While it is essential that Periodic Tables display important trends in element chemistry we need to keep our eyes open for unexpected chemical behavior in ambient, near ambient, or unusual conditions. The combination of experimental data and theoretical insight supports a more nuanced understanding of complex periodic trends and non-periodic phenomena.

The Periodic Table, and the unique chemical behavior of the first element in a column (group), were discovered simultaneously one and a half centuries ago. Half a century ago, this unique chemistry of the light homologs was correlated to the then available atomic orbital (AO) radii. The radially nodeless 1s, 2p, 3d, 4f valence AOs are particularly compact. The similarity of r(2s)≈r(2p) leads to pronounced sp‐hybrid bonding of the light p‐block elements, whereas the heavier p elements with n≥3 exhibit r(ns) ≪ r(np) of approximately −20 to −30 %. Herein, a comprehensive physical explanation is presented in terms of kinetic radial and angular, as well as potential nuclear‐attraction and electron‐screening effects. For hydrogen‐like atoms and all inner shells of the heavy atoms, r(2s) ≫ r(2p) by +20 to +30 %, whereas r(3s)≳r(3p)≳r(3d), since in Coulomb potentials radial motion is more radial orbital expanding than angular motion. However, the screening of nuclear attraction by inner core shells is more efficient for s than for p valence shells. The uniqueness of the 2p AO is explained by this differential shielding. Thereby, the present work paves the way for future physical explanations of the 3d, 4f, and 5g cases.

The Periodic Law, one of the great discoveries in human history, is magnificent in the art of chemistry. Different arrangements of chemical elements in differently shaped Periodic Tables serve for different purposes. “Can this Periodic Table be derived from quantum chemistry or physics?” can only be answered positively, if the internal structure of the Periodic Table is explicitly connected to facts and data from chemistry. Quantum chemical rationalization of such a Periodic Tables is achieved by explaining the details of energies and radii of atomic core and valence orbitals in the leading electron configurations of chemically bonded atoms. The coarse horizontal pseudo-periodicity in seven rows of 2, 8, 8, 18, 18, 32, 32 members is triggered by the low energy of and large gap above the 1s and nsp valence shells (2 ≤ n ≤ 6 !). The pseudo-periodicity, in particular the wavy variation of the elemental properties in the four longer rows, is due to the different behaviors of the s and p vs. d and f pairs of atomic valence shells along the ordered array of elements. The so-called secondary or vertical periodicity is related to pseudo-periodic changes of the atomic core shells. The Periodic Law of the naturally given System of Elements describes the trends of the many chemical properties displayed inside the Chemical Periodic Tables. While the general physical laws of quantum mechanics form a simple network, their application to the unlimited field of chemical materials under ambient ‘human’ conditions results in a complex and somewhat accidental structure inside the Table that fits to some more or less symmetric outer shape. Periodic Tables designed after some creative concept for the overall appearance are of interest in non-chemical fields of wisdom and art.