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Periodic Classification of the Elements04:00

Periodic Classification of the Elements

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The periodic table arranges atoms based on increasing atomic number so that elements with the same chemical properties recur periodically. When their electron configurations are added to the table, a periodic recurrence of similar electron configurations in the outer shells of these elements is observed. Because they are in the outer shells of an atom, valence electrons play the most important role in chemical reactions. The outer electrons have the highest energy of the electrons in an atom...
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Transition metals are defined as those elements that have partially filled d orbitals. As shown in Figure 1, the d-block elements in groups 3–12 are transition elements. The f-block elements, also called inner transition metals (the lanthanides and actinides), also meet this criterion because the d orbital is partially occupied before the f orbitals.
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Coordination compounds and complexes exhibit different colors, geometries, and magnetic behavior, depending on the metal atom/ion and ligands from which they are composed. In an attempt to explain the bonding and structure of coordination complexes, Linus Pauling proposed the valence bond theory, or VBT, using the concepts of hybridization and the overlapping of the atomic orbitals. According to VBT, the central metal atom or ion (Lewis acid) hybridizes to provide empty orbitals of suitable...
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The alkali metal sodium (atomic number 11) has one more electron than the neon atom. This electron must go into the lowest-energy subshell available, the 3s orbital, giving a 1s22s22p63s1 configuration. The electrons occupying the outermost shell orbital(s) (highest value of n) are called valence electrons, and those occupying the inner shell orbitals are called core electrons. Since the core electron shells correspond to noble gas electron configurations, we can abbreviate electron...
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In most main group element compounds, the valence electrons of the isolated atoms combine to form chemical bonds that satisfy the octet rule. For instance, the four valence electrons of carbon overlap with electrons from four hydrogen atoms to form CH4. The one valence electron leaves sodium and adds to the seven valence electrons of chlorine to form the ionic formula unit NaCl (Figure 1a). Transition metals do not normally bond in this fashion. They primarily form coordinate covalent bonds, a...
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The hemoglobin in the blood, the chlorophyll in green plants, vitamin B-12, and the catalyst used in the manufacture of polyethylene all contain coordination compounds. Ions of the metals, especially the transition metals, are likely to form complexes.
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Lanthanoid-, Yttrium-, and Thorium-Centered Polyoxopalladates.

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Polyoxopalladates (POPs) exhibit two main structures: nanostar (Pd15) and cube (Pd12). Lanthanide and actinide central cations influence POP topology, with size impacting structure preference.

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Area of Science:

  • Inorganic Chemistry
  • Materials Science
  • Supramolecular Chemistry

Background:

  • Polyoxopalladates (POPs) are a class of inorganic clusters related to polyoxometalates.
  • Two common POP topologies are the Pd15 nanostar and the Pd12 cube.
  • The central metal cation is hypothesized to influence POP topology selection.

Purpose of the Study:

  • To investigate the influence of lanthanoid and actinide central cations on POP topology.
  • To synthesize and characterize phenylphosphonate-capped POPs with various central metal ions.
  • To correlate crystallographic data with computational and mass spectrometry results.

Main Methods:

  • Single-crystal X-ray diffraction for structural determination.
  • Powder X-ray diffraction (PXRD) for bulk material analysis.
  • Computational modeling to support structural hypotheses.
  • Electrospray ionization mass spectrometry (ESI-MS) for cluster identification.

Main Results:

  • Most lanthanoid-centered POPs crystallized as Pd15 nanostars, while Yb and Lu favored the Pd12 cube.
  • Computational studies indicated a topology transition from Pd15 to Pd12 in the third quarter of the lanthanide series.
  • PXRD suggested Pd15 is the favored topology in bulk materials, potentially due to Na+ interactions.
  • ESI-MS confirmed the presence of both Pd12 and Pd15 for smaller lanthanides, only Pd15 for larger ones, and no clusters for mid-series lanthanides.

Conclusions:

  • Central metal cation size and electronic properties play a role in POP topology selection, but it is not solely determined by size.
  • Discrepancies between single-crystal and bulk analyses highlight the complexity of POP crystallization.
  • Specific cation-lattice interactions, like Pd15-Na+, can influence observed bulk structures.