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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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Electrocyclic reactions are reversible reactions. They involve an intramolecular cyclization or ring-opening of a conjugated polyene. Shown below are two examples of electrocyclic reactions. In the first reaction, the formation of the cyclic product is favored. In contrast, in the second reaction, ring-opening is favored due to the high ring strain associated with cyclobutene formation.
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For transition metal complexes, the coordination number determines the geometry around the central metal ion. Table 1 compares coordination numbers to molecular geometry. The most common structures of the complexes in coordination compounds are octahedral, tetrahedral, and square planar.
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Tetrahedral Complexes
Crystal field theory (CFT) is applicable to molecules in geometries other than octahedral. In octahedral complexes, the lobes of the dx2−y2 and dz2 orbitals point directly at the ligands. For tetrahedral complexes, the d orbitals remain in place, but with only four ligands located between the axes. None of the orbitals points directly at the tetrahedral ligands. However, the dx2−y2 and dz2 orbitals (along the Cartesian axes) overlap with the ligands less than the dxy,...
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Isomerism in Complexes
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Cycloheptatriene is a neutral monocyclic unsaturated hydrocarbon that consists of an odd number of carbon atoms and an intervening sp3 carbon in the ring. The three double bonds in the ring correspond to 6 π electrons, which is a Huckel number, and therefore satisfies the criteria of 4n + 2 π electrons. However, the intervening sp3 carbon disrupts the continuous overlap of p orbitals. As a result, cycloheptatriene is not aromatic.
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NIR-II Emission from Cyclometalated Dinuclear Pt(III) Complexes.

Irene Melendo1, Sara Fuertes1, Antonio Martín1

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New platinum(II) dinuclear complexes were synthesized and oxidized to platinum(III) derivatives. These diplatinum(III) complexes exhibit tunable near-infrared emission, influenced by axial ligands and temperature.

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Area of Science:

  • Coordination Chemistry
  • Organometallic Chemistry
  • Materials Science

Background:

  • Dinuclear platinum complexes are of interest due to their unique electronic and photophysical properties.
  • Understanding metal-metal interactions and the influence of ligands is crucial for designing novel functional materials.

Purpose of the Study:

  • To synthesize and characterize novel half-lantern Pt(II) dinuclear complexes.
  • To investigate the oxidation of these complexes to diplatinum(III) derivatives.
  • To explore the photophysical properties, particularly near-infrared emission, of the resulting Pt(II) and Pt(III) systems.

Main Methods:

  • Synthesis of half-lantern Pt(II) dinuclear complexes with specific ligands (1-naphthalen-2-yl-1H-pyrazole and mercaptopyrimidines).
  • Oxidation reactions using haloforms under various conditions (air, sunlight, dark).
  • Single-crystal X-ray diffraction for structural elucidation.
  • Spectroscopic analysis (absorption and emission) and Density Functional Theory (DFT) calculations.

Main Results:

  • Selective synthesis of single isomers of Pt(II) dinuclear complexes with short Pt-Pt distances.
  • Formation of oxidized diplatinum(III) derivatives with Pt-Pt bonds, influenced by axial ligands.
  • Observation of tunable low-energy absorptions and broad near-infrared (NIR) emissions (985-1070 nm at RT) dependent on axial ligands and temperature.

Conclusions:

  • The synthesized Pt(II) and Pt(III) dinuclear complexes demonstrate controllable photophysical properties.
  • Axial ligands play a significant role in tuning the electronic structure and emission characteristics.
  • These findings provide insights into the structure-property relationships of platinum complexes for potential optoelectronic applications.