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Crystal Field Theory - Tetrahedral and Square Planar Complexes02:46

Crystal Field Theory - Tetrahedral and Square Planar Complexes

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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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Ladder Diagrams: Complexation Equilibria01:07

Ladder Diagrams: Complexation Equilibria

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Ladder diagrams are useful for evaluating equilibria involving metal-ligand complexes. The vertical scale of the ladder diagram represents the concentration of unreacted or free ligand, pL. The horizontal lines on the scale depict the log of stepwise formation constants for metal-ligand complexes and indicate the dominant species in all the regions.
The formation constant, K1, for the formation of Cd(NH3)2+ complex from cadmium and ammonia is 3.55 × 102. Log K1 (i.e. pNH3) is 2.55, and...
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Valence Bond Theory02:42

Valence Bond Theory

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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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EDTA: Auxiliary Complexing Reagents01:26

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EDTA titrations are usually carried out in highly basic conditions, where the fully deprotonated form of EDTA, Y4−, actively complexes with the free metal ions in the solution. Several metal ions precipitate as hydrous oxide (hydroxides, oxides, or oxyhydroxides) under these conditions, lowering the concentration of free metal ions in the solution. For this reason, auxiliary complexing agents or ligands such as ammonia, tartrate, citrate, or triethanolamine are used in EDTA titrations to...
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Coordination Number and Geometry02:57

Coordination Number and Geometry

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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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Formation of Complex Ions03:45

Formation of Complex Ions

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A type of Lewis acid-base chemistry involves the formation of a complex ion (or a coordination complex) comprising a central atom, typically a transition metal cation, surrounded by ions or molecules called ligands. These ligands can be neutral molecules like H2O or NH3, or ions such as CN− or OH−. Often, the ligands act as Lewis bases, donating a pair of electrons to the central atom. These types of Lewis acid-base reactions are examples of a broad subdiscipline called coordination...
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Thermochemical Studies of NiII and ZnII Ternary Complexes Using Ion Mobility-Mass Spectrometry
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Quantifying Triplet State Formation in Zinc Dipyrrin Complexes.

Norah Z Alqahtani1, Toni G Blevins1, Catherine E McCusker1

  • 1Department of Chemistry , East Tennessee State University , Johnson City , Tennessee 37614 , United States.

The Journal of Physical Chemistry. A
|October 31, 2019
PubMed
Summary

Zinc dipyrromethene complexes show potential as earth-abundant photocatalysts. Their triplet quantum yields, especially with heavy atoms, rival successful organic photosensitizers.

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Area of Science:

  • Photochemistry
  • Materials Science
  • Solar Energy Conversion

Background:

  • Photocatalysis utilizes solar energy for chemical synthesis, but relies on expensive rare metals.
  • Earth-abundant alternatives are needed to advance photocatalysis.
  • Zinc dipyrromethene complexes offer a potential sustainable solution, yet their photophysical properties require investigation.

Purpose of the Study:

  • To quantify triplet state formation in zinc dipyrromethene complexes.
  • To investigate the influence of heavy atoms and solvent polarity on triplet yields.
  • To assess the potential of these complexes as photocatalytic sensitizers.

Main Methods:

  • Transient absorption spectroscopy was employed to measure triplet state formation.
  • Two zinc dipyrromethene complexes, with and without heavy atoms, were studied.
  • Experiments were conducted in different solvents (toluene and THF).

Main Results:

  • Without heavy atoms, triplet quantum yields were 16% (toluene) and 27% (THF).
  • With heavy iodine atoms, triplet quantum yields increased significantly to 62-63%.
  • Heavy atom effect on triplet yield was independent of solvent polarity, unlike the unsubstituted complex.

Conclusions:

  • Triplet formation pathways differ between heavy-atom substituted and unsubstituted zinc dipyrromethene complexes.
  • The observed triplet yields are competitive with established organic photosensitizers.
  • Zinc dipyrromethene complexes demonstrate considerable potential for solar energy applications.