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Structural Isomerism02:34

Structural Isomerism

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Isomerism in Complexes
Isomers are different chemical species that have the same chemical formula. Structural isomerism of coordination compounds can be divided into two subcategories, the linkage isomers and coordination-sphere isomers.
Linkage isomers occur when the coordination compound contains a ligand that can bind to the transition metal center through two different atoms. For example, the CN− ligand can bind through the carbon atom or through the nitrogen atom. Similarly, SCN− can...
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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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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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Ziegler–Natta polymerization is another form of addition or chain‐growth polymerization used for synthesizing linear polymers over branched polymers. The catalyst used for polymerization is the Ziegler–Natta catalyst, named after Karl Ziegler and Giulio Natta, who developed it in 1953. This catalyst is an organometallic complex of titanium tetrachloride and triethyl aluminum, with the active form of the catalyst being an alkyl titanium compound. Using the Ziegler–Natta...
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Ionic crystals consist of two or more different kinds of ions that usually have different sizes. The packing of these ions into a crystal structure is more complex than the packing of metal atoms that are the same size.
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Amide-Driven Secondary Building Unit Structural Transformations between Zn(II) Coordination Polymers.

Daniel Ejarque1, Teresa Calvet2, Mercè Font-Bardia3

  • 1Departament de Química, Universitat Autònoma de Barcelona, Bellaterra, 08193 Barcelona, Spain.

Crystal Growth & Design
|August 16, 2022
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Summary
This summary is machine-generated.

Four new zinc coordination polymers (CPs) were synthesized and exhibit reversible structural transformations. These CPs show potential as molecular switches, with distinct photoluminescence properties influenced by their amide moieties.

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Area of Science:

  • Coordination Chemistry
  • Materials Science
  • Supramolecular Chemistry

Background:

  • Coordination polymers (CPs) with reversible molecular arrays are promising for molecular switches.
  • External stimuli can induce structural changes in CPs, altering their properties.

Purpose of the Study:

  • To synthesize and characterize four Zn(II) coordination polymers (CPs) using α-acetamidocinnamic acid (HACA) and 4,4'-bipyridine (4,4'-bipy).
  • To investigate the structural transformations and reversibility of these CPs.
  • To explore the effect of amide moieties on CP structure and photoluminescence.

Main Methods:

  • Synthesis of four Zn(II) CPs via reaction of Zn(OAc)2·2H2O, HACA, and 4,4'-bipy.
  • Dissolution-recrystallization structural transformations (DRSTs) to generate different CP structures.
  • Single-crystal X-ray diffraction to analyze crystal structures and secondary building units (SBUs).
  • Solid-state photoluminescence spectroscopy to study emission properties.

Main Results:

  • Four Zn(II) CPs were synthesized, including an initial CP and three others formed via DRSTs.
  • The crystal structures revealed diverse SBUs (monomeric, dimeric, trimeric) linked by 4,4'-bipy ligands.
  • Solvent and temperature influenced SBU formation and amide moiety orientation.
  • Reversibility and interconversion between the four CPs were demonstrated.
  • Solid-state photoluminescence showed distinct emission for one CP (4) compared to others (1-3), attributed to amide effects.

Conclusions:

  • The study successfully synthesized and characterized four interconvertible Zn(II) coordination polymers.
  • Structural diversity and reversibility were achieved through DRSTs, influenced by solvent and temperature.
  • The amide moieties play a crucial role in dictating SBU formation and solid-state photoluminescence properties.