Ligand field theory and CuCl2 colors

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SUMMARY

Copper(II) chloride (CuCl2) is a light brown solid that forms a blue-green dihydrate upon moisture absorption. According to ligand field theory, water acts as a stronger field ligand than chloride, leading to larger d orbital splitting in the dihydrate form. This should result in a longer wavelength color for the dihydrate compared to the anhydrous form; however, the observed color change contradicts this expectation. The discussion highlights the potential influence of charge-transfer transitions and the lack of octahedral symmetry in the hydrated complex as factors affecting the color observed.

PREREQUISITES
  • Understanding of ligand field theory
  • Knowledge of d orbital splitting
  • Familiarity with charge-transfer transitions
  • Basic concepts of coordination chemistry
NEXT STEPS
  • Research the effects of ligand strength on d orbital splitting in transition metal complexes
  • Study the role of charge-transfer transitions in color changes of coordination compounds
  • Examine the structural differences between hydrated and anhydrous forms of metal halides
  • Consult "Advanced Inorganic Chemistry" 6th edition for detailed insights on CuCl2 behavior
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Chemistry students, inorganic chemists, and researchers interested in coordination chemistry and the optical properties of transition metal complexes.

khanhhung2512
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Copper (ii) chloride is a light brown solid, which slowly absorbs moisture to form a blue-green dihydrate.
According to ligand field theory, water is a stronger field ligand than chloride. As a result, the dihydrate form should have a larger d orbital splitting than the anhydrous form. Thus, the color (complementary to the wavelength absorbed) of the dihydrate form should have a longer wavelength than the anhydrous form's. But why is the opposite observed here?
If my reasoning is not correct, then please tell me the reason for the color change above.
Thank you very much.
 
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Unless I am missing something, you got it wrong. Larger d orbital splitting means higher energy difference so a shorter wavelength.
 
Well, the color we see is complementary to the color absorbed.
 
There are a zillion of possible explanations.
There can be charge-transfer transitions invoved which have a much higher oscillator strength than the weak d-d transitions.
Also in the hydrated chloride there are two water molecules along the axis and four chlorines in the equatorial plane, so this complex doesn't have a symmetry octahedral symmetry.
 
khanhhung2512 said:
Well, the color we see is complementary to the color absorbed.

That's what I missed
grumpy_borek.png
 
These are two answers I found on the net http://answers.yahoo.com/question/index?qid=20110915202418AA2v9AN
While both answers seem wrong to me, one mentioned Advanced Inorganic Chemistry 6th ed (1999). p 868-869 (F. A. Cotton, G. Wilkinson, C. A. Murillo, M. Bochmann). If anyone has access to that book, please tell me what it really said.
Thanks.
PS: I only have access to the third edition of that book, so I don't know the corresponding pages.
 

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