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I had given an examination recently in which the question asked was:

Write the decreasing order for the intensity of color in $\ce{[CoCl4]^{2-}}$, $\ce{[Co(CN)4]^2-}$, $\ce{[Co(H2O)6]^2+}$

What my approach was to first find out the geometry of compounds after which I found the geometry as follows
$\ce{[CoCl4]^{2-}}$ : $\mathrm{sp^3}$,
$\ce{[Co(CN)4]^2-}$ : $\mathrm{dsp^2}$,
$\ce{[Co(H2O)6]^2+}$ : $\mathrm{sp^3d^2}$

Now, I approached the question with the thought that more the symmetry less is the intensity of the color of the compound, which gave me a conclusion about what I had learned earlier that intensity of color in $\mathrm{sp^3 > sp^3d^2}$. And as the symmetry of $\mathrm{dsp^2}$ is comparable to that of $\mathrm{sp^3d^2}$, in that the intensity of color would be more for strong field ligand.

This made me conclude to the answer $\ce{[CoCl_{4}]^{2-}$ > $[Co(CN)_{4}]^{2-}$ > $[Co(H2O)_{6}]^{2+}}$.

But I am really confused and not sure about this answer as maybe the intensity of the color is completely determined only by the nature of the ligand, or geometry is involved or not. I also have confusion about how should I compare the intensity of color in $\mathrm{dsp^2}$ and $\mathrm{sp^3d^2}$.

P.S.: If possible please answer the question with basics as I am a High School student and don't know much about Higher Chemistry.

TRC
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Bhanu Kiran
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    I don't think hybridization helps to predict intensity. Can you add what the textbook says? – AChem Jul 21 '21 at 14:22
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    Unfortunately: Why is it wrong to use the concept of hybridization for transition metal complexes? There won't be a simple answer; there might be a retrofit of an explanation using simpler models, but that will fit the situation only. – Martin - マーチン Jul 21 '21 at 21:06
  • @M.Farooq I have been taught about this by a teacher. He taught me that the intensity of colour in sp3 compound would be higher than sp3d2 as sp3 is more asymmetric. – Bhanu Kiran Jul 21 '21 at 21:32
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    Bhanu, I never heard of that. Ask your teacher to give a reference. – AChem Jul 21 '21 at 21:56
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    Qualitatively, asymmetric complex may allow breaking of the selection rules and its intensity may be higher. I do not recall seeing your teacher's explanation. – AChem Jul 21 '21 at 23:00
  • I'm giving JEE this year too, and so far I've always used this: More the crystal field splitting energy, more is the intensity of colour. Your reasoning of symmetry I'm hearing for the first time. (P.S - If your teacher gives a reference, please share it here. Also, when NTA releases the answer key, please update the final order. Thank you.) – TRC Jul 22 '21 at 13:57
  • @TRC If it was only on the basis of Crystal field splitting energy then I am definitely losing marks over here as then the answer would clearly be CN>H2O>Cl. – Bhanu Kiran Jul 22 '21 at 22:04
  • That is why I am scared of this question, losing 5 marks in this would literally bring me down like 700-800 rank. – Bhanu Kiran Jul 22 '21 at 22:12
  • Forget about hybridization in coordination chemistry. This is nothing to do with colors! This question is really poorly worded by your examination board and please tell them to update this century old chemistry syllabus. By color intensity, are they implying that hue of the color of the complex or the intensity of eletronic transition? – AChem Jul 22 '21 at 23:25
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    Anyway, let us take it literally that they want you to predict intensity of transitions in complexes. "Intensity" in absorption spectroscopy has a different meaning altogether. It means how strong is the absorption of light (molar absorptivity). It is not a trivial task to predict just by this given information. It is a cruelty to ask this question from college students. The second problem with this question is that it is asking you to compare three tetrahedral or perhaps square planar complexes with an octahedral one. – AChem Jul 22 '21 at 23:25
  • Try to look at this link. Orgel diagrams

    With that tetrachloro cobalt complex should absorb strongly than octaherdral cobalt complex.

    enter image description here

    – AChem Jul 22 '21 at 23:25
  • @M.Farooq I could probably go on ranting about this exam for an hour. But that's not going to help anyone. If the OP, and I, want to get into a good engineering college, we have to bear with them. The worst part is that they don't even have a fixed syllabus - they just give the broad topics and we are expected to memorize as much as we can (and afterwards? Over 90% of students going into engineering will never need chemistry knowledge (except those in metallurgy branch) - obsolete methods, useless theories that have been long proven wrong.) – TRC Jul 23 '21 at 03:58
  • @BhanuKiran I'm not completely sure, but yes, that's the option I'd have marked, had I been in your shift. From the feedback you got here you must have realized that it's an utterly nonsensical question they asked. When CBSE conducted JEE Mains till 2-3 years ago the questions were better - they made you think, not score easy marks based on rote memorization. I don't think they'll ask such questions in Advanced either. It's just the gift of our dear N-T-A. – TRC Jul 23 '21 at 04:11
  • Yep, that's what I was thinking during the examination, how are they even comparing the intensity of colour in completely different hybridisations (considering hybridisation is valid in coordination compounds). I hope the questions are better framed in advance. – Bhanu Kiran Jul 23 '21 at 04:19
  • @BhanuKiran What is the answer given by NTA? – TRC Jul 31 '21 at 04:18
  • @TRC I uploaded the question wrong over here, It was for Ni and not Co. The answer for Ni was [NiCl4]2->[Ni(H2O)6]2+>[Ni(CN)4]2-. – Bhanu Kiran Jul 31 '21 at 04:48
  • I thought the same way, sp3 hybridization would have had the highest intensity but I completely don't understand how they have compared between H2O and CN. – Bhanu Kiran Jul 31 '21 at 04:51
  • @TRC I mean if they had considered strong field ligand then the answer would have been reversed, most probably something with hybridization? – Bhanu Kiran Jul 31 '21 at 04:54
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    Seeing the answer now, the best I can do is to hazard a guess - for weak field ligand the energy gap for electronic transitions is less. Less energy gap means it's easier for electrons to jump back and forth. More electrons jumping implies more photons being emitted/absorbed - so more intense colour. – TRC Jul 31 '21 at 07:06
  • @TRC I think that's right and also splitting energy of octahedral complex is less than square planar hence octahedral will have more intensity, but there's also a problem that Cl is weaker ligand than H2O which becomes contradictory. Feels like this question was data-based and we had to memorise it. – Bhanu Kiran Jul 31 '21 at 08:07
  • Exactly - it cannot be explained theoretically, as others have already pointed out. – TRC Jul 31 '21 at 14:21

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