LOYOLA COLLEGE (AUTONOMOUS), CHENNAI – 600 034

M.Sc. DEGREE EXAMINATION – CHEMISTRY

WD 52

FOURTH SEMESTER – April 2009

CH 4956 – ADVANCED COORDINATION CHEMISTRY

 

 

 

Date & Time: 28/04/2009 / 9:00 – 12:00     Dept. No.                                              Max. : 100 Marks

 

 

PART-A

Answer all questions. Each question carries two marks

 

1. Define relaxivity. What are contrast enhancing agents for MRI?
2. The direct excitation of lanthanide ions does not give rise to significant emission. Comment.
3. Mention the structural components of dendrimers and cite a few functional dendrimers.
4. How do you differentiate low-spin and high-spin octahedral complexes of Fe(II)?
5. How do you infer spin-orbit coupling from electronic spectroscopy? Mention one example where such an effect is very predominant.
6. Illustrate transmetallation reaction with an example.
7. What are radiopharmaceuticals? Cite two examples.
8. What are optically transparent electrodes? Where is it employed?
9. What is pseudorotaxane? Cite an example.
10. Define quantum-up and quantum-down conversion processes.

 

PART-B

Answer eight questions. Each question carries five  marks

 

11. Explain the theory of relaxivity by Gd(III)-based contrast agents for MRI and highlight the parameters of relaxivity optimization.
12. Explain the synthetic strategies of polynuclear supramolecular assemblies involving d,d– and d,f -metal ions.
13. Explain the synthesis of any three supramolecular architectures.
14. What are the general methods of constructing rotaxanes? Explain the construction of such assemblies by each method.
15. The ³¹P NMR spectrum of [Rh(PPh₃)₃Cl₃] consists of two triplets and two doublets. Interpret the spectrum and comment upon its geometry.
16. Explain the principle and methodology of constructing a dye sensitized solar cell.
17. Explain the synthesis and properties of dendrimer-encapsulated gold nanoparticles.
18. Discuss the structural features of ferredoxins and rubredoxins.
19. Explain the electronic spectral features of tetragonally distorted octahedral complexes of low-spin Co(III) with a qualitative energy level diagram.
20. Explain the template synthesis of catenanes with illustrative examples.
21. Explain template synthesis of macrocyclic ligands and their complexes with illustrative examples.
22. Define molecular machine. Explain the construction of two such devices.

 

 

 

 

 

PART-C

Answer four questions. Each question carries ten marks

 

23. What is an A-ET-E molecular device?

Explain the photochemistry of encapsulated complexes of Eu(II) and Tb(III).

24a.Explain zero field splitting and hyperfine splitting.

1. The EPR spectrum of a high spin Mn(II) complex doped onto a diamagnetic host consists of 30 lines. Explain the spectrum with the help of hyperfine splitting energy level diagram.
2. Explain the synthetic strategies for compartmental macrocyclic- and macroacyclic ligands and their complexes of lanthanides and actinides.
3. What are molecular shuttles? Give an account of the construction of molecular shuttles controlled by (a) electrochemically, (b) pH, and (c) redox process.

27a. Explain the principle and methodology of cyclic voltammetry.

b.The cyclic voltammogram of a Co(III) complex consists of two cathodic waves at     E_pc = -0.65  and -0.42 V and two anodic waves at E_pa = -0.52  and -0.35 V at the scan rate of 50 mV s^-1 with i_pc values of 25 and 19 mA, and i_pa values of 23 and 19 mA. Explain the electrochemical behavior of the system from the computed parameters.

28a. Explain the synthesis of dendrimers with two examples.

1. Give an account of the application potential of dendrimers.

 

 

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