LOYOLA COLLEGE (AUTONOMOUS), CHENNAI – 600 034

GH 49

M.Sc. DEGREE EXAMINATION – CHEMISTRY

FOURTH SEMESTER – APRIL 2008

    CH 4956 – ADVANCED COORDINATION CHEMISTRY

 

 

 

Date : 25/04/2008            Dept. No.                                        Max. : 100 Marks

Time : 9:00 – 12:00

 

PART-A

Answer all questions. Each question carries two marks  (10 x 2 = 20)

 

1. Give the term symbol of a d² metal ion for the ground state.
2. What is nephelauxetic series? How is it constructed?
3. Sketch the EPR spectrum of [VO(glycollate)₂]^2-.
4. Explain the ¹⁹F NMR spectrum of SbF₅.base adduct.
5. Draw the structural unit of (a) 2Fe-2S (b) 4Fe-4S proteins.
6. Illustrate transmetallation reaction with an example.
7. Explain metal ion induced ring contraction in the synthesis of macrocycles.
8. What are optically transparent electrodes?
9. What is rotaxane? Cite an example.
10. Cite an A-ET-E device involving a lanthanide metal ion.

 

 

PART-B

Answer eight questions. Each question carries five  marks  (8 x 5 = 40)

 

11. How is the electronic spectrum of [Ti(H₂O)₆]³⁺ interpreted using Orgel diagram.
12. Write a note on charge transfer transition in metal complexes.
13. What are Racah parameters? Explain their significance.
14. Explain the application of Mossbauer spectroscopy in the study of p-back bonding in transition metal complexes?
15. Discuss the role of manganese cycle in splitting water during photosynthesis.
16. How do metal porphyrin complexes act as model systems for electron transfer processes?
17. Explain the synthesis of dendrimer-encapsulated gold nanoparticles.
18. Explain the synthetic strategies of (a) a molecular grid and (b) a molecular rectangle.
19. What are the general methods of constructing rotaxanes? Explain the construction of such assemblies by each method.
20. Explain the template synthesis of catenanes with illustrative examples.
21. What are molecular shuttles? Explain the synthesis of such species controlled by (a) electrochemical methods, (b) pH, and (c) redox process.
22. Define molecular machine. Explain the synthesis of a molecular gear.

 

 

 

PART-C

Answer four questions. Each question carries ten marks    (4 x 10 = 40)

 

23. Discuss the ¹H NMR spectral studies of two organometallic fluxional molecules.

24a. Explain zero field splitting and hyperfine splitting.

1. Explain the EPR spectrum of [Mn(H₂O)₆]²⁺ with the help of hyperfine splitting energy level diagram.
2. Discuss the photo- and redox chemistry involved in photosystem-I.

26a.  Explain the principle and methodology of cyclic voltammetry.

1. 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.
2. Explain template synthesis of macrocyclic ligands and their mono- and dinuclear complexes with illustrative examples.

27a. Explain the principle and methodology of constructing a dye sensitized solar cell.

1. Give an account of Ru(II) polypyridyl complexes used in the construction of solar cells.

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

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

 

 

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