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Electronic spectra

: 1.why do many d-block metal complexes exhibit dd bands in their electronic spectra? A spin-forbidden transition becomes allowed if, for example, a singlet state mixes to some extent with a triplet state. This is possible by spinorbit coupling but for first row metals, the degree of mixing is small and so bands associated with spin-forbidden transitions are very weak . Spin-allowed dd transitions remain Laporte-forbidden and their observation is explained by a mechanism called vibronic coupling . An octahedral complex possesses a centre of symmetry, but molecular vibrations result in its temporary loss. At an instant when the molecule does not possess a centre of symmetry, mixing of d and p orbitals can occur. Since the lifetime of the vibration ( 10power 13 s) is longer than that of an electronic transition ( power 18 s), a dd transition involving an orbital of mixed

p-d character can occur although the absorption is still relatively weak In a molecule which is noncentrosymmetric (e.g. tetrahedral), pd mixing can occur to a greater extent and so the probability of dd transitions is greater than in a centrosymmetric complex. This leads to tetrahedral complexes being more intensely coloured than octahedral complexes. What Is ESR??? It is a branch of absorption spectroscopy in which radiation having frequency in microwave region is absorbed by paramagnetic substance to induce transition between magnetic energy level of electron with unpaired spin. Magnetic energy splitting is done by applying a static magnetic field.

ESR Phenomenon Is Shown By... Atoms having an odd number of electrons. Ions having partly filled inner electron shells. Molecule that carry angular momentum of electronic origin. Free radicals having unpaired electrons. Molecule with paired electrons and zero magnetic field Diamagnetic Molecules with unpaired electrons and magnetic moment-

Basic Principle Of ESR

The unpaired electrons are excited to a high energy state under the magnetic field by the absorption of microwave. The excited electron changes its direction of spin and relaxes into the ground state by emitting phonons. Microwave absorption is measured as a function of the magnetic field by ESR spectroscopy.

Spin Spin Splitting (Hyperfine Splitting . The interaction between an unpaired electron an nuclei with non zero nuclear spin is called the hyperfine interaction. This leads to splitting of the ESR line and is known as hyperfine spectrum

Absorptions arise from transitions between electronic energy levels: transitions between metal-centred orbitals possessing d character (dd transitions); . transitions between metal- and ligand-centred MOs which transfer charge from metal to ligand or ligand to metal. max = Amax c l ( max dm3 mol-1 cm-1) Values of "max range from close to zero (a very weak absorption) to >10 000dm3 mol_1 cm_1 (an intense absorption). Some important points (for which explanations will be given later in the section) are that the electronic spectra of: . d 1, d 4, d 6 and d 9 complexes consist of one absorption; . d 2, d 3, d 7 and d 8 complexes consist of three absorptions; . d 5 complexes consist of a series of very weak, relatively sharp absorptions. Selection rules Electronic transitions obey the following selection rules.Type equation here. Spin selection rule: S=0 Transitions may occur from singlet to singlet, or triplet to triplet states and so on, but a change in spin multiplicity is forbidden. Laporte selection rule: There must be a change in parity: allowed transitions: g u g, u u

forbidden transitions: g l=_ 1

This leads to the selection rule:

, allowed transitions are s " p, p -" d, d" f ; forbidden transitions are s" s, p " p, d " d, f" f ,s " d, p f etc.

2.Explain why an electronic transition for high-spin [Mn(H2O)6]2+is spin-forbidden, but for [Co(H2O)6]2+is spin-allowed? [Mn(H2O)6]2+ is high-spin d 5 Mn(II): A transition from a t2g to eg orbital is impossible without breaking the spin selection rule: S = 0, which means that S must remain the same. [Co(H2O)6]2+ is a high-spin d 7 Co(II) complex: A transition from a t2g to eg orbital can occur without violating the spin selection rule. NB: Transitions in both complexes are Laporte-forbidden.

ADDITONAL INFORMATION Laporte Allowed Partially allowed (some p-d mixing) Forbidden Partially allowed (some p-d mixing) Forbidden SPIN Allowed Allowed allowed Not allowed Forbidden Types of Spectra Charge transfer d-d d-d d-d d-d value 10000 500 8-10 4 0-0.2 Examples [Ticl6]2-,Kmno4 [CoBr4]2-,[Cocl4]2[Ti(H2O)6] 3+, [V(H2O)6]3+ [MnBr4][Mn (H2O)6]2+

The quantity (2S + 1) is the multiplicity of the term where S is the total spin quantum number. Terms for which(2S + 1) =1, 2, 3, 4 . . . (corresponding to S = 0, 1,2,3 etc are called singlets, doublets, triplets, quartets . . .

3..The electronic spectrum of an aqueous solution of [Ni(en)3]2+exhibits broad absorptions with ma 325, 550 and 900 nm.

(a) Suggest assignments for the electronic transitions. (b) Which bands are in the visible region? (a) [Ni(en)3]2+is a Ni(II), d 8 complex. From the Orgel diagram in the three transitions can be assigned; lowest wavelength corresponds to highest energy transition: 900nm assigned to 3T2g 3A2g 550nm assigned to 3T1g(F) 3 A2g 325nm assigned to 3T1g(P)3 A2g (b) Visible region spans 400750 nm, so only the 550nm absorbtion in this range

4.The term symbol of boron is? Ans;Boron (Z= 5) For boron (1s2 2s2 2p1) we need only consider the p electron for reasons outlined above. For this, j=1 so L= 1 (a P term); S = 1 2 and so (2S+1) =2 (a doublet term). J can take values (L+ S); (L+ S- 1) . . . (L S), and so J = 3/2 or 1/2 2. The term symbol for boron may be 2P3/2 or 2P1/2.

Microstates Term Components in an octahedral field S A1g P T1g D Eg + T2g F A2g + T2g + T1g G A1g + Eg + T2g + T1g 5.why KMno4 shows pink color intense?, give the reason Ans; yes its give Reason; in KMno4 the Mn7+ has d0 configuration, so no d-d transition occurs. Still it gives intense pink color due to LMCT. Absorb pale yellow& transmit pink color LMCT-charge transfer from ligand to metal Additional; LMCT which is reduced in the excited state, ESR is also give the internal Redox reaction, LMCT transition in visible the region spectra gives pink color 5a] in the ESR K2Cro4 gives a broad band of higher frequency& Kmno4 gives a band low frequency compared to that of K2cro4.Explain? Reason;; in KMno4 has Mn7+ & K2Cro4 has cr6+. Both are having no d-d transition due to LMCT The charge of the atom is required for some minimum amount of energy to promote ligand to metal level with in this case of higher oxidizing power (Mn7+) of KMno4 compared to that of cr6+, so charge transfer of the band occurs at low frequency(18012 cm-1) ADDITIONAL; Reo4- does not shows any color its nothing but white color.why? Ans;Reo4- energy required to charge transfer in UV region,it shows white color it absorbs Uv region& transmit white color 6.In UV visible region the f-orbital metal ions shows sharp band& d-orbital metal ions shows broad band.why? Ans; In d-orbital metal ions are absorped peaks appear to d-d transitions& effected by external environment such as a ligand& salvation effects,so absorption is broad band 7. in ESR spectrum of [Mo(CN)8]3- in solution consist of 1 line,but that of a c*13 enriched sample shows 9 lines. Why? Ans; Mo(1v) in [MO(CN)8]3- has a d1 configuration& only 1 line is expected in its ESR spectrum. But for the c*13 enriched sample, the n.o of hyperfine lines will be 9 by using 2nI+1formula.

C*13 I=1/2 & n=8, because 8 carbons in the cyanide group[s surround the Mo atom ,
8.[(NH3-Co-O-O-Co-(NH3)5 ]5+ The following structural formulate of the above complex are possible 1, The two cobalt (111) atoms may be connected by an o2- bridge 2. The cobalt (111 & 1v) may be connected by peroxy bridge 3. There may be two equivalent cobalt atoms, the unpaired electron is undergoing equal interaction with both cobalt atoms 4. There may be two equivalent cobalt atoms, but the unpaired Electron is Undergoing more interaction with one cobalt atom than the other Explain;If structure (1) is correct, expect single line in ESR

For structure (2), 8 lines are expected (I=7/2 for Co). For structure (3), 15 lines are expected. For structure (4), 64 line are expected, But actual ESR spectrum shows 15 lines This is reveals that structures (2) & (4) are not correct. But this supports structure (3). But this does not out the rule possibility of contribution of structure (1). Thus, it may be solid that the actual structure of cobalt complex may be a combination of structures (1) & (3). However the final structure of will depend upon the information obtained from o*17 Hyperfine splitting

Applications All application of ESR is based on three aspects, which are, Study of free radicals, Investigation of molecules in the triple state, and Study of inorganic compounds. . Biological systems From the ESR studies of variety of biological system such as, leaves, seeds, and tissue preparation, it is found that a definite, correlation exists between the concentration of free radicals and the metabolic activity of the plant material. ESR has studied the presence of free radicals in healthy and diseased tissues. Most of the oxidative enzymes function via one electron redox reaction involving the production of either enzyme bound free radicals or by a change in the valence state of transition metal ion. This has been conformed by ESR studies. Much of the ESR work on photosynthesis has been carried out with photosynthetic bacteria. The oxidation of bacteriochlorophyll in vitro produces an ESR signal.