ELECTRONIC ENERGY LEVELS OF

SOME TETRAGONAL Co2+ AND Cr2+ COMPLEXES

by

Mortaza Davari

A Thesis Submitted to the Faculty of

The College of Science

in Partial Fulfillment of the Requirements for the Degree of

Master of Science

Florida Atlantic University

Boca Raton, Florida

August 1996
 Electronic Energy Levels of

Some Tetragonal Cu2+ and C~+ Complexes

by

Mortaza Davari

This thesis was prepared under the direction of the candidate' s thesis advisor,

Dr. Jayarama Reddi Perumareddi, Department of Chemistry, and has been approved by

the members of his supervisory committee. It was submitted to the faculty of the College

of Science and was accepted in partial fulfillment of the requirements of the degree of

Master of Science.

SUPERVISORY COMMITTEE:

~c-•.:vv,_a-vv-~~
Thesis Advisor

~oCru J. ~

151/t~
I
Date

ii
 ABSTRACT

Author: Mortaza Davari

Title: Electronic Energy Levels of Some Tetragonal Cu2 + and Cr2+

Complexes

Institution: Florida Atlantic University

Thesis Advisor: Dr. J. R. Perumareddi

Degree: Master of Science

Year: 1996

The electronic spectrum of Cu(Il)(L-His )z has been measured in the visible-near IR

and UV regions. By assigning ligand field bands and by fitting the band maxima with

calculated energies using angular overlap model, the structure of the complex has been

deduced to be five-coordinate C4v· The observed bands in the UV spectrum have been

assigned as due to ligand-to-metal charge transfer transitions. Electronic spectra of

Cu(Il)( diphenylcarbazide)2 and Cr(Il)( diphenylcarbazone)(HzO )4 complexes have also

been measured. By interpretation of the ligand field bands in these spectra, tentative

structures of these complexes in solution have been proposed.

iii
 ACKNOWLEDGEMENTS

I would like to express my deepest appreciation and gratitude to my thesis advisor,

Dr. Jayarama Reddi Perumareddi, without whose help and support this work would not

have been possible. In addition, I would like to gratefully acknowledge the support of Dr.

Patricia Snyder and Dr. Theodore Emmanuel Bieber for the intellectual enlightenment and

challenge which they provided throughout my academic endeavors.

Furthermore, I would like to thank my brothers Mohsen and Mehadi and my dear

friend Katherine for their support.

iv
Dedicated to my parents

v
 TABLE OF CONTENTS

Abstract. .............. ......................... ... ... ............ ... ............ ............ ... .. .... ......... ... .... .... .iii

List ofTables ........... .... ....... ......... ....... ..... .. ... ............................. .......................... .... ix

List of Figures .. .. ................... .... ................................ ... .......... ... .... .. ...... .................. ..x

I. Introduction ................................ ... ....... .................. ...................................... 1

A Cu(II)(L-Histidine)2 Complex .... ..... ............................ .......... ....... ........... . 1

B. Copper-diphenylcarbazide .......... ...... ... ............. .. .................. ...... ... ........... 3

C. Cr(ll)(diphenylcarbazone)(H20)4 Complex ............ ...... ... ... .... .... ..... .......... 4

II Experimental Procedures ........ ..... ........... ....... ... ..... ................ ... ..................... 9

A Preparation of copper-histidine complex ..... .... .. ....... ... .................... ..... .... 9

1. Near IR .................................................. ..... ....... ........... .... ................. 9

2. Visible Region ....... ............. ..... ............. ....... ............. .. ......... .............. 9

3. Ultraviolet Region ..... .... ... ............. ......................... .. ................ ... .. ... I 0

B. Preparation of Chromium Carbazone Complex ............ ... ... ... .. ................. 10

1. Visible Region ................... .... .............. .. .... .. ....... ....... ...... .... .. ... ..... ... 10

2. From 600 - 900 nm Region ...... ...... .......................... ......................... I 0

3. Near IR Region ... ..... .... .............. ..... ........ .. ... .. ..................... .... .......... 1I

C. Preparation ofCopper-Diplenylcarbazide Complex ............. .... ....... ......... 11

1. Visible Region .... ......................... .. ... .. .................. ... .......... ................ 11

2. Ultraviolet Region ....... .... .......... ..................... ........ .... ... .... ..... ...... ..... 11

vi
 III. Instrumentation ....... ..... ... .... .... ... .. ... ... ...... .... .. .... .. .. ..... ... ... ....... ......... ...... ..... 12

A Spectral Measurements .... ...................... .. .. ................... ....... ..... ......... ..... 12

B. pH Measurement. ... .... ........... .. ........ .. ................ ....... ... ..................... ....... 12

C. Magnetic Susceptibility Measurements ....... ... ... .. ........... .. ....... ... .. .. ........... l2

IV. Theory ... ....... ..... ....... ........... ........ ..... ... ....... ...... ...................... ...... ... ... ....... .. . 13

A Applications ofthe Angular Overlap Method (AOM) to Inorganic

Complexes ...... ..... .. ............................ ........................ .... ....................... .... 13

AI . Ideas Behind AOM ...... ..... ....... ........ ........ ....................... ........ .. ...... 13

A2. cr Donor and Pi Acceptor Interactions .. ............. .. ...... .. ....... ...... .... .. .20

B. Energy Levels ofCu(II) and Cr(II) Ions ........... .. ................................. ..... 28

C. Energy Expressions and Transition Energies for Cu(II) Complexes in

Various Geometries ... ........ ..... .. ...... .... ................. ... .... .. .. .. ... .. ........ ...... .... 33

V. Results and Discussion .......................... ..... .. ...... ..... ... .. .. ..... .. .. .. .... .. .. ........... ..36

A. Cu(II)(L-His)2. ......... .. .. .... ... ............. ... ... ..... ... ................ ....... .. .. ... ......... ... 36

A. I. Visible, Near IR Spectrum ofCu(II)(L-His)2 ........ ..... ............ ......... .36

A.2 . Calculation and Comparison of Transition Energies in the Ligand

•
Field Spectrum ofCu(L-His)2 ... ...... ..... ... ..... .............. .. ... ....... ..... ... 41

A3 . UV Spectrum ofCu(II)(L-His)2 ...... .... .... ........... ....... ... .... .............. 48

B. Cu(II)-diphenylcarbazide ............................ .. ...... ... .......... .... ......... ... ..... ... .54

C. Cr(II)-diphenylcarbazone ... ...................... .... .... ..... .. ....... ... ....... ...... ... ..... ... 60

C.I. Spin-State ofC~+ in the Complex [Cr(dpco)(H20)4]. ........ ....... ....... 61

vii
 C.2. Electronic Spectrum ofCr(dpco)(H20)4. ...... .... ....... .... ............... .... .62

VI. Conclusions .. ..... .... ... ... ............. .. .... .... .... ...... ... ................ ... ........... .. ... ... ......... 68

VII. Further Studies .. ... .. ... ..... ..... .. ...... ..... ... ..... ...... ...... ............. ................. ............ 69

References ............ ... .... ... ....... ........ ....... ... ... .. .. .. ...... ....... ........ ...... ... ... ... ..................... 70

viii
 LIST OF TABLES

Table 1: Possible positions on each d orbital ... ........... ......................... ...... .. ... ... 22

Table 2: Factors of eo. at different geometrical positions .... .. ...... ........................ 23

Table 3: Factors of en at different geometrical positions .. ... ... .... ... .......... ....... .. .. .24

Table 4: Terms of dn configuration ............ ... ............... ...................... .... ...... .... ..30

Table 5: Transitions energies for Cu(II) complexes in various geometries .. ........ 35

Table 6: Polarized crystal spectral data of some tetragonal Cu(II)

complexes ....... ................ ...... .... ........ ..... .. ..... ... .... ... .... .. .... .. .. ..... .. ....... 44

Table 7: Extracted AOM parameters in (kK) .... ..... .. .................... .... ... ............... 46

Table 8: Calculated angular overlap parameters for Cu(H)(L-His)2, D4h

Or c4V·•··· ·· ···· ···· .. ... ........ ..... .... ..... ........................... ... ... .. ..... ... ....... ..... .47

Table 9: Calculated band positions (kK) for 5-coordinate C4v and 6-

coordinate D4h Cu(II)(L-His)2 ........... .......... .... .. .. .... ... ... ..... ..... ............. 49

Table 10: Assignment of the bands and a comparison of the calculated and

observed transiton energies (kK) of the L.F. bands in

• [Cu(II)(L-His)2]. .. ........... ........................................................... ..... ..... 50

Table 11 : Assignment of the charge transfer bands in the UV spectrum of

Cu(Il)(L-His)2 and comparison with Cu(Im)l+................................ .. ... 53

Table 12: Assignment of ligand field bands in the visible spectrum of

[Cu(dpcz)2] (dpcz = diphenylcarbazide) .... ..... ..... ... .... ... ... .. ... ... .. ..... ... ... 58

Table 13 : Assignment of the bands in the visible-near IR spectrum of

[Cr(II)( dpco )(H:lO)4] (dpco = diphenylcarbazone) ..... ........ .... .... ....... ..6 7

ix
 LIST OF FIGURES

Figure 1: Proposed structures ofCu(His)2. .. .... ...... .. .. ............. .. ... ....... ....... ............ 2

Figure 2: Structure of trans(Cr(II)(Nic-N) 2(H20 )4 ..... ..... .... .... .. .. ........... ......... ....... 5

Figure 3: Formulas of diphenylcarbazide, diphenylcarbazone, and

diphenyldicarbazone ... ...... ... ....... .. ...... ....... .... ....... ........... ... .. .................. 7

Figure 4: a-interaction betweenp orbital ofligand and d/ orbital ofmetal .......... . 15

Figure 5: n-interaction between n·, or d orbital ofligand and dzx orbital of

metal. .. ...... ... .................... ... ....... ... ................. ......... .... .... ... .... ... ............ 19

Figure 6: Illustration of octahedral, tetrahedral and trigonal bipyramidal sites

around the central atom ... ....... ... ..... ..... .. ........... ....... .. ... ... .............. ....... .21

Figure 7: Energies of d orbitals in octahedral complexes with cr donor and 1t

acceptor ligands ......... .... ......... ........... .... .. ... ... .......... ......... ..... .. .... ... ...... 26

Figure 8: Qualitative splitting of d orbitals in:............. ..... ... ... ............. ........... ..... .. 29

a) Octahedral ligand field (0..) ........................ .. ..... .... .... .... .. ... ............... 29

b) Tetragonal ligand field (D4h, C4v) ........................ ................ ...... .. ....... 29

Figure 9: Qualitative energy level diagram for Cu(II) ion in:.. .... ........ ...... ......... .. .. 31

a) Octahedral ligand field .... ...................... .. .. ......... ............... ..... ... .. ....... 31

b) Tetragonal ligand field ......... ..... ... .... ....... .................. ... ... ... .. ... ........... 31

c) Including spin-orbit interaction .... .... ........ .... ......... .... ...... ....... .... ..... .. .. 3 1

Figure 10: Qualitative energy level diagram for Cr(II) ion .. ........... .. .............. ...... .... .32

a) Octahedral ligand field .......... ... ... .... .......... .. .... ...... ..... ...... ............ .. ... .. 32

X
 b) Tetragonal ligand field ............. ... ... .. ... ............ .......... .... .... ... ... ............ 32

c) Including spin-orbit interaction ....................................... ................... 32

Figure 11 : Various geometries exhibited by Cu(II) ion ....... .. ........................ .... ... .... 34

Figure 12: Visible spectrum ofCu(L-His)2 ... ... .... .... ... ... .... .. .... .. .. ............. .... ... .... ..... 37

Figure 13 : Near IR spectrum ofCu(L-His)2. ......... ....... ........... ................................. 38

Figure 14: Gaussian curve-fit of ultraviolet spectrum ofCu(II)(L-Hisb ................... 39

Figure 15: Gaussian curve-fit of visible spectrum ofCu(II)(L-His)2 .......................... 40

Figure 16: Shift in IR frequency as a function ofpD ..................... .. .......................... 46

Figure 17: Molecular, orbital diagram of octahedral transition metal

complexes ............ ...... ..................... ....... ... ....................................... ....... 51

Figure 18: Probable structure for Cu(II) diphenylcarbazide .. ..................................... 55

Figure 19: Visible spectrum of Cu(II) diphenylcarbazide ................. .... ... ... .. ... .... .. .... 56

Figure 20: Charge transfer bands ofCu(II) diphenylcarbazide .... ...... ..... .. ................. 57

Figure 21 : Visible spectrum of Cu( dpco )(H20)4. ..... ... .. ... .. .......... ...... .... ....... ......... ... 63

Figure 22: Tail (on the long wavelength side) ofthe intense visible peak of

Cr(dpco )(H20)4 ....... ....... ...... ... ............ ..... .......... ........ ... ..... .... ............... 64

Figure 23 : Near IR spectrum of the chromium-diphenylcarbazone

complex .. .. ... ...................... ...... ......... ... .. .. ..................... .. ... ...... ....... ........ 66

xi
 I. Introduction

A. Cu(II)(L-Histidine)z Complex

Copper-histidine is a drug that has been used for Menkes disease therapy

for almost 19 years. Menkes disease is an X-linked genetic disorder which retards

Cu-transport in the human body. This disease was discovered in 1962 by pediatric

neurologist John H. Menkes and co-workers at Columbia University [1]. Later

three independent research groups reported the discovery of the gene for Menkes

disease [2].

Copper-histidine was found in normal human serum and detailed study has

revealed the physiological importance of Cu-histidine [3]. Injection of Cu-L-

histidine into patients with Menkes disease at a very early age has proven

successful. However, due to the fact that only 20-30 percent of patients have

responded positively to this therapy, this subject has been a controversial one. In

order to deteniline the exact structure, or distribution of structures, of copper-

histidine at physiological pH, Sarkar and his group began a series of

potentiometric studies, along with IR spectra, using carbonyl frequency as the

marker at different pH levels [4-6] . In that extensive study, they concluded two

possible structures for Cu(II)(L-His)2 at physiological pH. (Figure 1).

1
Six-coordinated tetragonal D4h Five-coordinated square pyramidal C4v

Figure I. Proposed structures ofCu(L-His)2 [4,5]

2
However, they could not further conclude which of their structures was possible in

human plasma. We have made several attempts to grow single crystals of copper-

histidine by the following two techniques: 1) slow cooling of a saturated solution

of complex salt and 2) diffusion of a concentrated solution of the complex into

aceton [7]. However, all of our attempts have failed . Meanwhile, we have studied

the electronic spectrum of the complex and have interpreted the observed ligand

field bands using the angular overlap model to arrive at its tentative structure.

B. Copper-diphenylcarbazide

Upon addition of diphenyl carbazide to a Cu(II) solution (green), red-

orange color appears immediately. In fact, one way to detect the presence of

copper is to add a few drops of 1 percent alcoholic solution of diphenylcarbazide

to the Cu(II) containing solution. Instantaneously, a red-orange color appears

with 1 part copper in 1,000 parts of solution [7]. Our interest is in studying the

electronic spectrum of the complex formed and in thoroughly interpreting the

electronic energy levels in order to deduce the coordination number and the

geometry of the complex.

3
C. Cr(II) (diphenylcarbazone) (H20)4 complex.

Most Cr(II) complexes are not air-stable. They easily oxidize to Cr(lll)

and they have to be studied in an inert atmosphere. One well known air- stable

monomeric complex reported in the literature is:

trans-[Cr(Nic-N)2] (H20)4 where

Nic-N is pyridine-nitrogen bonded nicotinate [8]. (Figure 2).

4
 (3)

Figure 2. Structure oftrans-[Cr(II) (Nic-N)2] (H20)4 [8].

5
 It is well-known that the colored reaction product between chromate and

diphenylcarbazide in an acid medium is air-stable. In fact, this is the best method

yet devised for the detection of trace amounts of chromium [9].

Cazeneuve, the pioneer in this field, believed that the intense coloration

was due to an organo-metallic chromium compound [9]. One of the striking

features of this classic reaction is that chromium has to be in a hexavalant state and

that the reaction medium has to be acidic, (0.2N) optimum acidity [10]. Bose has

indicated that the color production is a result of the complex formation between

Cr(II) and diphenylcarbazone (Figure 3) which are formed as products in an

oxidation-reduction reaction.

6
 / NH-NH-C 6H5 /NH-NH-C 6H5
0 = c 0 = c
'\.NH-NH-C H '\._N=N-C H
6 5 6 5
DIPHENYLCARBAZIDE DIPHENYL CARBAZONE

/N=N-C 6H5
0 = c
"N=N-C6H5
DIPHENYLDICARBAZONE

Figure 3. Formulas ofDiphenylcarbazide, Diphenylcarbazone, and

Diphenyldicarbazone

7
 In order to re-examine Bose's view of such complexation, we have

repeated the following reactions and have noticed complete agreement with Bose' s

results.

chromate + diphenylcarbazide red-violet color

chromate + diphenylcarbazone red-violet color

chromous + diphenylcarbazone ~ red-violet color

chromous + diphenyldicarbazone ~ no reaction

chromic + diphenylcarbazide ~ no reaction

chromic + diphenylcarbazone ~ no reaction

Our aim is to characterize the exact structure of the Cr(II)-diphenylcarbazone

complex through measurement of its magnetic susceptibility and its UV-visible

electronic spectra.

8
 IT. Experimental procedures

A. Preparation of copper-histidine complex [3].

Anhydrous copper chloride, 20.0012 grams, was dissolved in a minimum of

deionized water. Then, the green solutior. was filtered through filter paper

containing solids of sodium hydroxide. Then, the solution was diluted with a

previously prepared 9% solution of sodium chloride to exactly 500 m1 (MW of

CuCb is 134.49 g and molarity is 0.2974 M). In a separate beaker, 13.1533 grams

of99.9% (0.2974 moles) pure L-histidine was dissolved in a minimum of deionized

water and then diluted to exactly 500 m1 with the previously prepared 9% sodium

chloride solution (MW of L-histidine is 15 5.16 and moalrity is 0 .1696M).

Three separate concentrations of Cu(ll) L-histidine were used for three

different regions of spectrum: near IR, visible and ultraviolet.

1. Near IR: 30 m1 of the (0.2974 M) CuCb solution and 70 m1 of the

(0.1696 M) L-histidine solution are mixed. A blue color appeared immediately and

the pH was about 5. Small crystals of sodium hydroxide were added to the

solution while stirring and the pH was adjusted exactly to 7.45 (molarity of

copper-histidine complex is 0.0595 M)

2. Visible region: 10.00 m1 ofCuCb (0.2974 M) and 46.00 m1 ofL-

histidine (0.1695 M) were mixed and diluted to 250 m1 using the previously

prepared 9% sodium chloride solution. Then, small crystals of sodium hydroxide

9
were added to adjust the pH to exactly 7.45 (molarity of copper-histidine complex

is 0.0119 M)

3. Ultraviolet region: 1. 1 ml of 0.0119 M copper-histidine was diluted

to 100 ml using the previously prepared 9% solution of sodium chloride (molarity

of copper-histidine complex= 0.0001309 M)

B. Preparation of chromium carbazone complex (10].

50.0355 grams ofK2Cr:!01 was dissolved in mnimum of deionized water

and diluted to exactly 500.00 ml, with 0.2 N acetic acid (molarity ofK2Cr201 is

0.3401 M). Similarly, 20.5999 grams of diphenylcarbazide was dissolved in about

100 ml of ( 1: 1) acetone/water and transfered into a 250 ml volumetric flask.

Finally, the solution was diluted to the mark using (1 :1) acetone/water.

Two separate concentrations of chromium carbazone complex were used

in visible and near IR regions.

1. Visible region: 8 ml of0.3401 M K 2Cr201 was mixed with 24 ml of

0.3401 M diphenylcarbazide and diluted to exactly 250.00 ml using 0.2 N acetic

acid (molarity of the complex is 2.17664 x 10"2 M). Thenl.OO ml ofthis stock

solution was further diluted to 500.00 ml using 0.2 N acetic acid (molarity of

chromium-diphenylcarbazone complex is 4.3533 x 10"5 M)

2. From 600 to 900 nm region: 20.00 ml of the original stock solution

2
(2.17664 x 10" M) of chromium-diphenylcarbazone complex was further diluted

10
to 250.00 ml using 0.2 N acetic acid (molarity of chromium-diphenylcarbazone

complex is 1.741312 x 10-3 M).

3. Near IR region: 40.00 ml of original stock solution (2.17664 x 10-2

M) chromium-diphenylcarbaxone complex was further diluted to 100.00 ml using

0.2 N acetic acid (molarity ofchromium-diphenylcarbazone complex is 8.70656 x

10-3 M)

C. Preparation of copper-diphenylcarbazide complex (9]

1. Visible region: 2.5 ml of0.2974 M CuCh and 6.5 ml of0.3401 M

diphenylcarbazide were mixed and diluted to 250.00 ml using ( 1: 1) acetone/water

mixture (molarity of copper-diphenylcarbazide complex is 2.974 x 10-3 M)

2. Ultraviolet region: 10.00 ml of2.974 x 10-3 M solution of copper-

diphenylcarbazide solution was further diluted to 100.00 ml using ( 1:1) acetone/

water mixture (molarity ofcopper-diphenylcarbazide solution is 2.974 x 10-4M)

11
 m. Instrumentations

A. Spectral measurements

All ultraviolet and visible spectrascophy were carried out with Cary 3

spectrophotometer. All near IR from 900 nm to 1,350 nm were carried out with

Lambda 9 Perkin Elmer spectrophotometer* .

B. pH measurement

All pH measurements were carried out with Corning pH Meter 215 .

C. Magnetic susceptibility measurements

All magnetic susceptibility measurements were caried out using Johnson

Matthey fabricated equipment.

*Lambda 9 spectrophotometer was kindly provided to us by Dr. Lewis Nita Aries

of the University ofMiami, chemistry department.

12
 IV. Theory

A. Applications of the angular overlap method (AOM) to inorganic

complexes

The ligand field approach is not applicable to geometries other than the

octahedral, square planar or tetrahedral for two main reasons. First, and most

important, is that the parameters in the ligand field (Dq, Ds, Dt) are symmetry

parameters and are not easily transferable between systems with different

symmetries. Secondly, angles at which the ligands approach d orbitals are ignored

or are not considered. In the angular overlap model, which is a form of molecular

orbital theory, such interactions are taken into full consideration. Also, the

parameters are perfectly transferable from one system to another with a different

symmetry.

A.l. Ideas behind AOM [11]

Considering the mono-coordinated complex ML with Coov symmetry, where

M is a transition metal and Lis a ligand, the d orbitals in Coov symmetry (with M-L

as the Z-axis) span the following respresentations:

d(/) is a

d(yz), d(xz) are 1t

d(xy), and d(x 2-i) are o

13
In the simplest case, where there is a sigma interaction between d/ orbital of the

metal and a p or ad orbital of the ligand (Figure 4), the following secular

determinant can be set up:

= 0 (I)

where HM0 and HLcr are the energies of metal and ligand orbitals respectively.

HMLa is the exchange integral and SMLa is the overlap integral.

Assuming that HMcr >>> HLcr [12], we can divide the energy E into two energy

components, E1 and E2. Further, if the diatomic overlap integral, SMLcr will be

0
small enough so that E1 will be quite closer in energy to HM and E2 will be closer

to HLa the following can then be constructed:

HMLC1 - SML~MC1
=0 (2)
HL(J- HM(J

0 0
HM - HL
= 0 (3)
HML0' - SML~L0'

14
 ,,'
,'',_ ''•
...~ ....... l.... .
~

Figure 4. a-interaction between p orbital of ligand and dz 2 orbital of metal

15
and the values of the roots can be written explicity:

ffiML~
2
- 2HMI.:&{SMLa + (SML~
Et = HM(J + HM(J- HL(J (4) (4)

~a) 2 - 2HML~!. SMI.a + (SMJ..~LJ:

0

E2 = HL<J - HMa- HL0 (5)

Using the Wolfsberg-Helmbolz approximation for the exchange integral:

(6)

Equations (4) and (5) can then be rewritten:

ffiMa - HL'J:_ · (SMLa) 2

= HM(J - HL(J (7)

Also:

-.(lh{ + H~,J: · (SML ai

= HMO- HL(J (8)

16
Breaking the overlap integral into a radial and an angular product:

(9)

Then:

~J2 . scr(rl . scr(9,0)2

Ea• = HMa- HLcr (10)

by letting:

(lh{ + HX:Y · S(rl

ea = HMCf -HLCf (11)

equation (10) becomes:

(12)

and:

(13)

In case of overlap between d/ of metal and a p orbital ofligand, S(9, 0) = 1,

therefore:

17
In case of 1t-bonding, ligands can interact with their low energy-filled orbitals, in

which case same conditions hold as for the cr case, or through their high energy-

empty orbitals so that HM"' <<< HL"', in which case the metal orbital becomes the

bonding type (Figure 5). With the same argument as in a-interaction, we can

arrive at E( dxz) = E( dyz) = e,...

Thus, from the above discussion one can easily see that in AOM some ligands

have maximum effect on one particular d orbital and less or no effect on other

orbitals. The effectiveness of such interaction is solely determined through the

S(8,0) function.

18
 .. T'"
u~~nd t~ ',,
X· or tl orbitaL
hM\I)' 1'-'" 'huwn,
...... l .... :·...
Jl • U( t/

Figure 5. 1t-interaction between 1t •, or d orbital of ligand and dzx orbital of metal

19
 A.2. o donor and pi acceptor interactions

From previous discussion, one can see that in o-interaction the d/ orbital

will become more anti-bonding and the ligand p orbital will become more bonding.

(Figure 4). Similar changes in orbital energy result from other interactions

between metal d-orbitals and ligand orbitals. Considering octahedral, tetrahedral

and trigonal bipyrarnidal geometries (Figure 6 and Table 1), the derived energy

changes of d-orbitals foro-interactions are given in Table 2. Similarly Table 3

gives values for 1t interactions for ligands at the same positions [ 13].

20
 1
: ,..-3
/v
4· M' r ·2
X
s/j
6
Octahedral
positions
1
11 .. i' I ...... -r -,--; ::1 7
I~ I, 8 r--1-f-r 1
~-:_,. 2
I I I I
-!- M 19!M:-r
12:--1
I

1 --
'AI't r - J
I ..-'/
I.L ___ ..... ..-

6 10
Trigonal bipyramidal Tetrahedral
positions positions

Figure 6. Illustration of octahedral, tetrahedral and trigonal bipyramidal sites

around the central atom.

21
Table 1. Possible positions on each d orbital

Site

22
Table 2. Factors of ea at different geometrical positions.

-.
2
dz
1

114 0 0

114 0 0

114 0 0

114 0 0

1 0 0

0 113 113

0 1/3 113

0 113 113

0 113 113

114 9/16 0

114 9/16 0

23
Table 3. Factors of e" at different geometrical positions

>· ·"

·' t ~- · · ~./
0 1 0

0 1 1

0 1 0

0 1 1

0 0 1

2/3 2/9 2/9

2/3 219 219

2/3 2/9 2/9

2/3 2/9 219

0 114 3/4

0 1/4 3/4

24
 In a given geometry, the sum of values in a column is the total energy

change for a particular d orbital, while some of the values in the horizontal rows

give the energy change for a given ligand. Then, in an octahedral complex

(ligands 1-6) with a donor and 1t acceptor ligands, energies of d orbitals can be

deduced from Tables 2 and 3 as shown in Figure 7.

In a tetragonal complex of CN6 we can distinguish ligands as axial ( 1 and 6

along z-axis) and equatorial (2-5 in xy-p1ane) and obtain the energies of the d

orbitals as shown in equation (14). Similarly, for 5-coordinate square pyramidal

complex ( 1 through 5 ligands) and 4-coordinate square planar complex (2 through

5 ligands) energy expressions given in equations (15) and (16) can be obtained. In

these expressions (e) and (a) stand for equatorial and axial ligands, respectively.

25
 ------... '''
''
' ' •,
'-'-----
Ligand Jt • orbitals
, _ - ;: . X : - \' :
' .
''
' ''
' ''
''
''
,'' 3~CJ
,/'
'

- - - - _,·' --..1--------·--
d Orbitals in ',,
uncoordinated ''
.I
6,

',
metal ''
' ',
''
'
'
-
.--- -- --- -- -- -- ---.$ ·.!! .f. f!. f! f!
f / Ligand CJ orb.itals
I
to

J----
f! fl f! f! f! f! /
...... ...,.,

metal complex ligand

Figure 7. Energies of d orbitals in octahedral complexes with a donor and 1t

acceptor ligands [ 13].

26
dx2 - y
2 = 3e a(e)

(14)
dxz = 4en (e)

d:rx = dyz = 2en (e)+ 2en(a)

(15)

d/ ./ = 3ea(e)

d/ = lea(e)
(16)

27
B. Energy Levels of Cu(ll) and Cr(ll) Ions

Energy levels of complexes in a given symmetry can be derived using either

the one-electron d-orbitallevels (Figure 8) or the terms of electronic configuration

of the transition-metal ion. Terms are nothing but energy states that arise when

electron-repulsions are included. The procedure to obtain the terms is well-known

and Table 4 lists the terms that arise out of all dn configurations. Cu(II) ion is of
9
d configuration which gives rise to only one term, 2D, and Cr(II) ion is of d4

configuration which if high-spin (see later) gives rise to only one term, sD. Thus

we are concerned with how the D-term splits in complexes of various symmetries.

These energy level diagrams are given in Figures 9 and 10. These diagrams also

inlcude final energy levels when spin-orbit interaction is included [ 14].

28
 , . - - - - b , (dx>.y>)
,. ,.
eg ,.. ,..
/~=====<,
/ ',
// ''""=====a, (dr)
/
/
/
d
<

(a) (b)

Figure 8. Qualitative splitting of d orbitals in:

a) Octahedral ligand field (~)

b) Tetragonal ligand field (D4h, C'*'.)

29
Table 4. Terms of d0 configuration

Terms

~,3p

1
G, •n, •s
4F, 4p

lH, lG, lF, 2lD, lp

SD

Ja, 3G, 2~, ~' 2Jp

1
1, 2 1G, 1F, 2 1D, 2 1S

6s
4G, 4F, 4D, 4p

2
1, 2H, 22G, 22F, 3 2D, 2P, 2S

30
 ,. ... ----r,
,. ,. .... .....
~

,. ,.
~~
2T2g '----r 6
til
/ ..... 28 2g
/ ..... .....

20 /
/
/ ...
.,. ----r,
(
\ u2
\
\ 2A,g
\
\
\
2Eg /
/
/ .,. ,----r6
u,
'' 281g
' ----r,
(a) (b) (c)

Figure 9. Qualitative energy level diagram for Cu(II) ion in:

a) Octahedral ligand field

b) Tetragonal ligand field

c) Including spin-orbit interaction

31
 sr29 /
----<< .....
/
/
.
til
~ •
/ ..... ..... 58 ,
/
/
A~
--"
/
so /
(
\ ii2
\
\
SA,
\
\
\ / A~
-
'
/
\ sEg /
\ ~--....(< VI

'' ss,
' '" ,._-~,--} f:
r,

Figure 10. Qualitative energy level diagram for Cr(II) ion.

a) Octahedral ligand field

b) Tetragonal ligand field

c) Including spin-orbit interaction

32
C. Energy expressions and transition energies for Cu(II) complexes in

various geometries.

Copper(II) ion is known to exhibit various geometries, 6-coordinate

tetragonal (distorted octahedron), 5-coordinate square pyramidal, and 4-

coordinate square planar (Figure 11 ). It should be noted that the qualitative

energy diagram given in Figure 9 applies to all these geometries although the

energy expressions will be different for different geometries. The expressions for

energy levels can be derived using the one-electron energies given in equations

14-16. As an example, the B 18 state arises out ofthe configuration e~/a1 b1

2 2

Figure 8) with an energy of5e0 (e) + 4ea(a) + 16en(e) + 8ela) in 6CN

tetragonal complex. The energy of 2A1 8 state in the same complex is that of

2 2
e4b/a1b1 2 which is 7ea(e) + 2ea(a) + 16e71(e) + 8e11(a). Hence the B1 8 ---)- A1 8

transition energy is given by 2ea(e) - 2ea(a). The transition energies obtained in

this fashion are given in Table 5. It sould be noted, though, that because of hole

formalism d9 configurat.ion can be treated as d 1 and transition energies can be

2
obtained in a very simple way. Thus B 18 ---)- 2A 18 transition corresponds to one-

electron transition a1 8 ~ b1 8 which gives the same expression 2ea(e) - 2ea(a) in a

6CN tetragonal complex.

33
6-coordinated

e
a

e
e
e
e

e
a(e)

5-coordinated

4-coordinated

Figure 11. Various geometries exhibited by Cu(ll) ion

34
Table 5. Transition energies for Cu(II) complexes in various geometries

I. Tetragonal (Me4az)

II. Square-pyramidal (Me4a)

III. Square-planar (Me.J

35
 V. Results and Discussion

A. Cu(ll)(L-His)2

The measured spectra in the visible, near IR and UV ofCu(II)(L-His)2

complex are given in Figures 12, 13 and 14, respectively.

Visible spectrum ofCu(II)(L-His)2 (Figure 12) seems to have an

asymmetry on the low energy side. We were able to resolve the spectrum into two

peaks by Gaussian analysis*, one at 15.7 kK and the other at- 11.50- 12.00 kK

(Figure 15). The near IR spectrum (at high concentration) shows no peak up to

7.5 kK. The rising absorption at - 9.5 kK is the tail of the low energy peak

observed in the visible spectrum

A.l. Visible, near IR spectrum of Cu(II)(L-His)l

We will discuss the visible-near IR spectrum first. The two bands observed

are the ligand field or d-d bands because of their low intensity. Consequently, we

assign these bands as follows (see Figure 9). The low energy 11 .50- 12.00 kK

peak is due to-2Bt ~ 2A1 transition and the 15 .70 kK peak is the

*Gaussian analysis was carried out by GRAM 386 software which was kindly

provided to us by Dr. P. A Snyder ofFlorida Atlantic University. Assistance in

executing the program by Michael Boulos is greatfully acknowledged.

36
 8

.6

A
4

12000 14000 16000 18000 20000 22000 24000 26000 28000

Figure 12. Visible spectrum ofCu(II)(L-His)2

(Cone. = 0.0119 M)

37
 5

_3

A
2

7500 8000 8500 9000 9500

v/cm·l

Figure 13. Near IR spectrum ofCu(ll)(L-His)2

(Cone. = 0.0595 M)

38
 3.5

2.5

w
u
z 2
<
IX)
a:
0
en
IX)
< 1.5

.5

30000 32000 34000 36000 38000 40000 42000

WAVENUMBER (cm-1)

Figure 14. Gaussian curve-fit of ultraviolet spectrum of Cu(II)(L-His)2

4
(Cone. = 1.309 x 10 M)

39
 .e

.IS

w
0

~
a:
g .4
aJ
<

, 2000 , 3000 , 4000 , 5000 , 6000 , 7000 18000 , !lOCO 20000 21000 22000

WAVENUMBER (cm-1)

Figure 15. Gaussian curve-fit of visible spectrum of Cu(II)(L-His)2

(Cone. = 0.0119 M)

40
average of the two transitions 2B1 ~ 2B2 and 2B1 ~ 2E. The reason we assign the
'
low energy peak to B 1 ~ A 1 transition is because there is no absorption all the
2 2

way down to 7.5 kK.

A.2. Calculation and Comparison of Transition Energies in the

Ligand Field Spectrum of Cu(L-His)2

Sarkar and co-workers have proposed two possible structures for the

complex Cu(L-His)2, one a six-coordinate in which each histidine ligand is

tridentate and another a five-coordinate in which one histidine is tridentate and the

other bidentate. The donor atoms of the tridentate histidine are imidazole

nitrogen, amino nitrogen and the carboxylate oxygen. In both structures the N-

donor atoms are in the equatorial plane with imine N' s trans to each other so that

the amino N' s are trans to each other and the carboxylate oxygens occupy the axial

positions, both in the case of 6CN and only one in 5CN. (See Figure 1). The

involvement of one or two carboxylate groups was strongly favored from their

study [5] of shift ofiR frequency as a function ofpD (Figure 16). Thus, in order

to calculate the transition energies, we need to know the angular overlap

parameters for these donor atoms. The extraction of these parameters has been

carried out as follows .

41
 .J
] ,0&4.1

., •

-~

,Ozt.O

2000 IICIO \600 1400 1200 'COO 100

,,,..._, &c.·'•
Figure 16. Shift in IR frequency as a function ofpD [5]

42
 First we have surveyed the polarized spectral data of various Cu(II)

complexes with similar donor atoms, namely, amine, imidazole, aqua, and formate

complexes. The data on these complexes [15] are given in Table 6. The band

positions then have been fitted with the energy equations (Table 5) to obtain the

parameters. It should be noted that in all of these cases, we have three equations

(for three transitions) and four unknown parameters, ea(e), ea(a), en(e), and en(a).

It is well-known that in Cu(II) complexes the axial bonding is considerably weaker

than the equatorial bonding. Considering that 1t-bonding is weaker than that of a-

bonding we could assume en( a) to be almost negligible. However, we have set

en(a) = (1/5) ea(a)

and evaluated the parameters. To give an example, consider Cu(lm)62+:

EeBt 8 ~ Atg} = 2ea(e)- 2ea(a) = 12.50kK

2

EeB1 8 ~ 2B2g) = 3ea(e) - 4en(e) = 10.70 kK

EeB1 8 ~ 2Eg) = 3ea(e) - 2en(e) - 2en(a) = 16.20 kK

Using the above assumption,

2ea(e) - 2ea(a) = 12.50

3ea(e) - 4en(e) = 10.70

3ea(e) - 2e11(e) - 0.4ea(a) = 16.20

43
Table 6. Polarized crystal spectral data of some tetragonal Cu(II) complexes [ 15]

44
from which we obtain the following values:

ea(e) = 7.59 kK

e,.(e) = 3.02 kK

ea(a) = 1.34 kK

and e,.(a) = 0.27 kK

for the imine N ofthe imidazole ligand which is the coordinating atom in Cu(lm)/+

complex. The extracted AOM parameters for the various ligands by this

procedure are given in Table 7.

With these extracted parameters, the AOM parameters for the target

complexes can be calculated as follows :

In equatorial positions since we have two imine N' s and two amine N' s, we

use the average ofthe corresponding parameters for ea(e) and e,.(e):

ea(e) = (5 .53 + 7.59)/2 = 6.56 kK

e,.(e) = 3.02/2 = 1.51 kK

For the ea(a) and e,.(a) we have used the parameters of the formate complex. These

values are summarized in Table 8.

Now, having these AOM parameters, one can calculate the transition

energies for the two possible structures using the energy equations of Table 5. As

an example considering the 6CN tetragonal complex:

45
Table 7. Extracted AOM parameters in (kK)

ligand eo( e) en( e) eo( a) en( a)

NH3 5.53 0 - 0

Im 7.59 3.02 1.34 0.27

H20 5.24 1.13 0.64 0.13

HC02 5.75 1.66 1.55 0.31

46
Table 8. Calculated angtilar overlap parameters for Cu(L-His)2, D4h or C4v

47
 = 2(6.56)- 2(1.55) = 10.02 kK

= 3(6.56)- 4(1.51) = 13 .64 kK

= 3(6.56) - 2(1.51) 2(0.31)

= 16.04 kK

The same procedure is applied to five-coordinated C4v and energies calculated.

The calculated band positions for these two structures are given in Table 9.

The observed band positions are compared with the calculated values for

the two possible structures in Table 10. We tentatively conclude from this

comparison that the Cu(II)(L-Hish complex is five-coordinate C4v.

A.3. UV Spectrum of Cu(II)(L-Hish

Gaussian analysis of the UV spectrum ofCu(II)(L-His)2 (Figure 14) shows

clearly three peaks and probably

. .
another at - 41.00 kK of which we are not sure of

at this time. Because of their high intensity, these peaks are due to charge transfer

(CT) transitions (Figure 16). In most Cu(ll) complexes, the CT transitions are

ligand to metal since Cu(I) is a stable oxidation state. Accordingly, we assign

these transitions as ligand to metal charge transfer. In particular the two lowest

48
Table 9. Calculated band positions (kK) for 5-coordinate C4v and 6-coordinate

D4h Cu(II)(L-His)2

Transition · Six-coordinate

10.02

13.64

16.04

49
Table 10. Assignment of the Bands and a comparison of the Calculated and

Observed Transition Energies (kK) of the L.F. bands in [Cu(L-His)2]:

15.70 (7l.Ot

Conclusion: SCN C4v (tentative)

a. This observed band is being assigned as due to both transitions 2B 1 ~

2 2
Bz, E.

b. These are the average values of the calculated transition energies for

the two transitions 2B1 ~ 2B 2 and 2B 1 ~ 2E.

50
 Cn+U P

complex ligand
metal

Figure 17. Molecular, orbital diagram of octahedral transition metal complexes

51
 energy transitions are from the two highest occupied molecular orbitals of

imidazole (1t1 and 1t2 HOMOs) to Cu(II) and the third band due to imidazole cr

(lone pair) to Cu(II). These assignments are shown in Table 11 along with the

observed LMCT transitions and their assignments in the spectrum of tetragonal

Cu(Im)62+ complex reported in the lilterature [16] for a comparison. Since axial

bonding in tetragonal Cu(II) complexes is weak, charge transfer transitions from

axiallignad to metal are usually not seen in their spectra. Hence we assume no

observed transitions from the axial carboxylate ligand to Cu(II) ion. Also we have

not uncovered the intraligand 1t 1 ~ 1t1• transitions of the imidazole ring of the

histidine which is observed in the spectrum of hexaimidazole copper(II) complex at

48 .50 kK (16].

52
Table 11. Assignment ofthe charge transfer bands in the UV spectrum ofCu(L-

His)2 and comparison with Cu(Im)/+

·38.50

45.50

48.50

53
B. Cu(II)-diphenylcarbazide

As mentioned in the introduction, upon the addition of diphenylcarbazide

to Cu 2+, using acetone as solvent, a light, red color appeared. The color is due to

chelate formation between Cu(II) and diphenylcarbazide [ 17]. It has been

suggested [ 17] that the chelate composition is one copper to two deprotonated

diphenylcarbazide ligands. Thus the complex can be a four-coordinate square

planar (- D4h) (Cu(II) tetrahedral complexes are uncommon) or a six-coordinate

tetragonal (- D4h) with two aqua ligands occupying axial positions. (Figure 18).

The visible and UV spectra of copper-diphenylcarbazide are shown in

Figures 19 and 20. Approximate band positions from the two shoulders in the

visible spectrum are given in Table 12. These are the only ligand field bands we

have uncovered for this compelx. The near IR spectrum shows only sharp peaks,

probably due to vibrational overtones of acetone/diphenylcarbazide and not to

broad d-d bands.

54
 ._

Figure 18. Probable structure for Cu(II) diphenylcarbazide

55
 1.2

17000 18000 19000 20000 21000 22000 23000 24000 25000

ii/cm·1

3
Figure 19. Visible spectrum ofCu(II) diphenylcarbazide (C = 2.974 x 10" M)

56
 ,...0
,...
N
N

A 2

25000 26000 27000 28000 29000 30000 31 000

wcm·l

5
Figure 20. Charge transfer bands ofCu(II) diphenylcarbazide (C = 2.974 x 10- M)

57
Table 12. Assignment of Ligand Field bands in the Visible Spectrum of

[Cu(dpcz)2 ] (dpcz = diphenylcarbazide)

-170

Conclusion: Square planar Cu(II) chelate because of

i) high transition energies and

ii) high intensities

58
 2 2
Hence we assign the lower energy band at- 18.0 kK to Bt 8 ~ At 8 transition

and the band at- 21 .5 kK to both 2Bt 8 ~ 2B2g, 2Eg transitions. Both the energies

and intensities of these bands are high indicating that the complex is square planar

[ 15]. Thus our tentative conclusion about the structure of the compelx is that it is

four-coordinate square planar [Cu(II)( diphenylcarbazide)2].

We have not attempted to interpret the UV spectrum of this complex. It is

obvious that these transitions, which are of very high intensity, are ligand to metal

charge transfer and intraligand. Any attempts for a thorough interpretation of the

transitions should await the study of the molecular orbitals of the

diphenylcarbazide molecule itself

59
C.. Cr(II)-diphenylcarbazone

Based on the findings mentioned in the introduction, there is no doubt that

the initial reactions of chromate and dephenylcarbazide are redox reactions

represented by the following balanced equations.

/NHNHC6Hs
2 Cr6+ + 3 0 = c
~C~s
3 0 = + 6l1

C~s

( diphenylcarbazone)

(diphenyldicarbazone)

60
 Then the origin of the intense purple coloration is due to the complex

formation between chromium(II) ion and the enolate of diphenylcarbazone as

shown in the following reactions [ 10] .

/ - NHCJis

~H
Keto enol
-
~- NCJis

--> C,;H,N ~ N - ~-

C~+ + dpcoH2 ~ Cr(dpco) + 2W

C.l. Spin-state ofCr2+ in the complex [Cr(dpco)(B20)4)

Preliminary experiments of Bose [10] showed that the complex is four-

electron paramagnetic. _We have measured the magnetic susceptibility of highly

concentrated chromium-diphenylcarbazone solutions and calculated the magnetic

moment to be 4.8 B.M .. Calculated spin-only magnetic moment for four-unpaired

electrons is 4.9 B.M. (J..lso = [n(n + 2)t B.M. where n is the number of unpaired

electrons). Chromium(II) being 3d4, four unpaired electrons means that the

4
complex is high-spin. It is well-known that high-spin d with e2geg 1 configuration

61
(if approximately octahedral) will make no orbital contribution to the magnetic

moment [18]. In order to study the ligand-field spectrum of high-spin d4

complexes, it is enough to examine the splitting of the 5D ground state term of d4

in a given complex. This is the reason why we discussed the splittings of the
5
D term only in the theoretical section of the thesis.

C.2. Electronic Spectrum ofCr(dpco)(H20)4

The visible spectrum of Cr(dpco) complex is shown in Figure 21 . The

spectrum consists of only one peak at 540 nm with an extinction coefficient of-

30,000 M" 1cm· 1. This band because ofvery high intensity is obviously a charge

transfer (CT) transition. Also the band is very symmetric when the spectrum is

plotted on wavenumber scale. We have obtained the tail of this spectrum on the

long wavelength side using very high concentrations of solutions to uncover any d-

d bands. This part of the spectrum shown in Figure 22 clearly shows a shoulder

with a maximum of absorption at about - 750 nm which must be a ligand field

transition. We have not. carried out Gaussian analysis to obtain a definitive

.

maximum of this band since this is a very low intensity tail of a very high intensity

charge transfer band.

62
A

0
450 500 550 600

J./nm

Figure 21. Visible spectrum ofCr(dpco)(H20)4

5
(C = 4.3533 X 10" M)

63
 DISPLAY DATA
4.8000

3.6000
3.2000
A 2.8000

2.4000

2.0000
600.00 700.00 800.00 900.00

).fnm

Figure 22. Tail (on the long wavelength side) of the intense visible peak of

3
(C = 1.741312x 10" M)

64
 In order to uncover any low energy d-d transitions (which are expected for

high spin d\ we have scanned the spectrum in the near IR region (Figure 23). In

addition to some vibrational overtones, we find a low intense broad absorption in

the range 8.00 kK to 11.00 kK. We believe there is a ligand field band in this

region with a maximum at -10.00 kK. Table 13 lists these transitions along with

their assignments. Charge transfer band has been assigned as Metal-to-Ligand

(MLCT) since chromium {III) is a stable oxidation state. It is interesting to note

that this MLCT band appears in the visible range (-540 nm) reflecting the ease of

oxidation of Cr(II) to Cr{III). Ligand field bands have been assigned assuming a

six-coordinate tetragonal complex [Cr(dpco)(H20)4] where dpco is a bidentate

ligand as shown below [See Figure 10 for the energy diagram].

It should be noted that both the transition energies of the ligand field bands

and their assignments are strictly tentative at this time and further experiments are

necessary to arrive at definite conclusions.

65
 <0
<0
5 N
10

4
C')
'O:t
.....

·3

2 N
10

(") N
1 10
C')
co
,...
0 .....
.....

5000 6000 . 7000 8000 9000 1 0000 11 000 12000

v/cm·1

Figure 23. Near IR spectrum of the chromium-diphenylcarbazone complex

(C = 8.70656 X 10"3 M)

66
Table 13. Assignment ofthe bands in the visible-near IR spectrum of

[Cr(II)(dpco)(H20)4] (dpco = diphenylcarbazone).

18.52 MLCT, c~+ ~ 1t.

10.00 1,550

13.33 57

67
 VI. Conclusions

In this study we have measured the UV-Visible-near IR electronic spectra

of a well-characterized copper-histidine complex, Cu(II)(L-His)2, and by a

comparison of the observed maxima of the ligand field bands with calculated

transition energies using Angular Overlap Model, we were able to conclude that

the structure of the complex is five-coordinate rather than six-coordinate D 4h . We

have interpreted the Gaussian components of the UV spectrum as due to Ligand-

to-Metal Charge Transfer transitions. We have also measured the electronic

spectra of a copper(II)-diphenylcarbazide complex, and a chromium(II)

diphenylcarbazone complex and by interpreting the ligand field bands have

tentatively concluded that the copper complex is four-coordinate square planar

[Cu(dpcz)2] and the chromium complex is six-coordinate tetragonal

[Cr(dpco)(H20)4]. In addition, we have assigned the intense band of540 nm in the

chromium complex as Metal-to-Ligand Charge Transfer transition.

68
 Vll. Further Studies

Further studies include the following:

1. Isolate solids

2. Grow single crystals for 1) crystal structure determination and ii) measurement

of polarized crystal spectral for a definitive assignment of electronic transitions in

the visible near-IR,

3. Measure and interpret CD and EPR spectral ofCu(L-Hist)2 complex,

4. Carry out combined Molecular Mechanics-Angular Overlap Model (MM-

AOM) calculations for structure determination and for a better comparison of

calculated and observed ligand field transition-energies,

5. Carry out semi-empirical molecular orbital calculations such as ZINDO for a

better understanding of the Charge-Transfer transitions.

69
 References

l . Chemical and Engineering News, December 13, 1993.

2 a. Vulpe, C eta/, Nature Genetics, 1993, 3, 7

b. Chelly, J eta/, Ibid 1993, 3, 14

c. Mercer, J. F. B. eta/, Ibid, 1993, 3, 20

3. Sarkar, B., Lingertat-walsh, K Clarke, J T R., J. Pediatrics, 1993, 123,

828

4. Kruck, T. P. A, Sarkar, B. Can J. Chem .. 1993, 61, 3563

5. Kruck, T P. A, Sarkar, B., Can. J. Chem . 1973, 51, 3555

6. Camerman, N . Fawcett, J K., Kruck, T. P. A, Sarkar, B. J., J. Am. Chem.

Soc., 1978, 100, 2690

7. Stanko, J A, Ph.D. thesis, University of Illinois, 1966.

8. Broderick, W. E., Pressprich, M. R., Geniser, U. , Inorg. Chem. , 1986,

25, 3372

9. Cazeneuve, M. P., C. R. Acad Sci., Paris, 1900, 131,346

10. Bose, M., Anal. Chim. Acta, 1954, IO, 201

11. a. Schaffer, C E., and Jorgensen, C K Mol. Phys. 1965, 9, 401

b. Larsen, E., LaMar, G . N.J. Chem. Ed, 1974,51, 633

12. Drago, R S., Physical Methodsfor Chemists, 2nd ed., Saunders, 1992.

70
13 . Miessler, G . L , Tarr, D . A Inorganic Chl!mist1 y, Prentice-HalL Englewood

Cliffs, N. l 1991.

14. a. Liehr, A D . J. Phys. Chem. 1960, 6-1, 43

b. Perumareddi J. R., unpublilshed results.

15 . Lever, A B. P Inorganic Electronic Spectros. copy, 2nd ed. Elsevier, 1986 ,

and references therein.

16. Fawcett, T. G ., Bernaducci, E. E ., Krog-Jespersen, K, Schugar, H. J., J. Am.

Chem. Soc ., 1980, 102, 2598.

17. Welcher, F. J. Organic Analytical Reagents, vol. 3, D. Van Nostrand Co.,

1947.

18. Figgii, B. N . Introduction to Ligand Fields, lnterscience, 1967.

71