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The relationship of configuration to color in some complex compounds of transition elements

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THE RELATIONSHIP OP CONFIGURATION TO COLOR IN
SOME COMPLEX COMPOUNDS OF TRANSITION ELEMENTS
A Dissertation
Presented to
the Faculty of the Graduate School
The University of Southern California
In Partial Fulfillment
of the Requirements for the Degree
Doctor of Philosophy
by
George N. Tyson, Jr.
June, 1941
UMI Number: DP21729
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This dissertation, w ritten by
.......... G
E
Q
R
&
E
^
.........
under the guidance of h.X.8 F a c u lty Com m ittee
on Studies, and app ro ved by a l l its members, has
been presented to and accepted by the C o u n cil
on G raduate Study and Research, in p a r t ia l f u l ­
fillm e n t o f requirements f o r the degree o f
D O C T O R O F P H IL O S O P H Y
Dean
Secretary
D a t e ....lV m .,... 1941
Committee on Studies
Chairman
TABLE OF CONTENTS
CHAPTER
PAGE
I.
INTRODUCTION..................................
I
II.
THE NATURE OF THE P R O B L E M ....................
6
III.
EXPERIMENTAL..................................
11
Measurement of empty tube and tube filled
with water to mark
............
Measurements on oobalt phthalocyanine
• . • •
Measurements on nickel phthalocyanine
• • • •
Measurements on copper phthalocyanine
....
15
16
17
Data collected from the hydrogenation of copper
disalicylaldehyde
........................
S3
Results from magnetic measurements on solutions
of copper disalicylaldehyde in pyridine, and
on pyridine alone
IV.
.............
DISCUSSION OF THE RESULTSAND RELATED LITERATURE
AS RELATED TO CONFIGURATIONS . . . . . . . . .
V.
24
28
THE RELATIONSHIP OF COLORTO CONFIGURATION IN
THE COMPOUNDS CONSIDERED, WITH A FURTHER
DISCUSSION OF RELATED LITERATURE............
VI.
SUMMARY AND C O N C L U S I O N S .....................
BIBLIOGRAPHY......................................
35
41
44
LIST OF TABLES
TABLE
I.
PAGE
Colors of Coordinated Phthalocyanines of Group
Ila M e t a l s ........................
II*
Possible Electronic Configurations of Divalent
Nickel in Complex Compounds
III.
6
. . . . . . . .
9
Empirical Formulae and Analytical Results on
Cobalt, Nickel, and Copper Phthalocyanine
Compared with the Theoretical
IV.
13
Diamagnetic Values of Atoms as Computed from
Volume VI of the International Critical
Tables, Page 365, for the Phthalocyanine
Radical
V.
• • • • • • •
.................
21
Resume/ of Colors of Some Complexes of Cobalt,
Nickel, and Copper . . . . . .
VII.
20
Summary of Computations on Cobalt and Nickel
Phthalocyanines
VI.
................ • •
............
27
Summary of Color to Configuration Relation in
Divalent Nickel Complexes of Diamines as
Found by Lifschitz and Co-Workers
. . . . .
36
CHAPTER I
INTRODUCTION
It is apparent that any study of color must be severely
restricted, and limited to but a small portion of the general
subject, if one individual worker is to achieve any experi­
mental progress in a reasonable length of time.
It is to be
particularly noted that a complete study of color is an ex­
ceedingly wide field, and that experimentally it is impossible
for one researcher to consider more than an aspect of the
general phenomena because of the limitations of time.
The title given to this experimental work is definitive
of the material investigated in the laboratory and will be
elaborated in the following pages.
However, it is first con­
sidered necessary to discuss some other closely related as­
pects of the phenomena of color, in order to differentiate
more clearly the scope of the material actually considered.
The color of.dyes is an almost distinct field of
investigation.
In 1907, Baeyer^- suggested that the color of
dyes was associated with the shift of an electron within a
molecule, and the frequency of the shift was related to the
color.
Another notable paper2 continuing this thought
1 A. Baeyer, Ami. 354, 152 (1907).
o
E. Qi. Adams and L. Rosenstein. J. Am. Chem. Soo..
36, 1472 (1914).
~
appeared a few years later, and more lately the concept of
3 4 5
resonance has been introduced. > »
More recently, L.
Pauling** has suggested that a quantitative calculation can
be made roughly of the frequencies and intensities of the
absorption bands of dyes.
Thus, with such compounds as
benzaurin, the resonance can be shown by the formulae:
==<_J>=o
By means of wave mechanics Pauling has been able to apply to
a limited number of the possible structures, equations which
permit the prediction of the intensities of absorption bands
The work to be described herein does not consider the
color of organic dyes, but is intended rather to evaluate
the contribution of the metallic portion of a metallicorganic complex to the color in certain transition complexes
3 C. R. Bury, J. Am. Chem. Soc,, 57, 2115 (1935).
^ L. Pauling, Organic Chemistry; H. Gilman, editor
(New York: John Wiley and Sons, 1936), 1880-1890.
(1935).
5 R. S. Mullikan. J. Chem. Phys.. 7. 121. 364. 570
“ ---~
6 L. Pauling. Proc. Nat. Acad. Sci.. 25. No. 11,
577-582 (1939).
3
It should also be noted that the description of color
is difficult, if done precisely.
Thus eye fatigue, succes­
sive contrastings of different colors, etc., are psychological
factors that have been described.7 * 8
However, in this work
under consideration, these factors do not have to be consid­
ered, as but a small number of distinctively colored materials
were investigated.
The effect of particle size is also important as often
the real color is masked by the degree of subdivision.
Blue
hydrated copper sulphate, for example, is white if the
particle size is made sufficiently small.
No such phenomenon
is involved in the products prepared for this investigation,
however, as the color remained relatively constant upon
vigorous subdivision of the precipitated material by mortar
and pestle.
It is also well known that the color may vary with
the source of illumination.
The colors described in this
research were viewed in bright daylight in all cases.
Coloring due to the chemical composition of a material
is caused by incident light striking the material.
Of this
light, generally part is reflected, part is absorbed, and
7 Helmholtz,s Treatise on Physiological Optics. Vol.
II; J. P. C. Southall, editor TKew York: Optical Society of
America, 1924).
8 D. B. Judd, J. Optical Soc. Am., 23, 359-374 (1933).
4
part is transmitted.
The mechanism of the absorbed portion
of the light is important, for it is this phenomenon which
chiefly explains the coloring evidenced.
The energy so
absorbed is used in the excitation of electrons from one
quantum state to a higher state.
The energy regained in
falling from the higher to the lower quantum state usually
degenerates into heat*
However, fluorescence and other
light conserving effects are possible.
In the experimental
work performed, no fluorescence was noted.
The excitation of electrons is accompanied by rela­
tively large energy changes, and corresponds to light in
the visible and ultra violet range.
However, change in the
amplitude of the vibrations of nuclei, and change in the
kinetic energy of rotation of molecules will give absorption
that is shown only in the near infra-red, and the infra-red
g
portions of the spectra, respectively.
No absorption spectra have been made of the materials
prepared, and the visible color alone has been used for
identification.
Selective absorption will give rise to definite
colors; if there is strong general absorption throughout
the visible portions of the spectrum, the color appears
9 F. H. MacDougall, Physical Chemistry (New York:
The Macmillan Company, 1936},203.
5
black.
The selective absorption is sometimes known as body
color.
Mason^0 discusses the phenomenon of surface color,
which is often observed in the case of materials which
absorb light strongly.
This phenomenon is caused by the
same mechanism as the absorption, yet the hue of the re­
flected light does not have to be the same, nor the compli­
ment of the absorbed light.
One of the materials prepared
exhibits a marked surface color, and will be described in
detail later.
Thus, by noting the body color (and surface
color also, if present) of particles that have been finely
ground, a sufficiently accurate description of the compounds
can be had for the purpose at hand,
10 C. W. Mason, J. Phys. Chem.. 27, 413 (1923).
CHAPTER II
THE NATURE OF THE PROBLEM
It has been found that in a series of compounds such
as the metallo-phthalocyanine complexes, the intensity of
color decreases with increase in the atomic weight of the
metals in a vertical group of the periodic table.
Thus, in
the series of phthalocyanine complexes coordinated with the
elements of group Ila, the following chart illustrates the
decrease in color of the compound, with increase in atomic
weight of the metali
TABLE I
COLORS OF COORDINATED PHTHALOCYANINES
OF GROUP Ila METALS
Phthalocyanine Coordinated
with:
Colora
Be +■+
dark green
Mg+ +
lighter green
Ca+*f
pale green
Sr + +
paler green
Ba+ +
faint green tinge,
almost white
a All of these compounds exhibit body color only.
It is apparent from the chart that the metallic por­
tion of the complex has a modifying effect on the color.
It
7
was therefore considered desirable to investigate this
problem further in an attempt to determine whether the con­
figuration of the molecule in this series and another avail­
able complex compound exerted a marked effect upon the color
of the compound, and the relative importance of the co­
ordinating group versus the configuration.
Determination of the magnetic susceptibilities can be
used for the establishing of the configuration of the mole­
cule in some cases.
The magnetic criterion for bond type
was first set forth by Pauling1*- in 1931 and has been much
amplified and discussed by Huggins.1^
It should be remem­
bered, however, that this work is limited in its application
and applies only to the elements and their ions through the
first long transition series.
For example, while the sus­
ceptibilities of compounds such as barium and strontium
phthalocyanines can be determined, the existing theories do
not allow the assigning of configurations to the molecules
on this basis alone.
However, in complexes containing ele­
ments of the first long transition series, and lower atomic
numbers, the theory is well able in many cases to show the
configuration of the molecule.
Thus, in the experimental
work considered later, divalent nickel phthalocyanine is one
11 L. Pauling, J. Am. Chem. Soc.. 53. 1391 (1931).
12
M. L. Huggins, J. Chem. Phys.. 5, 527 (1937).
8
of the compounds considered.
The possible electronic arrange­
ments in the orbitals (with the 3d, 4s, and 4p orbitals shown
in detail) and the corresponding configurations are given in
Table II, page 9.
It is immediately apparent that the magnetic suscepti­
bility is not definitively exclusive in this example.
Thus,
if the magnetic susceptibility of a coordinated divalent
nickel ion indicates two unpaired electrons, the compound
can be either planar or tetrahedral in configuration.
This
is due to the fact that because the planar structure is more
stable than the tetrahedral in the transition metals, and
because there is little difference in energy involved in the
3d and 4p orbitals, an electron from the 3d can be moved to
the 4p o r b i t a l . H o w e v e r , if the magnetic susceptibility
shows no unpaired electrons, the compound is planar without
question.
The results of X-ray diffraction work,T.whsn it is pos­
sible to find such work in the literature, coupled with the
results of magnetic measurements, offer convincing proof of
the structure of molecules.
This technique will be employed
in the examination of the experimental results obtained, and
the influence of configuration on the color of molecules
will be noted, as the main purpose of this research.
13
(1935).
The
E. G. Cox and K. C. Webster. J. Chem. Soc.. 731.
TABLE II
POSSIBLE ELECTRONIC CONFIGURATIONS OF DIVALENT
NICKEL IN COMPLEX COMPOUNDS®
Possible Electronic Arrangements of Ni
in the Orbitals
(1)
Configuration
Coordinating
Bonds
1
2
3
3
4
4
s
sp3
sp3
d d d d d
s
tetrahedral
AGSTT
2
£ £ £
SAIL I ?
2
ss r
planar
dsp2
HAAGS
2
22-
planar
dsp2
(2)
s
sp3
sp3
(3)
s
sp3
sp3
sp3
2 2 2
The nomenclature used seems to conform to standard usage. For example, see
L. Pauling, Nature of the Chemical Bond (Ithaca, New York: Cornell University Press,
1939), 94. In the aEove table, t h e w2f* in each case represents a pair of electrons
donated by the coordinating organic compound to the orbitals of the metallic ion, while
the wl" in each case represents an electron in the designated orbital of the metal ion*
The five 3d, 4s, and three 4p orbitals only are shown in detail. All other orbitals
listed are assumed to contain two electrons. Thus, in the above, the Is, 2s, three 2p,
3s, and three 3p orbitals (which are shown as ls2sp33sp3) contain two electrons each,
for a total of eighteen electrons. Likewise, in the coordinating bonds, the same con­
vention is used. For instance, sp3 bonds indicate one's, and three p orbitals used for
bonding, and each of the four orbitals contain two electrons.
10
actual experimental work, and the calculations involved,
are given in the following pages*
CHAPTER III
EXPERIMENTAL
Metallo-phthalocyanines were synthesized by practi­
cally the same method as first given by Linstead and ooworkers.*4
The synthesis used is as follows:
(The molecular
ratios of J. T. Baker Co. C. P. metal chloride salts and
boric acid, and Eastman C. P. phthallic anhydride and urea
are given).
One and thirty-four hundredths (1.34) moles of urea
are placed in a 1500 ml Erlenmeyer flask in a sand bath
together with .05 moles of boric acid for a catalyst.
When
the temperature of the melt reaches 150°C, .4 moles of
phthallic anhydride which has been intimately mixed with .1
mole of the divalent metal chloride is added slowly with
stirring.
The temperature of the reactants is then raised
to 200-220°C, and held at this temperature until the color
of the melt remains constant for one half hour.
The reactant mass is allowed to cool, and the crude
pigment is then removed from the flask, and ground to a
fine powder.
The impurities are removed by warming the
finely ground crude pigment first with five times its weight
of normal sodium hydroxide, filtering; then warming the
^
Linstead and Co-Workers, £. Chem. Soc.. 1016 (1934).
IE
filtered pigment with five times its weight of normal hydro­
chloric acid, and filtering again.
The precipitate is
repeatedly washed with water, until the filtrate gives no
test for chloride ion.
The precipitate is then thoroughly
dried in an oven at 105°C for several hours, and the pigment
is then ground again with mortar and pestle, and the sodium
hydroxide and hydrochloric acid treatment again repeated as
above.
In all, the whole purification was repeated three
times.
After the last drying, the finely ground powder is
weighed and then dissolved in eight times its weight of
concentrated sulphuric acid.
After standing for forty-eight
hours the concentrated sulphuric acid solution is poured
into an amount of water such that the final volume yields a
5 per cent weight solution of sulphuric acid.
The pigment
is highly insoluble in the 5 per cent sulphuric acid
solution, and the precipitate is filtered off and washed
until free from sulphate ion.
The finished pigment is then
dried overnight in an oven at 105°C and the dried pigment
is then thoroughly ground, in an attempt to get small parti­
cles of relatively uniform size.
Copper, cobalt and nickel
phthalocyanine were synthesized by this procedure; a yield
of approximately 50 per cent was obtained of each.
The formulae for these compounds has been rigorously
established by Linstead and co-workers*^® as being the
15 Ibid*, 1016.
13
following, in which M++- represents the divalent metal:
N
rv
.N — c
A/ 1
c
II
c=
N
The empirical formulae and molecular weights, for the
respective compound considered, together with the calculated
and found percentages of the metal, are shown in the follow­
ing table:
TABLE III
EMPIRICAL FORMULAE AND ANALYTICAL RESULTS ON COBALT, NICKEL,
AND COPPER PHTHALOCYANINE COMPARED WITH THE THEORETICAL
$a MetalT
Compound
Molecular
weight
Calcu­
lated
Found
(by ash)
Found by
electrolytic
deposition
571.07
10.30
9.80
9.92
G3 2 H l 6 % N i
570.82
10.25
7.74
7.82
G32H1 6 % Gu
575.70
11.04
G32^16N8Go
10.4
10.59
14
The percentages of metals shown in Table III were
found both by ashing and by standard electrolytic deposition.
The phthalic anhydride and urea were shed also, and the
metal content was found to be negligible in each case (i.e.,
less than .03 per cent, which is approximately the experimental
error involved in the ashing procedure).
It should be noted
that the calculated and experimentally found values are in
fair agreement, except in the case of the nickel compound,
and as the synthesis establishes the structure, the metal
analyses are considered to validate the correctness of the
synthesis.
The ashing must be done by slow heating and careful
watching to avoid volatilization.
There is a tendency for
fumes to appear from the crucible if the firing is done too
rapidly.
Check results can be obtained, however, by using
an additional burner above the crucible and lid.
The results
are shown in the accompanying Table III.
The method used for effecting a solution of the
phthalocyanine samples for the electrolytic deposition was
as follows:
The sample was dissolved in concentrated sul­
phuric acid and heated to practical dryness.
It was found,
however, that this procedure had to be repeated several
times before the destruction of the complex was completed.
The results of the electrolytic determinations are compared
with the results obtained from ashing in Table III.
15
As shown in the table, the value for the nickel in
the experimental work is found to be low.
However, as the
complex was found to be diamagnetic (as discussed later) it
was not necessary to purify the compound further, for this
investigation.
The construction and theory of the electromagnet used
for the determination of the magnetic susceptibilities has
been previously described in d e t a i l , T h e measurements
were made using calibrated gold weights, which were stand­
ardized against a Bureau of Standards ten gram weight.
Rest
points were found for each weight, as was the sensitivity,
enabling corrections to zero rest point to be made where
necessary.
obtained:
Using this technique, the following data were
(All weights are given in grams.)
A.
MEASUREMENT OF EMPTY TUBE AND
TUBE FILLED WITH WATER TO MARK
(1) Weight of glass tube used in the suscep­
tibility determinations.
(The Gouy
apparatus and tube has been fully de17
scribed and illustrated previously.)
8.9114
George N. Tyson, Jr., "The Construction and Use of
a Strong Electromagnet in Certain Chemical Studies" (unpub­
lished Master*s thesis, University of Southern California,
Los Angeles, July, 1939).
^
Loc. cit.
16
(2) Weight of glass tube when subjected to
influence of magnetic field used*
(4*1 Anrp.)*
8 9114
(3) Weight of tube filled to lack with
15 9279
distilled water
(4) Weight
ofwater (3-1) at 22°G.
(5) Volume
of tube (taking density of
HgO at
(6) Weight
22°C as
.99777)
7 0165
7 032 ml
of tube plus water when sub­
jected to field of 4.1 Amps.*
15 8989
(7) Apparent loss in weight of the
0290
water (3-6)
B.
MEASUREMENTS ON COBALT PHTHALOCYANINE
(0) Weight of tube plus cobalt phthalocyanine
to mark (i.e.,
former level of water)
(9) Weight of cobalt phthalocyanine (8-lj
11 1840
2 2726
(10) Weight of tubeplus cobalt phthalocyanine
when subjected
to field of 4.1 Amps.*
11 2108
(11) Apparent increase in weight of the cobalt
phthaloc yanine
0268
(12) Density of the cobalt phthalocyanine
as packed in the tube, 2.2726/7.032
C.
323
MEASUREMENTS ON NICKEL PHTHALOCYANINE
(13) Weight of tube plus nickel phthalocyanine
to mark (i.e., former level of water)
11.7908
17
(14) Weight of nickel phthalocyanine (14)-(1)
2.8794
(15) Weight of tube plus nickel phthalocyanine
when subjected to field of 4*1 Amps.*
11.7836
(16) Apparent loss in weight of nickel
phthalocyanine
D.
.0072
MEASUREMENTS ON COPPER PHTHALOCYANINE
(17) Weight of tube plus copper phthalocyanine
to mark (i.e., former level of water)
(18) Weight of eopper phthalocyanine (18-1)
11.9633
3.0519
(19) Weight of tube plus copper phthalocyanine
when subjected to a field of 4.1 Amps.*
11.9948
(20) Apparent increase in weight of the copper
phthalocyanine
.0315
(21) Density of the copper phthalocyanine as
packed in the tube, 3.0519/7.032
.434
* 4.1 Amperes were used consistently throughout the
magnetic measurements.
The field developed with the distance
between pole pieces used throughout was approximately 15,000
oersteds.
From the foregoing data, together with the volume
susceptibility of water as given in the International Critical
Tables, Volume VI, page 340, which has the value of
K s -.720 x 10"6 e.g.s. units,
the magnetic moments of the copper and cobalt phthalocyanines
can be calculated.
18
The computations for the cobalt phthalocyanine are
as follows:
It is seen from the data that equal volumes of cobalt
phthalocyanine and water were used in the determination of
the apparent changes in weight of the respective materials
in the magnetic fields.
That isf 7.032 mis of cobalt phthalo­
cyanine apparently increased in weight .0268 grams (see item
B—11) while an equal volume of water lost .0290 grams (see
item A-7).
The magnetic field exerted no measureable influ­
ence on the empty glass tube (see items A)•
Knowing the
volume susceptibility of water (K - -.720 x 10"^), the volume
susceptibility of the cobalt phthalocyanine can be simply
computed:
-0.0290
B 0.0268
-0.720 x 10-6
g
K « 0.664 X 10“° c.g.s.
The volume susceptibility can be readily converted
to the unit weight basis or specific susceptibility, X s , by
dividing by the "density," (which will depend on the relative
degree of tightness of the packing)•
Thus
X 8 s | a 0.66.4_ x 10~6. „ 2.055 x 10=6
d
0.323
The specific susceptibility is converted to the molecular
susceptibility (Xm ) merely by multiplying by the molecular
weight.
Thus
X 3 x M : 2.055 x 10“6 x 571.03 « 1150. x 10“6
The molal magnetic susceptibility, containing dipoles
19
“IQ
of one kind only has been equated by Langevin, ° in which the
effect of both the diamagnetic organic portion and the para­
magnetic metallic portions of the molecule are considered.
It has already been seen that the diamagnetic is opposite to
the paramagnetic effect, and so the equation must take into
account this factor.
The equation is:
Xm = Na f Nu2/ 3kT
where, a - the diamagnetic molecular susceptibility
N = 6.06 x 1023
k s Boltzmann* s constant
T a Absolute temperature
u * permanent magnetic dipole moment (magnetic moment)
The diamagnetic effect is present, because the action
of a magnetic field causes a negative polarization (known
as the Larmor Precession) in all substances.
It can be
sufficiently precisely computed from tables, by merely add­
ing the diamagnetic values for the atoms present.
Thus Na
has been computed from the values in Volume VI of the
International Critical Tables, page 36, as follows:
The
empirical formula of the phthalocyanine radical as given by
18
Bulletin of the National Research Council, Theories
of Magnetism. 55.
19
E.
C. Stoner, Magnetism and Matter (London: Meth
and Company, 1934), 110. The whole subject of magnetic sus­
ceptibilities is discussed in this work, and in particular also,
J. H. VanVleck, The Theory of Electric and Magnetic Suscepti­
bilities (London: Oxford University Press, 1932).
20
Linstead20 is
0 3 2 ^ 1 6 ^8
*
structural formula of the com­
pound has been shown previously on page 13.
In this formula
it can he seen that, per molecule, there are twenty-four
carbon atoms in the benzene rings, and eight carbon atoms
with ethylenic linkages.
The diamagnetic effect of an
ethylenio and benzene carbon vary, and this has been accounted
for in the following table.
TABLE IV
DIAMAGNETIC VALUES OF ATOMS AS COMPUTED FROM VOLUME VI
OF THE INTERNATIONAL CRITICAL TABLES, PAGE 365, FOR
THE PHTHALOCYANINE RADICAL
Number of atoms
Value per atomic wt.
(cgs units x 10+6)
Value per molecule
(cgs units x 10+6)
24 benzene carbons
- 7.75
- 176.0
16 hydrogens
- 3.05
—
48.8
8 Ethylenic carbons
-11.95
-
95.6
8 Nitrogens
- 5.8
-
46.4
Thus, the total diamagnetic effect of the organic
portion of the phthalocyanine compound is the sum of the in­
dividual atoms, which is obtained by adding the last column,
or -376.8 x 10"° e.g.s. units, which is the value of Na.
20
Linstead and Co-Workers, J. Chem. Soc.. 1016 (1934).
El
Boltzmann’s constant has a value of 1.572 x 10“6
.
N
ergs/degree, and thus when T *> 295, the value of -gj-fj? has a
value of 4.97 x 10~36.
Thus, with the previously found
values of Xm and Na, the value of the magnetic moment u, can
easily be found.
It is most convenient to convert this
value into Bohr magnetons, by dividing by the Bohr conversion
unit, which is taken as .9174 x 1020.
The theoretical spin
dipole moment, in Bohr magnetons, is given by the equation:
u s V n(n
S)
where n is the number of unpaired eleotrons.
PI
Thus it can
be easily computed that the values of 1, E, and 3 unpaired
electrons are 1.73, 2.83, and 3.88 Bohr magnetons, respectively.
The observed moments are usually somewhat higher.22
The following table summarizes the results of the
computations on the cobalt and copper phthalocyanines.
TABLE V
SUMMARY OF COMPUTATIONS ON COBALT AND NICKEL PHTHALOCYANINES
Compound
X s x 106
Xm x 106
Bohr magnetons
Exptl. Calcd.
Unpaired
electrons
present
Cobalt
phthalo cyanine
2.06
1155
1.8
1.73
1
Copper
phthalocyanine
1.80
1038
1.8
1.73
1
0
0
0
Nickel
phthalocyanine
—
—
L. Pauling, Nature of the Chemical Bond (Ithaca, New
York: Cornell University tress, 1939), 106^
22 Ibid.. 107.
22
The nickel phthalocyanine was diamagnetic, and ac­
cordingly has no unpaired electrons.
The phthalocyanines of Be+*+, Mg+-<-, Ca++, Sr-*-+, and
Ba++ were synthesized using the same procedure as effected
the synthesis of cohalt, nickel, and copper phthalocyanine,
except that it was not found possible to purify them by the
acid and base washing.
In order to avoid the decomposition
of these phthalocyanines, purification was effected by re­
peated washings with 96 per cent ethyl alcohol.
The yields
obtained were approximately 30 per cent in all cases.
The
phthalocyanines prepared in this manner, again supporting
the work of Linstead, were all found to be diamagnetic.
Another phase of the experimental work consisted in
the reduction of copper disalicylaldehyde.
This compound,
along with cobalt and nickel disalicylaldehyde, has been
Oft
thoroughly described previously in the literature. ° In
this work, the copper disalicylaldehyde was dissolved in
pyridine, and the magnetic moment measured.
The solution
was then put into a Pyrex flask and evacuated by a vacuum
pump to 15 mm of Hg pressure.
By means of a two-way stop­
cock, hydrogen from a cylinder was introduced, in great excess
of the theoretical amount required to reduce the cupric to
cuprous ion.
The flask was then heated to approximately 98°C
prc
G. N. Tyson, Jr., and S. C. Adams, J. Am. Chem. Soo..
62, 1228 (1940).
for several hours, and the originally green pyridine solution
of eupric disalicylaldehyde changed to a deep ruby red color,
provided the original material was allowed to stand for some
time before the hydrogenation was attempted.
The data for
this work follow:
DATA COLLECTED FROM THE HYDROGENATION OF
COPPER DISALICYLALDEHYDE
1.
2.4016 grams of copper disalicylaldehyde diluted to
100 ml with pyridine.
2.
(.0079 moles of compound.)
50 mis of the above solution.
(0040 moles of Cu disalicylaldehyde) used in hydro­
genation set-up.
3.
System evacuated to 15 mm Hg pressure.
The pump was
kept in operation for ten minutes, and as the vapor
pressure of pyridine is appreciable at this temperature,
it is assumed that most of the air was swept out during
the evacuation.
4.
Approximately .008 moles of hydrogen is allowed to enter
the evacuated flask.
5.
Solution heated to 98°C for two hours and no change of
color was noted.
The material was allowed to stand un­
disturbed for six days.
6
.
After standing for six days, the solution had developed
a brown cast, as had the remainder of the solution which
24
had not been put into the hydrogenation set-up.
The
50 ml of solution in the flask was again treated as
previously, that is, evacuation)- to 15 mm of Hg pres­
sure, then the introduction of approximately .008
moles of hydrogen.
On heating at 98°C for thirty
minutes, a ruby red solution developed.
RESULTS FROM MAGNETIC MEASUREMENTS ON SOLUTIONS
OF COPPER DISALICYLALDEHYDE IN PYRIDINE,
AND ON PYRIDINE ALONE
The pyridine used was J. T. Baker and Company C. P.
grade.
The calibrated weights previously mentioned were
used, and the weighing technique was the same.
That is,
actual rest-points were determined in all cases, as were
the sensitivities, and the appropriate correction to a zero
rest-point was made for the weighings.
The same tube was
used in the magnetic field as was used for the previous
measurements, and the tube each time was filled with the
solution to an etched mark which was found in the phthalo­
cyanine measurements to be 7.032 mis.
are as follows:
The results obtained
(All temperatures are at 23°C.)
7. Apparent loss in weight of 7.032 mis of
pyridine
3. Apparent loss in weight of solution of
7.032 ml of solution made by diluting
.0241 gr.
25
2.4016 gr. of Cu disalicylaldehyde with
98.2 gr. of pyridine.
(Measurement made
within five minutes of the mixing of the
complex in the pyridine
,0202
gr,
9# Apparent loss in weight of 7.032 mis of
the above solution of copper disalicy­
laldehyde after standing six days.
(Brownish tint.)
.0202 gr,
10. Apparent loss in weight of 7.032 mis of
the original solution that had been
"hydrogenated" with change in color
after standing six days.
(Color is
ruby red.)
.0206 ^r;
The computations with the above values are as follows:
Items (7)-(8 ) - .0241 - .0202 - .0039 gr.
This is a paramagnetic value and actually represents
an apparent increase in the weight due to the presence of
the copper disalicylaldehyde.
The value is identical for the
solution that had stood for six days.
It is found in Volume
VI, page 364 of the International Critical Tables that the
volume susceptibility of pyridine is -.611 x 10“6.
Thus,
using this relationship to find the volume susceptibility of
the copper disalicylaldyhyde, the following relationship is
valid:
- 0.0241
-.611 x
10"6
"
.0039
K
K - .103 x 10“ 6
26
The "density” of copper disalicylaldehyde in the sample isj
2*4016
98.2 4 2,4016'
— ni>A
""
So, the specific susceptibility is
Xs - 0-103 x IQ - 6 „ 4.29 x 10“®
.024
When by converting this value and the value of Xs obtained
by computing the apparent change of weight in the hydrogenated
material, it is found that approximately 1.9 Bohr magnetons
are exhibited in all three cases.
Thus it is seen that one
unpaired electron is found in all cases, and it is to be
particularly emphasized that the complex, whether it colors
the pyridine solution green or ruby red, still exhibits one
unpaired electron.
In the table following, page 27, the colors of the
compounds to be discussed later are listed as a resumed
The results of the magnetic measurements on the com­
pounds described and the relationship to color, will be dis­
cussed fully in the following pages.
27
TABLE VI
RESUME OF COLORS OF SOME COMPLEXES OF
COBALT, NICKEL, AND COPPER
Compound
Body color
Surface color
Cobalt phthalocyanine
Extremely deep
Blue with purple
Black cast
Metallic copper
Lustre
Nickel phthalocyanine
Rich deep blue
None
Copper phthalocyanine
Deep purple
Metallic copper
Lustre
Freshly prepared copper
disalicylaldehyde
solution
Green
None
Copper disalicylaldehyde
solution stored six days
Green with a
brownish tint
None
Copper disalicylaldehyde
solution stored for six
days, and hydrogenated
Ruby red
None
CHAPTER IV
DISCUSSION OF THE RESULTS AND RELATED LITERATURE
AS RELATED TO CONFIGURATIONS
It was found as listed in the experimental section
that cohalt phthalocyanine exhibits a magnetic moment cor­
responding to one unpaired electron.
The twenty-five
electrons of divalent cobalt ion are arranged in the orbit­
als as follows:
3
Is
2sp3
3sp3
4
d d d d d
nsmi
s
P P P
2 ft*
This arrangement accounts for the experimentally ob­
served magnetic moment of one unpaired electron, and as the
bonding (shown by the "2 s") occurs as dsp2 , the resulting
compound is coplanar.
The convention used in the nomencla­
ture of the orbitals above was shown on page 9 in detail*
The w2sw refer to electron pairs donated to the metallic ion
by the coordinating group, etc.
This nomenclature is adhered
to strictly in the following pages*
In the case of the copper, it was seen that one un­
paired electron was present in this compound also.
value could be interpreted in one of two ways.
This
The cupric
ion has twenty-seven electrons which must be accounted for,
and the possible arrangements are as follows:
First, a tetrahedral structure would exhibit one un­
paired electron:
29
3
Is
2
sp3 3sp3 d d d d d
111111 1 11
4
j3
E E E
2
2
2
2
Or, secondly, as previously noted, the planar con­
figuration which has been found to be more stable than the
tetrahedral could be formed by the shifting of the unpaired
3d electron to a 4p orbital, with the bonding then occurring
in the 3d orbital which is now available for this purpose,
together with bonds in the 4s and two 4p orbitals.
Thus the
configuration of planar copper phthalocyanine would have an
electronic configuration of the cupric ion as follows:
3
4
Is
2sp3 3sp3 d d d d d
nanus
s
PPP
s fff
This structure, it should be repeated, is in accord
with the results of other investigations.
Cox and Webster,
in studying quadricovalent complexes of cupric ion by means
of X-ray analysis, found planar configurations. 2 4
The
theoretically greater strength of the planar molecule has
been discussed by Pauling. 2 5
In an X-ray study of phthalo­
cyanines, it was established that the structure of the
molecules was planar. 2 5
24
Thus it is successfully established
Cox and Webster, J. Chem. Soc.. 731 (1935).
2 5 Pauling, The Nature of the Chemical Bond (Ithaca,
New York: Cornell University Press, 1939), 10O.
Robertson, £. Chem. Soc.. 1195 (1935).
30
that the cupric compound must he considered as planar in
structure.
The divalent nickel complex was found to be diamagnetic,
i.e., no unpaired electron was present.
This indicates with­
out doubt that the only feasible arrangement is as follows
for the twenty-six electrons of divalent nickel:
3
4
Is
2sp3
3sp3
d d d d d
1111 n i l 2
_s £ £ £
2 2 2
The planar configuration of the nickel compound had been
previously noted. 2 7
Thus it has been established that the
phthalocyanine complexes with the divalent ions of cobalt,
nickel, and copper are all coplanar.
It has been established previously that the copper
disalicylaldehyde is planar also. 2*8
this compound is green.
It was also noted that
The color of the compound does not
change when put into solution in pyridine.
The structure
suggested for this compound is as follows:2 9
27
L. Kleram and W. Klemm, J. Prakt. Chem.. 143. 182
“
28
Tyson and Adams, £. Am. Chem. Soc., 62. 1228 (1940).
(1935).
Loc. cit.
31
It has heen shown in the experimental section that
this compound in solution exhibits a magnetic moment cor­
responding to one unpaired electron.
As the compound is
planar in the solid state, it is assumed that the compound
in solution has the same structure.
Thus, the electronic
configuration of the cupric ion would be:
3
Is
2sp3
3sp3
d d d d d
nHllH 2
and this structure is planar.
s
2
4
PPP
2 2 1
It was noted in the experi­
mental section that this compound was changed from green to
ruby red in solution, when a solution of the green material
which had stood for six days at room temperature was
hydrogenated with an excess of hydrogen.
It was noted that
by means of magnetic susceptibility measurements the ruby
red solution showed that one impaired electron was still
present.
If a reduction of the cupric ion had occurred, and
cuprous ion was formed, the compound should have become dia­
magnetic, because the cuprous ion does not have an unpaired
electron.
Thus, the electronic configuration of the twenty-
eight electrons of cuprous ion are arranged as:
3
4
Is
2sp3
3sp3
d d d d d
s
PPP
1111313111
2
2 2 2
Thus, cuprous ion is diamagnetic, and has a tetra­
hedral structure.
However, the experimental section shows
that the red compound exhibits one unpaired electron.
This
32
is in direct contradiction to the assumption made by Calvin, 3 0
that the change in color is ascribed as being due to the
reduction of the cupric ion*
In this work, the uptake of
hydrogen was measured and rates of reaction considered.
Calvin did not measure the solutions, in which quinoline
was used as the solvent, by means of the susceptibilities
exhibited.
The experimental values in this work have been
consistently checked and definitely refute the assumption
made by Calvin.
A reasonable explanation can be given for
the experimental results observed, however.
It can be
reasonably postulated that the planar structure is converted
to a tetrahedral structure by the hydrogenation, and the
electronic structure of the cupric ion is as follows:
3
4
Is
Ssp3
3sp3
d d d d d
nnain i
s
z
PPP
222
From this arrangement it is seen that the unstable
tetrahedral arrangement is attained.
This is in good agree­
ment with the chemical behavior observed by Calvin^ in
which the red form is unstable, and cannot be recovered in
the crystalline form, as the red compound changes to the
green on exposure to air.
On the basis of experimental work of susceptibilities
30
•stn
M. Calvin, Trans. Farad. Soc., 34, 1181 (1938).
Loc. cit.
33
measured in this research, the hydrogenation of cupric dis­
alicylaldehyde is explained by the following equations:
This mechanism would account for the uptake of hydro­
gen, and the ready conversion of the reduced compound to
the original form in the presence of oxygen#
One further experimental fact must still be explained,
however#
In the previously eited work of Calvin, as well
as in this experimental study, it was noted that the green
cupric compound became brown on standing.
It was found, as
previously noted, that the brown solution still exhibited
one unpaired electron.
This is taken as indicating the
breakdown of the complex structure, at least partially, with
a resulting formation of cupric oxide.
No marked change in
magnetic moment would be expected, however, as cupric ion
has the following electronic arrangement in cupric oxide:
3
Is
2sp3
3sp3
d d d d d
n n n m
34
It is evident, however, that this postulated meehanism
of the so-called reduction of copper disalicylaldehyde is
catalyzed by an agent not shown.
This factor has been dis­
cussed at some length in the work as reported by Calvin.
A summary of the work related to configuration is:
Cobalt, nickel, and copper phthalocyanine as well as green
copper disalicylaldehyde are all planar, while red cupric
disalicylaldehyde is tetrahedral.
The relationship of the configuration to color, and
the pertinent literature will be discussed in the following
pages.
CHAPTER V
THE RELATIONSHIP OF COLOR TO CONFIGURATION IN THE
COMPOUNDS CONSIDERED, WITH A FURTHER DISCUSSION
OF RELATED LITERATURE
Recently Lifschitz and his collaborators®** have pre­
pared, and measured magnetically, many complexes of nickel.
This work appears to indicate that the color of the com­
pound is closely related to its bond and coordination type.
The compounds prepared were the nickel complexes of stilbenediamine (1 ,
2
diphenylethylenediamine, which is desig­
nated as "stien" in Table VII to follow) and monophenylethylenediamine (which is designated as "phenen" in Table
VII),
In these complexes, two molecules of the diamine are
coordinated with divalent nickel.
These workers have found
that all of the diamagnetic complexes are yellow, and all
of the paramagnetic complexes are blue.
Their results are
summarized in Table VII.
It is readily seen that this work lends striking
credence to the theory that the color is dependent on the
configuration.
From Table VII it is noted that compounds
of identical composition, such as Ni phenen2 (NOgIg,
Ni stieng(ClgCCOO)g, Ni phenengtClO^Jg, can be either blue
or yellow, depending only on the magnetic susceptibility.
In the remaining compounds, the differences other than the
3 2 Lifschitz, Bos and Dijkema, Z. Anorg. Alle.1. Chem.
242, 97 (1939).
~
36
TABLE VII
SUMMARY OF COLOR TO CONFIGURATION RELATION IN
DIVALENT NICKEL COMPLEXES OF DIAMINES AS FOUND
BY LIFSCHITZ AND CO-WORKERS*
Diamagnetic complexes
(yellow)
Paramagnetic complexes
(hlue)
Ni stien2S04 'H£0
Ni st ien2 S04 *2H20
Ni stien2(Cl3CC00)2
Ni stien2(Cl3CC00)2
Ni stien2(HCOO)2 *4H20
Ni stien2(HC00)2
Ni phenen£(0 1 0 4 ) 2
Ni phenen (0 1 0 4 ) 2
Ni phenen2(N03)2
Ni phenen2(N03)2
Ni stien2Cl2*2H20
Ni phenen2(N03 )2 «2H20
Ni stien2Cl2
Ni stien2(0 ^
Ni stien2(N03)2
Ni stien2(CH3C00)2
Ni stien2(0 1 0 4 ) 2
Ni phenen2Cl2#2H20
5000)2
Ni stien2 (C^q H-^g04BrS)2^
a
Lifschitz, Bos and Di.ikema. Z. Anorg. Alle.i. Chem.,
242, 97 (1939).
~
* ---13
d-a-Bromocamphor-S- Sulfonate
37
susceptibility is not great.
Thus, the yellow Ni stiengSO^HgO
which is diamagnetic contains only one less molecule of water
than the blue paramagnetic Ni stiengSO^'EHgO.
Inspection of
the remainder of Table VII indicates that the differences
between the diamagnetic and paramagnetic complexes are not
striking except for the magnetic effect of the unpaired elec­
trons.
The differences in color (and corresponding differ­
ence in susceptibilities) of the blue and yellow compounds
were obtained by slightly changing the conditions of the
syntheses.
Thus, such differences as rate of cooling, the
solvent used for precipitation, etc., would determine whether
a diamagnetic or paramagnetic compound would result.
Lifschitz and his co-workers3 3 have conclusively
assigned the planar structure to the yellow diamagnetic com­
pounds on the basis of other experimental work.
compounds are assumed to be tetrahedral.
The blue
The generalization
is then made that all diamagnetic nickel complexes of this
type are yellow, and the paramagnetic complexes are blue.
In a discussion of this problem, Pauling3 4 also notes
that the color is determined by the nature of the attached
atons as well as the type of coordination.
33
34
Thus, the
Lifschitz, Bos and Dijkema, op. cit., 843. 97 (1939).
Pauling, Nature of the Chemical Bond, 123.
38
diamagnetic divalent nickel disalicylaldimine complex is
orange, and the paramagnetic disalicylaldehyde is green.35
Other divalent compounds of nickel which show the influence
of the attached groups are the diamagnetic compounds
Ni(P(C3 H 5 )3 )gX2 (with X = Cl, Br, or CIO4 ); these are red,
and are to be contrasted with the paramagnetic nitrate,
colored a deep red.36
Thus it can be seen that the evidence
tends to support the fact that a change in color is marked
when a configuration is changed, but that the colors are
affected also by the nature of the atoms in the coordinating
group.
For purposes of comparison, the preferred formula of
a yellow diamagnetic compound as given by Lifschitz and
collaborators® 7 is contrasted with the formula previously
given for the diamagnetic planar compound of divalent nickel
phthalocyanine. 5 8
35
Tyson and Adams, J. Am Chem. Soc., 62, 1228,
(1940).
36
K. A. Jenson, Z. Anorg. Allg. Chem.. 229, 265,
(1936).
37
Lifschitz, Bos and Dijkema, Z. Anorg. Allej. Chem..
242. 97 (1939).
33
(1934).
Linstead and Co-Workers, J. Chem. Soc.. 1016
39
H
—
—
H
C ~ N
X
H
I
1
c —
H
H
N
H
H
H
N -c - c6 Hr
H
^ - C - C £Hr
H
/J/e-
An inspection of the above formulae show that in both
complexes the divalent nickel is bonded to four nitrogens
atoms.
Although both complexes are diamagnetic, and possess
planar structures, the Ni stien2 X 2 is yellow and the nickel
phthalocyanine is an intense blue.
The differences in the
40
coordinating groups are seen to exert a dominating influence
on the color, and slight differences may cause a marked
change.
It should also be stressed that when the configura­
tion of the divalent metal is changed in the molecule, the
color will also undergo a marked change.
Thus, it seems
reasonable on this basis, when coupled with the previous
discussion of the stability of planar and tetrahedral con­
figurations, to assume that the planar green copper disali­
cylaldehyde changes to the red tetrahedral configuration
when the hydrogen is taken up.
An inspection of the experimental data shows that
cobalt, nickel, and copper phthalocyanines are of varying
shades of blue.
This data indicates that there are but
slight gradations in color, when the same coordinating group
is used, with the change in increasing weight of the central
metal ion.
This appears to indicate definitely that the co­
ordinating portion of the complex molecule, at least in the
phthalocyanines investigated, has the dominant influence
on the color, and the choice of the metallic ion merely
modifies the color slightly.
Certainly it is evident that
the difference of diamagnetism and paramagnetism does not
radically alter the color in the cases of the paramagnetic
cobalt and copper phthalocyanines and the diamagnetic nickel
phthalocyanine.
However, the nature of the coordinating group
precludes the formation of bonds other than the planar type,
and it is to be stressed that no radical change in color occurs.
CHAPTER VI
SUMMARY AND CONCLUSIONS
In experimental work with the compounds formed by co­
ordinating divalent ions with phthalocyanine, and the analysis
and determination of the magnetic susceptibility of some of
the compounds, it has been found possible to verify and
deduce some limited conclusions concerning the color of co­
ordinated compounds.
It has been found that in the series of complex sub­
stances formed with phthalocyanine and the ions of the
elements of Group Ila of the periodic table, beryllium
phthalocyanine is deep green, and the color becomes progres­
sively lighter with increase in atomic number, until In the
case of barium phthalocyanine, the compound has but a faint
tinge of green.
Because of the nature of the coordinating
group, as found in the literature, it is known that all of
the compounds are planar in configuration.
In a more extensive investigation of the compounds
cobalt, nickel, and copper phthalocyanine, it has been found
that cobalt and copper phthalocyanine are paramagnetic, and
exhibit one unpaired electron, while nickel phthalocyanine
is diamagnetic.
All of the compounds are planar in con­
figuration as found from their measured susceptibilities,
and that these compounds show varying shades of blue.
Thus
42
it is indicated that the configuration functions as an im­
portant factor in the determination of color, and the metal
ion modifies the color.
It has also been noted that the color of planar nickel
compounds varies with the atoms in the coordinating group,
as seen by a comparison of probably planar nickel disali­
cylaldehyde, which has been previously described.
compound is green.
This
The effect of the coordinating group
can be more fully illustrated by a further search of the
literature.
Thus, the planar complex of divalent nickel
diphenylethylenediamine is yellow.
Both this compound and
blue nickel phthalocyanine are coordinated to four nitrogen
atoms, thus lending further support to the statement that
the color of the complex, of the configuration under consid­
eration, is strongly affected by the nature of the coordin­
ating groups.
The marked change in color with change in configura­
tion has been shown by the change of color of copper disali­
cylaldehyde in pyridine solution, upon hydrogenation.
This
compound, which had been previously shown to be green when
occurring as a planar structure, was found to change to a
red color on assuming the tetrahedral structure after
hydrogenation.
The magnetic measurements on these solutions
conclusively showed that there was no change in the elec­
tronic configuration of the divalent copper after the
43
hydrogenation.
Substantiation of the hypothesis concerning
the change of color involved when complexes undergo change in
their configuration was found in the literature in the case
of the nickel diamines.
It was noted in this case that the
planar compounds were yellow, while the tetrahedral compounds
were blue.
A reasonable reaction to explain the change in color
in copper disalicylaldehyde in pyridine solution when treated
with hydrogen has been given.
The reaction is:
<0
Cx)
In this reaction, the compound (1) is green, with a
planar configuration, and on hydrogenation of the aldehyde
group the compound is changed to a tetrahedral structure (2 ).
The measurements of the magnetic susceptibilities are in
conformity with this hypothesis.
BIBLIOGRAPHY
BIBLIOGRAPHY
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~
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C.
UNPUBLISHED MATERIAL
Tyson, George N . , Jr., ’’The Construction and Use of a Strong
Electromagnet in Certain Chemieal Studies.” Unpublished
Master’s thesis, University of Southern California, Los
Angeles, July, 1939.
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