Colour of 3D Transition Metal Compounds. Part 1. Experimental Quantitative Studies and Ligand-Field Based Predictions For D / D, D and D Systems

COLOUR OF 3d TRANSITION METAL
COMPOUNDS. PART 1. EXPERIMENTAL

QUANTITATIVE STUDIES AND LIGAND-FIELD
BASED PREDICTIONS FOR d \ d 4 , d 6 AND d 9 SYSTEMS
A d a m Bartecki a and Krzysztof Kurzak b *
a
Faculty of Chemistry, University of Technology, 50-370 Wroclaw,
Poland
b
Department of Chemistry, University of Opole, 45-052 Opole,
Poland
CONTENTS
Abstract 389
Abbreviations 390
1. Introduction 392
2. Experimental and simulation procedure 394
3. Colour and simulations for d" ions 397
2 4
3.1. High spin Cr (d ) compounds 397
3.2. Cu 2+ (d 9 = d 5+4 ) compounds 412
3.3. V0 2 + (d 1 ) compounds 419
3.4. High spin Fe2 (d 6 = d 5+l ) compounds 424
4. Some general remarks 426
4.1. Colour of Ti 3 (d1) and Mn3+ (d 4 ) compounds 429
5. Appendix 431
5.1. CIE chromaticity diagram and coordinates 431
5.2. CIELAB and CIELUV spaces 438
6. References 439
* Author to whom correspondence should be addressed;

E-mail: Krzvsztof.Kurzak@uni.opole.pl
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Vol. 26, No. 4, 2006 Colour of 3d Transition Metal Compounds.
Part 1.
ABSTRACT
An account was elaborated on interrelation of Vis-NIR spectroscopy and

quantitative colorimetry of d1, d4, d6 and d9 (coloured) coordination
compounds. Based on literature sources, own experimental data and a
proposed simulation procedure applied to about 250 compounds interesting
results were obtained allowing for better understanding and predicting colour
characteristics. Assuming the Dq parameter as a key quantity (for a given
symmetry and applying the CIELAB (or CIELUV)) colour coordinates,
characteristic curves of colour travel were simulated and experimentally
supported for Cr(II), Cu(II), VO(II) and Fe(II) complexes. Preliminary data
were also obtained for Ti(III) d 1 and Mn(IlI) d 4 coloured compounds. The
discussion in detail of colorimetric data on some of these compounds would
be a proof for a meaningful application of colour in coordination chemistry.
ABBREVIATIONS
2Meiz 2-methylimidazole
3,5-dichloropyridine
3-bromopyridine
3-chloropyridine
3-iodopyridine
3-methylpyridine
4-methylpyridine
5-methylpyrazole
acetyloacetonate
amine
amq 8-aminoquinoline
bi biuret
BN benzonitrile
bpy 2,2-bipyridyl
CHC13 chloroform
DCE 1,2-dichloroethane
dctu Ν ,N' -dicyclohexylthiourea
uien diethylenetriamine
DMF N,N-dimethylformamide
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Bartecki and Kurzak Reviews in Inorganic Chemistry
dmp l,2-diamino-2-methylpropane
dmpz 3,5-dimethylpyrazole
DMSO dimethyl s u l f o x i d e
en ethylenediamine
EtOH ethanol
etu N,N'-ethylenethiourea
FM formamide
H2B{4,5-(5-N02benzo)pz}2 indazole, 4,5-substitued pyrazole
H2Cdmpz2 I, I ' - m e t h y l e n e b i s ( 3 , 5 - d i m e l h y l p y r a z o l e )
H2Cpz2 1,1 ' - m e t h y l e n e d i p y r a z o l e
Hisalen salicylideneethylenediaminc
HBrsap 5-bromosalicylidene-2-aminopyridine
HCpz-s tris(l-pyrazolyl)methanc
hexH h e x a m i n e , hexametylenetetraminc
Hgly-o glycine
Hhis-o hisiidine
Hmcys-o S-methyl-L-cysteine
Hmel-o methionine
H n B(pz) 4 .„ polypyrazolylborate (n = 0, 1 or 2): B(pz) 4 , HB(pz)^, H 2 B(pz) 2
HNsap 5-nitrosalicylidene-2-aminopyridine
Hsalan salicylideneaniline
Hsap salicylidene-2-aminopyridine
HsapN salicy!idene-2-amino-5-nitropyridine
Hsal salicylidene-2-aminolhiazole
iz imidazole
M e 2 | 1 4 | a n e N 4 meso-5,12,-dimethyl-1,4,8,11 -tetraazacyclotetradecane
Me^cyclam 1,4,8,11 -tetramethyl-1,4,8,11 -tetraazacyclotetradecane
M e 6 j 14]aneN 4 meso-5,7,7,12,14,14-hexamethyl-l,4,8,11-tetraazacyclotetra-
decane
MeCN acetonitrile
McOH methanol
MeTPyEA tris(3,5-dimethyl-1 -pyrazolylelhyl)amine
mur methylurea
NEtiz 1-ethylimidazole
NMepz l-methylpyrazole
Nmiz N-methylimidazole
NN'dmn Ν,Ν'-dimethylenediamine
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phen 1,10-phenanthroline
pic 2-aminomethylpyridine, 2-picolylamine
pn 1.2-diaminopropane, propylenediamine
py pyridine
pz pyrazole
sh shoulder
THF tetrahydrofuran
tmd 1.3-diaminopropane
tmen N,N-tetramethyldiamine
TPyEA tris(l-pyrazolylethyl)amine
tu thiourea
ur urea
vb very broad (band)
I. INTRODUCTION
In the world of coloured objects one class, namely chemical (coloured)

compounds, deserves our special interest. The reason for such a statement is
simple. There is a huge number of such compounds known, natural and
synthetic, and new coloured compounds are steadily obtained accompanying
various studies and research. On the other hand all coloured objects could
appear as having different hues, the number of which is roughly estimated to
be 5-10 millions. In the early thirties, studies on coloured objects succeeded
by formulation of chromaticity coordinates and chromaticity spaces based on
three-colour theory (RGB), which then allowed to specify colour systems:
CIE, CIELAB and CIELUV. These systems were and are broadly applied in
chemical industry and technologies, e.g. for pigments production, colouring
procedures, to food technology, and this turned out useful even in biology,
i.e., in the animal world /I/.
In chemistry, generally speaking, colour can serve as an important factor
not only to consider or suggest the probably structure or even the
composition of a chemical compound, but also colour changes could provide
the user with information about the reaction course in the system studied.
It is well known that: (1) many elements and their compounds are
coloured, for instance, transition metal and inner transition metal (lanthanide)
compounds, iodine, sulphur, NO; (2) colour arises during the course of
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chemical reactions when not only the intermediate is coloured but also the
final product (or products) (even when the starting substrates are colourless).
Now, if our target is to describe precisely the colour (of coloured objects)
not only by (subjective) naming its hues, but rather reach some objective
data, then quantitative measures are needed.
Since about the year 1931 colour science has in its disposition a firm base
to express the colour hue in a quantitative manner. The CIE, CIELAB and
CIELUV colour systems were invented then and broadly applied to many
coloured objects and to many technologies. The data obtained by these
methods, i.e., chromaticity coordinates and chromaticity diagram, are
strongly helpful for colour characterization and its stability. Moreover, colour
parameters were used as standards for products quality.
In chemistry these (and many other) parameters are used for analytical
purposes and a lot of papers devoted to this problem has been published /2-9/.
However, colour quantitative measures could also be helpful as one of the
physicochemical properties characterising the structure and properties of
chemical compounds. To show that colour deserves to be considered as such
a property, and by logical reasoning to choose a strongly defined class of
chemical compounds (with main properties identical), we started
investigations on quantitative aspects of transition metal objects.
Being strongly engaged in chemistry of these compounds, especially of
the first row of transition elements, we tried to show how colour does depend
on electronic configuration of the d-element, geometrical structure and
symmetry of its compounds, and the kind of ligand in the coordination
sphere. At this point let us mention the papers of F r e m y / 1 0 , 1 1 / published in
1852 about the colours of cobalt(III) compounds, describing their colour hues
by naming them, e.g., luteo-, croceo-, flavo-, purpureocobalt chloride.
As colour is determined and evaluated from the absorption (transmission)
spectrum, it is reasonable to look on the course of the spectrum. The right
understanding of colour appearance is supplied by taking into account the
energy levels and transitions between them (besides basic optical
phenomena). When such a transition takes place within the optical region,
then a part of light is transmitted (or reflected), causing a concrete colour of
the object. Without going into (spectroscopic) details some principal rules
may be cited here.
When the ground state atomic term (generally denoted 2S+I
LJ) is S (which
means that L = 0), then no other term exists having the same (highest)'
multiplicity). In such a case no allowed transition to other states could
appear. Electronic configurations d°, d 5 (high-spin) and d 1 0 create such a
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situation and corresponding compounds are expected to be colourless, and in

reality, e.g. Mn 2+ is colourless. All this applies to colour caused by d-d
transitions, and e.g. the purple colour of M n 0 4 must be of the effect of
another reason. Charge transfer transitions from metal energy levels to ligand
levels or vice versa, or even ligand inner transitions, could also cause the
appearance of colour. Changes of the colour caused by charge transfer (CT)
transitions are commonly understood and widely studied but change by
ligand-field transitions (LF) is unusual.
2. E X P E R I M E N T A L A N D S I M U L A T I O N P R O C E D U R E
The near infrared (NIR) and visible (VIS) spectra (both solutions and
solid state) were carried out (digitally with 1 nm step) on a Cary 5E (Varian).
A comparison of the aqueous solution spectra of: [Cr(H20) 6 ](C10 4 ) 2 (1),
[ C U ( H 2 0 ) 6 ] S 0 4 (2), [ V 0 ( H 2 0 ) 5 ] S 0 4 (3), [ F e ( H 2 0 ) 6 ] S 0 4 (4) in NIR-Vis
region is presented in Fig. 1. The measurement conditions for the spectra in
v, c m 1
Fig. I : Comparison of the aqueous solution spectra (c = 0 . 2 M , 1=1.0cm)

of: [Cr(H 2 0) 6 ](C10 4 ) 2 (I), [Cu(H 2 0) 6 ]S0 4 (2), [ V 0 ( H 2 0 ) 5 ] S 0 4 (3),
[Fe(H 2 0) 6 ]S0 4 (4), in NIR-Vis region
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this region were the same, i.e., c=2.0xl0"' Μ, 1 = 1.0 cm. The spectral data at
selected ca. 1500 wavenumbers over the range 7000-27800 cm"1 were used to
resolve into the Gaussian components. These spectra were applied for
calculations of ligand-field parameters (in NIR-VIS region), simulations and
finally of chromaticity coordinates (in VIS region).
The convenient approach has been presented for the tetragonal distorted
Cr(III) complexes in previous works /12, 13/. In the present work, the matrix
elements of the excited states presented in paper /12/ were used for species in
aqueous solutions of d 1 , d 6 ( V 0 2 + and Fe 2+ ) directly, and d 4 , d 9 (Cr 2+ and
Cu 2 + ) assuming hole-electron formalism. For the d4, d6 electronic
configurations only spin-allowed transitions have been taken into account.
The total one-electron orbital energy equations given by Kurzak/12/ were
applied for complexes with D 4h symmetry. All band maxima reported in this
work are determined from Gaussian analysis of the experimental spectral
contours and used for simulation. Absorption spectra were fitted with
Gaussian components using CFP computer program/14/ (and refs. herein),
based on the Slaviö /15/ algorithm, which for the last few years has been
successfully applied by us to the resolution of d-d (ligand-field) spectra. The
ligand-field parameters (CFM) were calculated using the LFP computer
program /13/ (CFM/AOM). The assignment of bands is based on fitting the
obtained band maxima (from Gaussian analysis) with the calculated
transition energies using the d' quadrate energy levels. In this work, all the
ligand-field (d-d) spectra of: [Cr(H 2 0) 6 ](C10 4 ) 2 , [Cu(H20)6]S04,
[ V 0 ( H 2 0 ) 5 ] S 0 4 , and [ F e ( H 2 0 ) 6 ] S 0 4 have been assigned, using ligand-field
model and D 4h symmetry. These were applied for simulation of the spectra
and chromaticity coordinates as a function of Dq parameter.
The simulation can show influence of both energetic shifts of absorption
bands and the solution colour. The latter effect is hardly to be observed by
human eye. T o precisely characterize the colour one usually uses tristimulus
colorimetry /2-9/. To this aim the CIE, CIELAB, and CIELUV systems were
applied for a quantitative description of sample colour. The chromaticity
coordinates have been calculated from the absorption spectra (in region 360-
830 nm) by the method described in R e f s / 4 , 1 6 , 1 7 / for non-uniform (CIE)
and two uniform (CIELAB or CIELUV) spaces. The calculation of these
coordinates has been accomplished using CIEC computer program /18/. This
is designed to calculate the colour parameters for the solution, solid

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Part I.
(reflectance) and simulated spectra. The CIE tristimulus values (X, Y, 2)

expressed as integrals (or sums) /4, 19/ are calculated as well as chromaticity
coordinates (.χ, y, z) and two space parameters: CIELAB (L*, a*, b*) and
CIELUV (L*, u \ v'). The standard data/2, 19/ are built in the routine, i.e.,
colour matching functions taken every 1 nm in the range 830-360 nm, as well
as standard illuminant D 65 . Absorption spectrum is transformed into
equivalent transmission spectrum. In the case of reflectance spectrum one can
use the Kubelka-Munk function 120/ for preliminary data transformation.
In the course of our studies on optical spectra of transition metal
compounds it was shown that their colour quantitative characteristics,
expressed by chromaticity coordinates, clearly correspond to properties and
structure of the studied objects. Colour parameters yielded by CIE, CIELAB
and CIELUV colour spaces are derived from the optical spectra and
described in detail in many sources. Our main goal was to find out relations
between the spectra and colorimetric data, if such relations do exist at all. As
a result of many investigations /4, 5, 7-9/ it has been demonstrated that the
ligand-field parameter, Dq, could create a basis for expressing such a relation
with colour characteristic parameters. This would approximately be true
when the colour of transition metal compound would be caused only by
ligand-field spectra, i.e., d-d transitions (and not by, e.g., CT transitions in the
optical region). Hence, using the Dq parameter, one should be able to
simulate the spectra and to predict the corresponding colour. Such
simulations were carried out for many systems and described in literature
/4, 5, 7-9/. The steps in using our model are as follows:
( 1 ) T h e experimental optical spectrum of the proper metal compound is
chosen, in this case a solution of sulphate salts in water (c=0.2 M,
1=1.0 cm), that characterized 'pure' tetragonal symmetry (D 4h ). Gaussian
analysis results (component bands parameters) and ligand-field
parameters are carried out.
(2) The set of resulting parameters is taken as constants: 8' m a x , δ ' ι / 2 , except
v' max set that depends on Dq values.
(3) The last is calculated for a variety of Dq values, that for simulation are
varied within a broad range ( 1 0 0 0 - 3 0 0 0 , with step 50 cm"1), i.e., the
transitions energy diagram is generated using LFP program /13/.
(4) For each new Dq value, the overall contour of the spectrum is calculated
and the chromaticity coordinates determined applying the CIEC computer
program /18/.
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The results of these simulations are demonstrated in Sections 3 and 4 for a

broad Dq range 1000-3000 cm' 1 (the graphical step is 200 cm"' for clarity).
3. COLOUR AND SIMULATIONS F O R I O N S
3.1 High spin Cr 2+ (d4) compounds
This paper is devoted to studies of spectra and colour of compounds with

d , d 9 , d1 and d 6 central atom configuration. At the beginning we decided to
4
look at Cr 2+ coordination compounds, as it was stated that a considerable

amount of such entities is blue and strongly similar to Cu 2+ compounds (of
which electronic spectroscopy is well known and understood). According to
Lux and Illman 1211, the compounds C r S 0 4 - 5 H 2 0 and C u S 0 4 - 5 H 2 0 have the
same colour hue (in German: Farbton) and colour depth (in German:
Farbtiefe) and are iso-structural. They explained the situation remembering
that in both these compounds there is a lack of one electron to fulfill the full
electron configuration (d 10 ) or the half of t 2g (which contains 6 electrons). In
other words this is equivalent to the statement d n Ξ i.e., that the energy
states are the same in a d" and d (n+5) (for η = 1,...., 4) or d(n"5> (for η = 9 , . . . , 6)
configuration.
The electronic configuration of the Cr 2+ ion is d 4 and in O h symmetry the
electron distribution is t 2g 3 e g ' or t 2g 4 . Schematically this situation is depicted
in Fig. 2 . It is evident that the left-side distribution corresponds to high-spin
and the right one to low-spin compounds. Accordingly the value of magnetic
moment is normal (about 5 B.M.), i.e., there are four unpaired electrons in
the first case and two in the second one.
As previously mentioned, the great majority of Cr 2+ compounds exhibit
normal paramagnetic properties, being mainly octahedral regular or
tetragonal distorted. Hence, the electronic spectroscopy would be very simple
and one expects one absorption band in the visible range. In fact, there is seen
at least one more absorption band due to {mainly) tetragonal distortion.
5
In O h symmetry this absorption band is caused by the E g —• 5 T 2 g
transition, in distorted (tetragonal) compounds three bands should appear
which are seen in Fig. 3 ..In practice many complexes of Cr 2+ exhibit only
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®9
l2
- 4 "
- H
high-spin low-spin
μ sο = 4.90 BM μ δ ο = 2.83 BM
Fig. 2: Occupancy of dorbitals in octahedral chromium(II) complexes
E 5
' · T2g 'Ba.
5 5
B2g Eg
5 5
Al9 ^ ^ B 1g
5 5
B19 " " " ^ \ A 1g
D4h Oh D4h
(elongated) (compressed)
Fig, 3: Energy levels of high-spin chromium(II) in ligand fields of O h and

D4h symmetry
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two bands as demonstrated in Table 1, in which magneto-chemical data are

also presented.
It is evident that wavenumbers of both absorption bands do not change
considerably in many of these compounds. The higher energy band laying at
approximately 14000 cm' 1 (714 nm) is assumed as the 10 Dq value.
All compounds with such a value are distinctly blue and it should be
stressed that this colour might characterise a wealth of Cr 2+ compounds. The
data extracted from Wilkinson's article 1221 and other data /23-51/ show that
among 171 compounds 138 ones were characterised by colour name. For the
last 57 are blue, 26 green and other colours are characteristic for 55 only
(yellow, red).
As mentioned previously, an idea to connect electronic absorption spectra
and the 10 Dq value obtainable by their analysis for prediction of colour of
the compound was put forward and described in /4, 5/. Lastly it was applied
to a Co 2 * complexes and the simulation procedure was described in our
work /52/. This method of colour predicting was shown to be very promising.
Colour of coordination compounds does not depend only on the central
(metal) ion, but is simultaneously governed by the ligand molecules attached,
which could be differently arranged towards the metal ion. The influence of
ligands on the colour of the complex compound could be formally anticipated
by considering their place in the spectrochemical series of ligands. The
spectrochemical series considers different ligands with (increasing) Dq
values extracted from the spectrum (directly or by calculations based on
solving energy matrices due to a given electronic configuration). The 10 Dq
value could approximately be estimated as f x g , where g denotes the value in
cm' 1 for the given element (and oxidation state) a n d / c h a r a c t e r i s e s the ligand
applied. As this product equals 14000 cm"' (for H 2 0 as ligand) one could
assume it as the g value for Cr 2+ .
The simulation of Cr 2+ colour hues was based on the Perchlorate salt, i.e.,
assuming [Cr(H 2 0)6](C10 4 )2.. Its colour characteristics were given in x, y,
CIE, and CIELAB and CIELUV colour systems (q.v. Table 7 in Section 5,
Appendix). Looking at the CIELAB chromaticity diagram, we see that at the
10 Dq value of 14000 cm"' (= v 2 ), transmission of light takes (approximately)
place: at about 20406 - 20833 cm"1 ( 4 9 0 - 4 8 0 nm), i.e., in the (χ, y) bluish
green area.
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Part 1.
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Part 1.
The results of the simulation for d 4 configuration based, on the spectrum

of [Cr(H 2 0) 6 ](C10 4 ) 2 ] /24/ as a function of a broad Dq range 1000-3000 cm' 1 ,
are demonstrated in Fig. 41a. Fig. Φ- shows CIELAB colour parameters for
assumed Dq range (the step is 50 cm"'). The CIELAB data (for the visible
part only) clearly shows that colour of the Cr 2+ solution, for instance in the
solution creating a low ligand-field, would change its hue from greenish-blue
v, cm
Fig. 4: Simulation of spectra in aqueous solutions (c = 2 . 0 x 1 0 " ' M ,

1 = 1.0 cm), as a function of Dq parameter: 1000 - 3000 cm' 1
1
(200 cm' step), for [Cr(H 2 0) 6 ](C10 4 ) 2 (a), and [ C u ( H 2 0 ) 6 ] S 0 4 (b),
with the experimental spectra 3 and 12, respectively; D 4h symmetry,
d 4 and d 9 electronic configuration.
410
Authenticated
Fig. 5: The CIELAB plane. The colour points correspond to simulated

spectra of [ 0 ( Η 2 0 ) 6 ] ( C l O ^ in aqueous solution, as a function of
Dq parameter: 1-1000, ... 41-3000 cm"1 (50 cm' 1 step), the 9th
point corresponds to experimental spectrum
Then we are in the position to predict colours for some frequently used
ligands, e.g., for OH", NH 3 , and EDTA. Starting with 6 OH groups we get a
band maximum at 13254 cm"' (754 nm), which means that the corresponding
value of light transmitted would result in a bluish green colour of the
complex, and for E D T A as a ligand calculation results in getting 16920 cm"1
(591 nm), the colour shifts then to blue green. According to this crude
prediction, a red Cr 2+ compound would contain an absorption band at about:
20450 cm"1 (490 nm), and in a yellow complex with a light transmission at
about 17000 cm"1 this band must be situated at about 480 nm.
411
Authenticated
Part 1.
3.2CU 2 + (d 9 = d 5 + 4 ) c o m p o u n d s
According to experimental data there is a great resemblance between Cu 2 t

and Cr 2+ coordination compounds. As was mentioned earlier, a striking
similarity exists between Cr2+ and Cu 2+ sulphates in their colour hues and
structures. These oxidation states correspond in the first case to d 4 .electronic
configuration and d 9 in the second one and the ordering of their electronic
states is the same. Such a situation results in many similarities between two
sets of corresponding compounds. Considering the purpose of this article,
devoted mainly to electronic spectroscopy and to its link to colour, we should
stress that, like Cr2+ compounds, a great majority of Cu 2+ compounds exhibits
a blue colour as well. Moreover, it is said to be a characteristic feature for
Cu 2+ compounds, although these compounds could exist in a variety of
geometrical structures and symmetries. This is shown in Fig. .6". Because of
that situation the case of Cu2+ compounds is more complicated than in Cr 2+
+
compounds. Fig.,: V. shows the Cu energy ranges of the d-d transitions of
CuN x chromophores. As seen, the d-d transitions are very close together and
structure of complexes cannot be uniquely deduced from wave numbers of
bands positions.
Energy (v-10'3, cm' 1 )
16 8 10 12 16 18 20
I I I I I I I I
Compressed tetrahedral Square coplanar
Restricted Tetragonal octahedral Elongated tetragonal octahedral
Square pyramidal
Trigonal bipyramidal
cis-distorted Octahedral
Fig. 7: The Cu 2+ energy ranges, 4000 - 30000 cm"', of the d-d transitions
of the CuN x chromophores
412
Authenticated
( a ) C o m p r e s s e d •< ** E l o n g a t e d
^ ^ d . ,
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tetrahcdral octahedral octahedral bipyramidal
T„ D 2d C2 Dj D3h
Fig. 6: The splitting of one-electron energy levels of the

Ctr* ion in crystal fields of axial and rhombic (a) and
tetrahedral, cis-distorted octahedral, trigonal symmetry (b).
413
Authenticated
Part 1.
Comparison of the J C r ^ O ) ^ 2 * and [Cu(H:0) 6 ] 2 ^ simulated spectra is

demonstrated in Fig. 4l · The simulation for d 9 configuration based on the
spectrum of [Cu(H 2 0)6](C10 4 )2 in aqueous solution is presented in Fig. ,4 b.
Hexacoordinated Cu 2 * compounds with the parent Oh structure are chiefly
tetragonal distorted and this is due to ligands along the ζ axis. In all cases the
absorption spectrum shows a single band at about 12500 till 16600 cm' 1 (800
till 600 nm). The first case corresponds to bluish green region and the second
one to blue green. However we also meet other colour hues, depending on
ligands attached to the metal as well on the geometry of the complex.
Particularly planar complexes are frequently red. First, let us remind that
colour of C u 2 ' compounds could be caused by several electronic transitions
as presented in Figure 8.
d-d copper(ll)
charge transfer
internal ligand
overtone
intervalence charge transfer
visible UV
near1R
10 20 30
Energy (νχΙΟ -3 , cm'1)
Fig. 8: T h e Cu 2 > energy ranges, 4 0 0 0 - 3 0 0 0 0 cm' 1 , of the four types of

transitions
In the. present paper several types of Cu 2 + complexes were prepared and

their spectroscopic properties and colour estimated. In the next tables, data
extracted f r o m literature /53-58/ and some eighteen of the above compounds
are given (Table 2 and Table 3). It is evident that d-d transitions mainly occur
in the 5 0 0 0 - 20000 cm' 1 n t a g i but. about th*20000 cm'1'-limit charge transfer
transitions also take place. Eight compounds are present in solid states and
their band positions and colours are given in (Schiff base complexes 159-65/.
Table 3 presents ten various complexes of Cu 2+ "in aqueous solutions as well
as their colour and absorption band positions.
414
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417
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Part 1.
T h e colours of these compounds are different, depending partly on the

symmetry (or on the coordination chromophore) but also on the solvent.
However, looking at the colorimetric properties of [Cu(en) 2 ](C104) 2 in some
solvents, we state thaFTfteSTtomplexes exhibit nearly 4he same colour hue
manifested by considerable values of (positive) a* and (negative) b*. These
solutions are purple (violet red) or even red. It was shown that the complex
has a considerable rigid square-planar structure, which is uninfluenced by
organic solvents. T h e maximum of the absorption spectrum does not depend
(or little) on the anion (outside the coordination sphere), e.g. for C 1 0 4 , N 0 3
and CI in water it is situated at 18182 cm' 1 (550 nm) and in ethanol at
18281 cm"' (547 nm) and 17391 cm' 1 (575 nm). But a strong shift to
17182 cm"' (582 nm) is observed for the Perchlorate compound in pyridine,
probably due to the formation of [(Cu(en) 2 (py)] (which is called
pentaammine effect). It is underlined that the d-d band shape is nearly
symmetrical without any notable band splitting.
A completely different picture occurs with the complex
[Cu(phen) 2 (H 2 0) 2 ](N03) 2 . Its colour is blue green in all solvents, with the
exception of D M F which is yellowish green having a hue angle. h ah = 123.7°,
and χ = 0 . 3 5 2 and y = 0.493. It is probably the effect of occupying the ζ axis
(perpendicular to the xy plane) by one or two solvent molecules.
T h e colour of another two complexes, Cu(sap) 2 and Cu(salan) 2 , is nearly
identical yellow although the c* value (colourfullness) is greater in the first
one.
T h e complex [Cu(en) 2 X 2 ] is a representative of copper(II) chelates.
Considerable importance for colour problems was stated for alike c o m p o u n d s
with acetylacetone, pure and mixed with amines, e.g., [Cu(acac) 2 ] or
[Cu(acac)(am)A], Spectroscopic properties of the first compound were
studied very early in the gaseous state as well as in organic solvents (in the
fifties of the 20th century). It is generally assumed that the square planar
complex changes its structure in solution by adding 1 or 2 solvent molecules.
Then a square planar or tetragonally distorted octahedron (square bipyramid)
is formed, and this effect is strongly dependent on the donor ability of the
solvent used. Extensive studies were undertaken with the complex
[Cu(acac)(tmen)]C10 4 on the absorption spectra and colour /66/. Such a
possibility was shown also during studies of thermochromism of Cu 2 + amine
complexes /67, 68/.
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Authenticated
When considering electronic spectroscopy and colour of Cu 2+ compounds

one more problem should not be omitted. As already discussed their
electronic spectra frequently are described and analysed as having one
absorption maximum. The 8ma.< values were exhaustive investigated by
Prenesti et al. /69, 70/ and correlated with the band position. The data for 121
complexes are presented in p a p e r / 7 0 / The curve equation was given as
y = a χ / (b + x), where a = 14.05 and b = - 465.03 with a correlation
coefficient equal to r = 0.733. From the curve is evident that a great majority
of Cu 2 * complexes might be characterized by having vma!< = 600-650 nm and
ε,™χ = 60-90. The complementary colour hues correspond to blue-green and
bluish green according to the CIE 1931 chromaticity diagram.
Much earlier Billo /71/ published results on 34 planar complexes with
peptides. The donor atoms were Ν from: amine, peptide, imidazole groups,
and Ο from: carboxylate, peptide and water as well as from OH", and each
ligand atom was given a concrete value. Such studies were also carried out by
Sigel and Martin 1121, and lastly by Ryde et al. 1131, and Pierloot et al. /74/
who executed quantum mechanical calculations on a great number of blue
copper proteins.
Although these authors did not tackle colour problems, it is easy to get
some firm conclusions about the colour hues accompanying the systems
under investigation. If the limits of absorption peaks were given as 13605 and
19231 cm"1 (735 and 520 nm), then the colours (complementary values)
would be (very approximately) blue green/bluish green and reddish purple for
both wavelength limits.
3 . 3 V 0 2 + (d 1 ) compounds
The next problem of spectroscopy and colour is with V 0 2 + and Fe 2+

compounds. Formally vanadium is in the +4 oxidation state, however, the
oxygen atom attached creates a strong oxycation entity, of which electronic
configuration is d'.
Electronic spectra and colour were considerably studied for simple salts
as V 0 S 0 4 and many complexes, chelates and, particularly, Schiff bases. Blue
green and green colour hues are given as characteristic for many of these
compounds; however, VOF 2 is yellow and VOBr 2 yellow brown (VOCK is
green).
The five-coordinate vanadyl ion [ V 0 ( H 2 0 ) 5 ] 2 + with C 4v symmetry should
exhibit 3 absorption d-d bands. Besides, a charge transfer transition O-V
takes place as in other oxycation groups, which increases intensity.

Authenticated
Part 1.
The results of spectra simulations for d1 and d6 are demonstrated in

Fig. 91, which shows the course of the spectra of [ ν 0 ( Η 2 0 ) 6 ] 5 0 4 and
[Fe(H 2 0) 6 ]S0 4 in aqueous solution for a broad Dq range 1000-3000 cm"'.
ω
ο
c
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XI
k—
ο experimental
in
.ο 5
CD
15000 20000 25000

v, cm
Fig. 9: Simulation of spectra in aqueous solutions (c = 2.0x10"' M,

1 = 1.0 cm), as a function of Dq parameter: 1000 - 3000 cm"'
(200 cm"1 step), for [V0(H 2 0) 5 ]S0 4 (a), and [Fe(H 2 0) 6 ]S0 4 (b),
with the experimental spectra; D4h symmetry, d' and d 6 electronic
configmation.
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CIELAB colour parameters for assumed Dq range for both compounds are
presented in Fig. 10, which compares all the electronic configurations
discussed.
Fig. 10: The CIELAB plane. The curves 1 - 4 correspond to the colour points
of simulated spectra in aqueous solution of: [ V 0 ( H 2 0 ) 5 ] S 0 4 - 1,
[Fe(H20)6]S04-2, [Cr(H 2 0) 6 ](C10 4 ) 2 [24 ] - 3, and
[Cu(H 2 0) 6 ]S0 4 , - 4, as a function of Dq parameter: 1000 - 3000 cm"'
(50 cm"' step); point (0,0) is a start and finish simultaneously
The CIELAB data clearly show that the colour of all the complexes
stydied, for instance in the complex creating a low ligand-field, could change
its hue from greenish-blue to purple or even red for higher Dq values. .This
kind of behaviour is formally the same as predicted in the case of simulation
of Cr(III) and Co(II) presented in papers /4, 5, 7-9, 52/. It is evident that the
course of colour changes remains as predicted in our earlier investigations.
Namely, applying a broad range of Dq values (as in this simulation) it is
possible to reach colour hues over the whole CIELAB plane.
421
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Part 1.
According to literature data /75-79/ in the vanadyl spectrum, three d-d

bands are to be expected (for C 4v symmetry and even four for C 2v ). Wave
numbers of these bands and colours predicted are presented in Table 4 on the
basis of the data extracted from /80/ and data cited /81-88/.
The corresponding transitions are described as originating from "T2
ground state splitted to 2 B 2 and : E , and to 2 A| and ' B | (from the splitted ΐ
state). Their wave number values are depending on the concrete geometrical
situation. From the literature data, an approximate conclusion could be drawn
that solvent molecules complete the coordination sphere "trans" to the
oxygen atom to form an octahedron. The effect in colour hue of the solutions
might be different depending on the role of solvent versus this atom. A firm
explanation of the electronic absorption spectrum of vanadyl complexes
seems to be difficult because of CT transitions which, as said previously, may
obscure the situation.
If we apply the data, e.g., from Lever's collection /80/, the v, and v 2
bands in the [ V 0 ( H 2 0 ) 5 ] 2 + are given the wavenumbers 13100 and 16000 cm' 1
(763 and 625 nm) respectively. At the CIE x, y chromaticity diagram this
denotes a blue green or bluish green colour hues (as complementary hues)
like in vanadyl sulphate pentahydrate. Considering organic solvents in the
system with vanadyl acetylacetonate, one important conclusion would be
made, namely their colours do not exhibit any purple or red hues. The area of
these last colours (in the CIE diagram) would correspond to about 21000 to
18500 cm' 1 (480-540 nm). But such values as due to the second absorption
band are extremely rare in the mentioned collection of Lever.
Many years ago Selbin 1111 formulated a new, totally empirical parameter
to interpret the shift of the second absorption band in organic solvents, which
(according to Ballhausen-Gray scheme) determines the 10 Dq value. This
approach is to assume dependence not on one band maximum but on both
maxima, i.e., V| and v 2 , on the solvent donor number. When expressed in
wavenumbers, the difference Δ = v 2 - v, increases strongly with the increase
of DN, whereas the differences between wavenumbers of the second band are
about 4 times smaller.
It was also shown that Δ = v 2 - v 2 is equal to (lODq + 3Ds - 5Dt). The
data for various organic solutions of [VO(acac) 2 ] were given in/75/. An
1
aqueous solution exhibiting a band wave number of 17820 cm" (b 2 - > b|
transition) must show a bluish purple hue and CC14 solution with a 1000 cm' 1
lower band should be blue green /75/.
422
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423
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Part 1.
Linert et al. presented another view /89/. Spectroscopic and

electrochemical investigations in organic solvents of the complex with acetyl
acetone were interpreted as due to the occurrence of two different species,
[VO(acac) 2 ] and [VO(acac)(solv)]. Their appearance did not allow finding a
unique relation versus the donor number of the solvent.
In our studies on colour of vanadyl acetylacetonate it was shown that,
among 12 organic solvents, half of them seem to occupy the free position
trans to the vanadyl oxygen atom, hence causing a yellow or yellow green
colour hue, and the rest do not show any influence on the parent compound,
giving a blue or green blue colour. Generally speaking solvents with high DN
like EtOH and MeOH belong to the first group, and solvents of low DN like
DCE to the second one. But BN, DN = 11.9, causes a strong green yellow
solution.
3.4High spin Fe z+ (d6 = d 5+1 ) compounds
It is known that colour changes, which are due to changes in the spin
state, but not to any remarkable change in geometry, are often observed with
Fe 2+ complexes. It should be noted that most of these complexes are
octahedral. The high-spin Fe 2+ complexes are paramagnetic (with t 2( , 4 e g 2
ground state), while the low-spin complexes are diamagnetic (with l 2g 6
ground state). The observed broad band for the high-spin Fe 2+ complexes
with common ligands lies below 12000 cm' 1 , i.e., Dq < 1200 (for example
[Fe(H20)6]2\ [Fe(H 2 0) 6 X 2 ], [Fe(phen) 2 X 2 ], where X=halides). For this
reason these complexes are colourless (or light yellow green). The change
colour from yellow green to purple is predicted by an increase in ligand field
strength, i.e., increasing the Dq, but in this case (for example [Fe(CN) 6 ] 4 \
[Fc(phen) 3 ] 2+ ) the complexes are low-spin. Moreover, the charge transfer
(MLCT) bands are frequently observed in the spectra of Fe 2+ chelates in the
colourful region.
This is in strong contrast to the Cu 2+ complexes, where the changes in
colour are accompanied by the changes in Dq, i.e., strength of the ligand field
(and in geometry), but not by those in the spin state.
Reported wave numbers of observed bands and colours predicted for
selected high-spin Fe 2+ compounds are presented in Table 5 on the basis of
the data extracted from 780/ and data cited /90-97/.
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Vol. 26, No. 4, 2006 Colour of id Transition Metal Compounds.
Part 1.
4. S O M E G E N E R A L R E M A R K S
As stated in the introduction, our chief aim was to search for a closer
dependence of colour quantitative characteristics and UV-VIS spectroscopic
data. Coloured objects considered are coordination compounds of transition
elements with 3d" electronic configuration, where η equals 1, 6, 4, and 9.
It was shown that in such a case UV-VIS spectra (band positions) could
be easily foreseen and, hence, also their colour hue. In this respect colour
characteristics of the object are very easily obtainable (for 0|, symmetry) and
by using the Dq parameter the colour travel (as a Dq function) could be
predicted.
Taking into account spectroscopic results, pure O h symmetry of these
compounds is rather very rare (even in the case of MiU) and frequently
tetragonal species do appear. Therefore, to get a realistic value for the Dq
parameter, the absorption spectra were resolved and term interaction
considered according to the procedure described in Section 2. In this respect,
we decided to apply curve resolution also to Cu 2+ spectra, although their
envelope sometimes does not show any trace of band splitting.
Simulation results in the terms of CIELAB parameters a* and b*, and
presented in the CIELAB plane, show a very characteristic course. In all
cases, there are evidently two parts of the figure, one for (+b*) values, the
second for (-b*) values. The lower part for the Cu 2+ casö is very flat, i.e., the
(-b*) is nearly constant showing increasing redness, and for Cr 2+ colour hue
of the solution is approximately caused by reaching (in the additive colour
mixture) the maximal amount of blue component and next travelling to a
nearly pure red colour hue. The yellow green part of the simulation curve is
4
characteristic, showing very small (-a*) changes and very strong lowering of
(+b*) values. It means that for increasing Dq values (in the range of 1 0 0 0 -
3000 cm" 1 ) the yellowness of the system almost suddenly diminishes.
Chroma c* value seems to be very interesting too. The next figure, Fig.
1 presents the dependence of the c* colour saturation on Dq, for all
systems. The picture demonstrates a characteristic course with two maxima at
about 1700 and 2200 cm"'. Indicating saturation or purity of the solution, c*
is seen here as an increasing value to the points 16 and 26. In the CIE
diagram, they correspond to bluish purple and yellow green colours.
In the previous paper devoted to Co(II) spectroscopy and colour of some
compounds /52/, a simulation curve for T d symmetry was obtained with a
course even more specific. It looks like a helix or logarithmic spiral (or some
other spirals).
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Fig. 11: The c* chrome parameters as a function of Dq: the curves 1 - 4

correspond to the . [ V 0 ( H 2 0 ) 5 ] S 0 4 - 1, [ F e ( H 2 0 ) 6 ] S 0 4 - 2,
[Cr(H 2 0) 6 ](C10 4 ) 2 [ ]-3, and [Cu(H 2 0) 6 ]S0 4 > - 4 complexes,
respectively.
Colour travel pictorial demonstrated within the CIELAB plane was

applied in different areas of colour technology. In reference /98/, the Figure
presents the angle dependency of such changes for F e 2 0 3 coated silica flakes
of different -thickness. A similar figure is shown in an article on optical
variable brilliant pigments containing different absorption addenda, e.g., Cu-
phthalocyanin 1991.
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Part 1.
Applying simulation curves based on the Dq parameter, we tacitly assume

that this value is the only one which characterises the colour of the system. In
other words, the spectrochemical series of ligand tells that if Dqi determines
a pair of (a*,, b*i) colour coordinates, then another pair (a*2, b*2) must deno-
te another colour hue, i.e., a different Dq2 value and a different ligand. How-
ever, in this series, some places are stated as being nearly equal and it should
be anticipated that this simultaneously does mean an existence of a very
similar absorption spectrum and colour. Hence probably, by applying colour
quantitative measurements and getting colour hue data, values that arc more
precise would be received.
In solutions studies of transition metal coordination compounds, there is
also a need for considering a situation in which two ligands would
participate, hence resulting in appearance of mixed entities. In aqueous
solutions, frequently mixed complexes could be detected having different
spectra and colour (when separately studied).
As a rule in such systems, one assumes the Dq value as a mean value of
both Dq values in respect of the number of both ligands. Such an approach is
based on the assumption that the symmetry of such a mixed complex is not
changed (or strictly, almost not changed). However, in the system of Cu2+ -
NH 3 - H 2 0 Bjerrum and Nielsen /100/ showed the "pentaammine effect"
many years ago. Their classical studies on stepwise formation of complexes
demonstrated that the spectrum of [Cu(NH3)5]2+ shifts in the reverse direction
as compared with complex forms having 1,2, 3, and 4 NH3 ligand molecules.
This reverse direction means that the Dq value corresponds now to a new
complex entity, which is shown to be [Cu(NH3)5]2+ - a 5-coordinate form
with C4v symmetry. Accordingly, the Dq is lower than for the complex
[CU(NH 3 ) 4 (H 2 0) 2 ] 2+ and the band maximum shifts to the red.
An analogical situation is observed for other ligands (instead of NH3),
e.g., ethylenediamine. Adding one or two moles of en results in appearing of
[Cu(en)]2+ and [Cu(en)2]2+, absorption spectra of which are shifted towards
the blue. In a large excess of the ligand, the resulting [Cu(en)3]2+ absorption
peak is shifted to the red. Shifting bands of these tris complexes
(six-coordinate) has been clarified by Sone and Fukuda /101/, and Cullen and
Lingafelter/102/, as caused by a different role of the equatorial and axial
ligands.

Authenticated
4.1 Colour of Ti3+ (d1) and Mn3+ (d4) compounds
At the end of this article we should also mention that all conclusions were
proven on the d' Ti 1+ complex compounds. Namely, applying the data for
V0 2 + colour simulation and the Dq value about 1800-1900 cm"1 (for the
complex [Ti(H 2 0) 6 ]Cl 3 ), we get a* = 93.5 and b*= -84.9, which denote a
strong recT-violet (purple) solution colour, just as given in Table
6 122, 103-113/ Moreover, when applying the values of the absorption band
positions given there for different Ti , + complexes (and simulation data), we
get nearly the same colour as presented in Table 6.
In Table 6 the colour hue and the transition energies are given as in the
books 122, 103/, then Dq is assumed as (nearly) a mean value of two bands.
Lastly the values of CIE x, y and the corresponding hues (from the
chromaticity diagram) and a*, b* are given. A very good coincidence is seen
except for two cases, as it is well known that orange colour hue corresponds
to 590-600 nm, which could be caused when the light absorption of the object
would take place at 500-490 nm or 20000-20450 cm"1. Most probably, the
orange colour is to be connected with another mechanism, e.g., charge
transfer transition.
The same pattern would be applicable to the case of Mn1+ (d4) high spin
coordination compounds that are isoelectronic with divalent iron compounds.
These are of the ML« type with almost non-disturbed octahedral symmetry.
For the [Mn(H 2 0>,] 1+ complex 10 Dq is given as 21000*cm"'. Heitce, looking
into the simulation in Table 7 (see Appendix) for Cr2+, we find out the
following colour parameters: x„ = 0.466, yn = 0.397, which at the CIE
chromaticity diagram defines its yellow green-yellow part. The CIELAB
parameters are a* = 29 and b* = 51 (for Cr2+ species) and the hab hue angle is
59°. The colour hue of some Mn3+ compounds in solution is frequently
estimated as brown or red-brown, as stated in the paper devoted to the
reaction course in the system KMn0 4 - SnCh - acetone in which such ions
appear /114/. Such a colour hue fully corresponds to the CIELAB coordinates
given above.
A general observation is clearly to be formulated, namely that all data
calculated as a function of the Dq parameter show one or two maximal values
in their course. The simulation procedure is starting with a green colour hue
429
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Part 1.
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which reaches its maximum at point 8, then getting more and more addition
of blue colour hue, hence increasing the (absolute) value of (-b*). Such a
situation is repeated in the further course of the graph when the colour
changes to red, yellow, and ending in the yellow green part of the diagram.
According to this picture, the L* value reaches its maximum = 100 for Dq =
2700 cm"1, which practically denotes such a solution as colourless.
Let us now compare simulation curves for all electronic configurations
considered and presented in Fig. 1C(. It is evident that all these curves
demonstrate the same character of fhe course, as has already been partly
discussed. Comparing them in the case of Cr(II) and Cu(II) we* reach some
interesting conclusions. For low Dq values about 1250 cm' 1 both curves show
nearly the same values of a* and b ^ ' h i s fact is in full concordance with the
earlier mentioned statement of Lux and Illman /21/; however, increasing .Dq
values cause distinct differences between them.
The hah hue angle, which was shown to be a characteristic colorimetric
parameter when investigating solvatochromism, is nearly constant in all
simulations. Namely, for Dq = 1950-2000 cm"' there is an abrupt changing of
this value corresponding to crossing a* axis. It nicely expresses entering the
red yellow colour field.
It is interesting to note that there is a distinct difference between the
course of both simulations, one in a*,Λ b* and the other in u*, v* coordinates.
The second is distinctly enlarged in the direction of (+u*) and (-u*), i.e., in
the direction of red yellow and blue green CIELAB planes..
5. APPENDIX
For a better understanding of the role of colour simulation procedure,

some calculated data are given in Table 7 and Table 8 as well as the
expressions for the colorimetric functions.
5.1 CIE chromaticity diagram and coordinates
The CIE 1931 chromaticitydiagram and names of colours that were used
in this work is presented in Fig. 12.

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Authenticated
Part 1.
520
0.7
23
1500 2
3 Λ /
0.5
/ / 5 ,> 5 8 0
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Λ^jDUU
Ci-γ-ι
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20
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19 / 15 \
/ /16
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0,1 0,3 0,5 0.7
Fig. 12: CIE 1931 chromaticity diagram and names of colours: 1 - white; 2 -
yellowish green; 3 - yellow green; 4 - greenish yellow; 5 - yellow;
6 - yellowish orange; 7, - orange; 8 - orange pink; 9 - reddish pink;
1 0 - r e d ; 11-purplish red; 1 2 - p i n k ; 13-purplish pink; 1 4 - r e d
purple; 15-reddish purple; 16-purple; 1 7 - b l u s h purple; 1 8 -
purplish blue; 1 9 - b l u e ; 20-greenish blue; 2 1 - b l u e green; 2 2 -
blush green; 2 3 - g r e e n ; from [5] p. 17; a coloured version of this
diagram appears in book [5], Figure CI.
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T h e C I E tristimulus values can be expressed mathematically as f o l l o w s :
X=830nm
X = k J φ(λ) Χ(λ) ά(λ)
λ=360nm
X=830nm
Y = k J φ(λ)χ(λ)ά(λ) (6-1)
λ=360nm
X=830nm
Ζ = k j φ(λ) ζ ( λ ) ά(λ)
λ=360πιπ
where χ(λ), y(X), and γ(λ) have already been defined and k is a
normalizing factor given by formula:
X=830nm
k = 100 / J φ(λ)γ(λ)ό(λ) (6.2)
X=360nm
Considering the colour o f an object which transmits or reflects light, the

spectral distribution o f the colour stimulus is g i v e n by the product o f the
spectral transmission or reflection coefficients, τ ( λ ) or ρ ( λ ) , and the relative
energy spectral distribution of the light source (illuminant), S, i.e.,
φ(λ) = τ(λ)8(λ) and φ(λ) = ρ(λ)8(λ) for transmission and reflection,
respectively. In practice summation is done instead o f integration:
λί
Υ = ^ φ ( λ ; ) γ ( λ ; ) Δ λ ( 6 3 )
λί
Z=k£<p(Xj)i(Xj)AX
where
k = 100 / Χ φ ( λ ] ) ί ; ( λ ] ) Δ λ ( 6 4 )
T h e λ intervals are usually 1, 5, or 10 nm; in the results presented in this

w o r k , a 1 nm interval was always applied.
437
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Part 1.
The tristimulus values lead to chromaticity coordinates x,y, and z:
x
Υ z
Ζ
y= ^ w ^ = v ^ ^ (6·5)
X+Y+Z X+Y+Z X+Y+Z
that are normalized, i.e., χ + y + ζ = 1.
5.2 CIELAB and CIELUV spaces
The CIELAB coordinates are given by the formulae below:
L* = 1 1 6 [ f ( Y / Y n ) - 16/116] (6.6)
a* = 5 0 0 [f ( X / X n ) - f ( Y / Y n ) ] (6.7)
b* = 200 [f (Y / Y n ) - f (Z / Z„)] (6.8)
where X„, Yn, Z„ are tristimulus values of white reference colour (in the
results presented in this work standard light source D65 has been assumed)
and f is a function /115/ defined by
f(r) = r 1 / 3 for r > 0.008856

f (r) = 7.787r + 16/116 for r < 0.008856
The CIELUV coordinates are given by formulae as foljows:
L , as above (6.6) (6.9)

f
4X 4X n
u* = 13L* (6.10)
V X + 15Y + 3Z Xn+15Yn+3Zny
f
9X 9X n
ν ' = 13L (6-11)
X + 15Y + 3Z Xn+15Yn+3Zn
For the better characterisation of the colour, other quantities are also used:
h a b =arctan(b*/a*) ( 6 12)
and saturation:
c* =[(a*) 2 + ( b * ) ] 1 / 2 (6.13)
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Colour of 3D Transition Metal Compounds. Part 1. Experimental Quantitative Studies and Ligand-Field Based Predictions For D / D, D and D Systems

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COLOUR OF 3d TRANSITION METAL

COMPOUNDS. PART 1. EXPERIMENTAL

A d a m Bartecki a and Krzysztof Kurzak b *

* Author to whom correspondence should be addressed;

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An account was elaborated on interrelation of Vis-NIR spectroscopy and

In the world of coloured objects one class, namely chemical (coloured)

situation and corresponding compounds are expected to be colourless, and in

Fig. I : Comparison of the aqueous solution spectra (c = 0 . 2 M , 1=1.0cm)

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(reflectance) and simulated spectra. The CIE tristimulus values (X, Y, 2)

v' max set that depends on Dq values.

The results of these simulations are demonstrated in Sections 3 and 4 for a

3. COLOUR AND SIMULATIONS F O R I O N S

3.1 High spin Cr 2+ (d4) compounds

This paper is devoted to studies of spectra and colour of compounds with

look at Cr 2+ coordination compounds, as it was stated that a considerable

Fig. 2: Occupancy of dorbitals in octahedral chromium(II) complexes

Fig, 3: Energy levels of high-spin chromium(II) in ligand fields of O h and

two bands as demonstrated in Table 1, in which magneto-chemical data are

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Β ΧOT ΧCO ΧΕΛ Χ<Λ Χ(Λ cc C

C3/ c/1 « ε C OC OC OC OC Oε ε ε C OC OC OJ3OJ3

ΟN οCN (οΝ *(οΝ νο(Ν

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ο>ο οο οο οο οο ο«ο οΙΟ οΙΛ) οΌ

CN of (Ν (Ν <Ν (Ν (Ν <Ν (Ν <Ν <Ν <Ν

The results of the simulation for d 4 configuration based, on the spectrum

Fig. 4: Simulation of spectra in aqueous solutions (c = 2 . 0 x 1 0 " ' M ,

Fig. 5: The CIELAB plane. The colour points correspond to simulated

According to experimental data there is a great resemblance between Cu 2 t

Energy (v-10'3, cm' 1 )

Compressed tetrahedral Square coplanar

Restricted Tetragonal octahedral Elongated tetragonal octahedral

- L a — - ' ' / ' X ~ \

Linear Tetragonal Octahedral Restricted Tetragonal Square Rhombic

Tetrahedral Compressed C is-distorted Trigonal Trigonal

Fig. 6: The splitting of one-electron energy levels of the

Comparison of the J C r ^ O ) ^ 2 * and [Cu(H:0) 6 ] 2 ^ simulated spectra is

intervalence charge transfer

Fig. 8: T h e Cu 2 > energy ranges, 4 0 0 0 - 3 0 0 0 0 cm' 1 , of the four types of

In the. present paper several types of Cu 2 + complexes were prepared and

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ο υ υ - τ υ CQ CQ —' Χ δ 'S" ' <sN

T h e colours of these compounds are different, depending partly on the

418 Brought to you by | Rutgers University

When considering electronic spectroscopy and colour of Cu 2+ compounds

The next problem of spectroscopy and colour is with V 0 2 + and Fe 2+

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The results of spectra simulations for d1 and d6 are demonstrated in

15000 20000 25000

Fig. 9: Simulation of spectra in aqueous solutions (c = 2.0x10"' M,

According to literature data /75-79/ in the vanadyl spectrum, three d-d

Linert et al. presented another view /89/. Spectroscopic and

3.4High spin Fe z+ (d6 = d 5+1 ) compounds

" " "

Fig. 11: The c* chrome parameters as a function of Dq: the curves 1 - 4

Colour travel pictorial demonstrated within the CIELAB plane was

Applying simulation curves based on the Dq parameter, we tacitly assume

428 Brought to you by | Rutgers University

4.1 Colour of Ti3+ (d1) and Mn3+ (d4) compounds

For a better understanding of the role of colour simulation procedure,

5.1 CIE chromaticity diagram and coordinates