J. Phys. Chem.
1989, 93, 5969-5972 5969
emergence of this liquid-crystalline microphase LC'mp constitutes
the transient phase separation L2 -* L2 + LC. The birefringence
of LC'mp is smaller than that of its progenitors. This can be seen
from the central oscilloscope trace of Figure 4b where the rate
of increase of turbidity is fortuitously balanced by the rate of
decrease of birefringence, yielding a steady-state signal.
5. After termination of the electric field, the system returns
to equilibrium, but via a route different from the forward path
just described. All but two (represented by ** in Figure 6) of
the forward steps are irreversible (-* ), connecting states that are
accessible only under electric field. For the species in those states
we have used primed symbols. The reequilibration at E = 0 is
characterized by three rate processes (Figure 4b—d). A large-
amplitude, fast (r_[ « 74 µ$) decay is followed by a slower (r„,
= 506 µ$), small-amplitude relaxation of the birefringence.
Although , = T_h the amplitude of the t_, process is smaller than
that of T[ because the population of A'„ has been depleted in the
preceding cluster-growth steps. The r.¡ relaxation corresponds
to the collapse of the micellar induced dipoles, i.e., A'„ —* A„, and
the t_2 to the disintegration of the anisotropic order of the liq-
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uid-crystalline microphase LC'mp. Subsequently, the turbidity
vanishes nonexponentially in about 1.5-2 s. This last, slow process
seems to involve subdivision of the macrodroplets by successive
constriction steps which requires a massive rearrangement of the
Trigonal Level Splittings of Cr3+ Doped in NaMg[AI(ox)3]*8H20 Single Crystals
T. Schónherr, J. Spanier, and H.-H. Schmidtke*
Instituífür Theoretische Chemie, Universitat Düsseldorf, D-4000 Düsseldorf, FRG
(Received: March 30, 1989)
The optical absorption spectrum of Crfox))3" doped in NaMg[Al(ox3)]-8H20 is reported. Since the chromium occupies equivalent
positions the band pattern arising from spin-forbidden transitions is less complicated compared to the corresponding compound
of nine-crystalline water. Anisotropic electric dipole selection rules allow for assignments of the Kramers doublets resulting
from 2Eg(0A) which is split by only 2-3 cm"1. The experimental energy level scheme, which is in some respect unusual compared
to other tris-chelated compounds, can be rationalized by angular overlap model calculations on the basis of D¡ symmetry,
demonstrating the importance of the angular geometry on quartet and doublet band splittings.
Introduction
Previous interpretations of electronic spectra of trisoxalato-
chromate(III) in neat crystalline surroundings or doped materials
were limited by the low-symmetry environment to which the
chromium chromophore is subjected.1"3 Band assignments were
further complicated by the presence of nonequivalent sites in
various crystals which concerns also the narrow doublet lines
arising from spin-forbidden transitions between t2g3 levels. In a
luminescence study, Coleman4 measured the amount of splitting
of the lowest 2Eg state (in Oh notation) varying by a factor of
almost 100 for different host materials which has been attributed
to outer-sphere interactions being generally not explicitly con-
sidered in conventional ligand field theory. On the other hand,
Hoggard5 6considered on the basis of an angular overlap model
(AOM) calculation, including anisotropic metal-ligand ir-bonding,
the possibility of very large 2Eg splittings. Forster et al.1,6 noted
(1) Condrate, R. A.; Forster, L. S. J. Mol. Speclrosc. 1967, 24, 490.
(2) Kawasaki, Y.; Forster, L. S. J. Chem. Phys. 1969, 50, 1010.
(3) Mortensen, O. S. J. Chem. Phys. 1967, 47, 4215.
(4) Coleman, W. F. J. Lumin. 1975, 10, 163.
(5) Hoggard, P. E. Coord. Chem. Rev. 1986, 70, 85.
(6) Coleman, W. F.; Forster, L. S. J. Lumin. 1971, 4, 429.
0022-3654/89/2093-5969501.50/0 ©
surfactant molecules as they reconstruct the original equilibrium
species and populations.
Conclusion
Electric field greater than 1.2 kV cm"1 induces L2 —
L2 + LC
phase separation in homogeneous microemulsions of Aerosol-
OT/isooctane/H20 with compositions sufficiently close to the
boundary between the L2 and L2 + LC phases, even at temper-
atures several degrees below the upper critical phase separation
temperature Tc. The evolution of birefringence and delayed
turbidity exhibited by the system are manifestations of distinct
steps associated with the formation of oriented anisotropic
structures, linear cluster growth, and fusion, leading to the
transient LC phase. The slow reequilibration of the LC phase,
which occurs upon termination of the field, represents the different
return path in the overall thermodynamic cycle.
Acknowledgment. Flelpful suggestions by Dr. A. C. Hall,
discussions with Professor V. Degiorgio and Dr. R. Zana, and
technical assistance by D. Miller are gratefully acknowledged.
This material is based in part upon work supported by the Texas
Advanced Research Program under Grant No. 1766, the National
Science Foundation (Grant No. CHE-8706345), and the R. A.
Welch Foundation.
that transitions in the intercombination band region (4A2g -* 2Eg)
of Cr(ox)33" are considerably dependent on the amount of crys-
talline water present in the NaMg[Al(ox)3]*xH20 (x = 8 or 9)
host materials. Similar observations have been reported from the
emission spectra of Cr(ox)33" doped in 3[ 1( )3]·4 20 where
partial dehydration on the crystalline surface was claimed to be
responsible for these band splittings.4 The quartet absorption
spectra, on the other hand, could be satisfactorily explained by
the presence of a trigonal ligand field acting on the Cr06 octa-
hedron.7
From EPR measurements, Bernheim and Reichenbecher8
concluded that the Cr3+ ion when doped in NaMg[Al(ox)3]-8H20
crystals is located on an axis of trigonal symmetry occupying
equivalent positions. Therefore, this system ought to be very
appropriate for investigating the electronic structure of Crox33'
in a specific environment, in particular for determining the
spin-orbit split levels in the sharp-line spectrum which arise from
transitions within the t2g3 configuration.
In the present Letter we report results on single-crystal emission
and polarized absorption spectra measured from the title com-
al Piper, T. S.; Carlin, R. L. J. Chem. Phys. 1961, 35, 1809.
(8) Bernheim, R. A.; Reichenbecher, E. F. J. Chem. Phys. 1969, 51, 996.
1989 American Chemical Society
5970 The Journal of Physical Chemistry, Vol. 93, No. 16, 1989
Figure 1. Single-crystal absorption spectrum of 1% Cr3+ doped in
NaMg[Al(ox)3]-8H20 obtained at T = 90 K. The
light is linearly po-
larized with the electric vector parallel, (---), or perpendicular, and
a (—), the trigonal molecular axis. The insets show band patterns of
intercombination transitions in more detail which were measured from
a 5% chromium-doped crystal.
pound. For rationalizing the experimental level scheme, crystal
field and AOM calculations are performed which closely depend
on the geometry of the coordination sphere.9
Experimental Section
The complex compounds NaMg[M(ox)3]-9H20, with = Cr
and Al, were synthesized by using standard methods.3 Crystals
containing eight molecules of water per formula unit were obtained
by annealing in the temperature range 96-98 °C.8 The loss of
one H20 molecule was checked by gravimetric and DTA methods.
Endothermic DTA peaks measured at 98 and 126 °C are due to
a stepwise loss of water molecules as has been described also for
K3[Cr(ox)3]-3H2O.t0 Mixed crystals were grown by slow
evaporation of aqueous solutions which contained varying amounts
of the two compounds. Under the polarization microscope the
crystals proved to be uniaxial.
Polarized absorption bands were measured on a Cary 17
spectrophotometer equipped with a microscopical device as de-
scribed earlier." High-resolution spectra in absorption and
emission were recorded with a McPherson 0.5-m double mono-
chromator and a red-sensitive GaAs photomultiplier. Temperature
down to 5 K were achieved by using commercial flow-cryostat
technique. In order to prevent water exchange with the atmo-
sphere, the samples were coated with silicon grease, which be-
forehand was checked for transparency in the considered spectral
region.
Results and Discussion
Optical Spectra. The low-temperature polarized absorption
spectra of doped single-crystals of NaMg[Al(ox)3]-8H20 con-
taining about 1% or 5% Cr(ox)33' anions are illustrated in Figure
1. Although the type of space group for the modification of the
host crystal has been controversially discussed,2·6·" all structural
investigations agreed that the Al ions are located on a trigonal
symmetry axis. From EPR measurements8 the site symmetry was
determined to be Z)3 which should not be significantly changed
when Al is substituted by Cr. Since the absorption band pattern
also does not alter very much between room and liquid helium
temperature, a structural phase transition will not be expected.
The trigonal contribution to the crystal field acting on Cr3+
is apparent from the highly anisotropic absorption observed for
the quartet-quartet transitions. Alignment of the E vector parallel
( ) or perpendicular ( ) to the optical axis of the crystal, the
direction of which is determined by the 3-fold axis of the anion,8
(9) Atanasov, M. A.; Schonherr, T.; Schmidtke, H.-H. Theor. Chim. Acta
1987, 71, 59.
(10) Nagase, K. Chem. Lett. 1972, 587.
(11) Teutsch, U.; Schmidtke, H.-H. J. Chem. Phys. 1986, 84, 6034.
(12) Frossard, L. Schweiz. Mineral. Petrog. Mitt. 1956, 36, 1.
Letters
Figure 2. (a) High-resolution spectrum of the 4A2g —-
2Eg origins in
different polarizations obtained at T = 5 K. (b) Level sequence and
electric dipole selection rules for zero phonon transitions. Polarizations
are (—) and (---).
was obtained with the aid of a polarization microscope. The
-spectrum was measured with light propagating along this axis
showing no azimuthal dependences for the polarization. Since
the polarization relations are found to be a = ir, the intensity
primarily arises from an electric dipole transition mechanism.
Then, according to £>3 selection rules, the -polarized quartet bands
must be attributed to the electronic transitions 4A2 -» 4E(4T2g)
and — 4E(4Tlg) in agreement with corresponding assignments
given in the literature for different host materials.3·7 In -po-
larization only one trigonal split component, i.e., 4A2 —4A,(4T2g)
is dipole allowed, whereas the forbidden 4A2 -* 4A2(4Tlg) transition
obtains some minor intensity by a vibronic coupling mechanism.
The low-energy part of the -absorption spectrum obtained from
a sample of higher Cr3+ concentration is depicted in the inset A
of Figure 1 showing a well-resolved vibronic structure (the intensity
profile of the -spectrum differs only for a few weaker sidebands).
The number of sidebands is, however, significantly smaller com-
pared to the corresponding band region of the nonahydrate com-
pound3 which can be attributed to the presence of nonequivalent
chromium sites in the latter species. The 2Eg(0A) zero-phonon
origin can be readily identified with the most intense band of lowest
energy in the absorption spectrum. This assignment is supported
by the emission spectrum which exhibits a corresponding line at
similar wavelength. At low temperature, recorded at high spectral
resolution, the zero-phonon line of 2Eß(0 ) in the - and -
spectrum is split by about 2-3 cm"1 (cf. Figure 2a) which is due
to the combined effects of trigonal molecular symmetry and
spin-orbit coupling. In the -spectrum this splitting could not
be resolved. The Z)3 low-symmetry component of the ligand field
is, however, large enough, destroying the inversion center (vide
infra), so that most of the intensity of the Eg zero-phonon lines
can be assumed to be due to electric dipole transitions. This is
supported by the relatively large intensity of these peaks compared
to the vibronic side bands (cf. inset A of Figure 1). Since from
the EPR investigation8 the zero field splitting parameter D is
calculated to be negative;13 i.e., the level sequence arising from
the 4A2g ground state is E3|Z2 < the D3* double group
E1(r2 (in
notation), the sequence for the resulting 2Eg split levels (E3/2, E1/2)
then can be determined from the - and -spectrum. When
electric dipole selection rules are applied, the slightly larger band
separation for the -polarized transitions supplies a level ordering
for these Kramers doublets of E3/2 < E1(,2 with an assignment as
given in Figure 2b. The observed band pattern cannot be explained
by two similar nonequivalent sites which might have been formed
by a structural phase transition. The level energies then are
determined from the -polarized absorption peaks arising from
a 2Eg splitting of about 3 cm"1 (±0.08 due to the limited spectral
resolution) in good agreement with the observed -polarized
transitions. The measured splitting is in the same order of
magnitude as the ground-state splitting which, on the other hand,
is much smaller in other comparable low-symmetry chromium(III)
complexes. It is noticed that the 2Eg splitting is drastically reduced
in the present compound also compared to the ninefold-hydrated
(13) Lahiry, S.; Kakkar, R. Chem. Phys. Lett. 1982, 88, 499.
Letters
species (20 cm"1)2,3·6 whereas the ground-state splitting is very
similar (ca. 1.5 cm"1).2,8
Bands due to the less intense 4A2g — 2Tlg lines at higher energy
are usually covered by the rich vibrational fine structure of
transitions into 2Eg and are difficult to detect. Likewise, emission
spectra cannot yield information about higher electronic states
since they rapidly decay after excitation by radiationless tran-
sitions. Band assignments are further complicated by the fact
that transition probabilities of corresponding vibrational sidebands
can be very different in the absorption and emission process. The
band pattern (cf. the inset A of Figure 1) can be, however, almost
completely interpreted in terms of vibrational fine structure upon
the 2Eg zero-phonon transitions. For the most intense lines fre-
quency intervals of 120, 140, 360, 411, 460, 640, and 970 cm"1
are calculated corresponding to vibrational modes of Cr(ox)33"
in the excited state. They all can be identified with frequencies
of the ground state as measured in the infrared14 or luminescence
spectra, which are expected to be almost equal since the electric
transitions occur between levels belonging to the same configu-
ration t2g3. Only one less intense band, which has no corresponding
peak in the emission or IR spectrum, would be a candidate for
a spin-orbit component of 2T(indicated by an arrow in the inset
A of Figure 1) being 565 cm"°higher in energy than the 2Eg lines.
This interval would be too large to be explained by the second
component of 2Eg, split by the low-symmetry field.
Some sharp peaks of low intensity are also found in the region
between the quartet bands (inset B of Figure 1) which correspond
to transitions into the highest levels of t2g3 electron configuration.
In trigonal symmetry, three spin-orbit states (Kramers doublets)
can result from 2T2g from which those arising from trigonal 2E-
(2T2g) are appreciably increased in energy due to interaction with
the lower 2E(2Eg, 2T,„) levels. On the other hand is the second
2T2g component, i.e., 2A,(2T2g), only influenced by the combined
effect of spin-orbit coupling and reduction of symmetry.
Therefore, we may assign the main peak at 20682 cm"1 to the
2A, electronic origin and the others to vibronic sidebands. This
assignment is in accordance with the higher intensity measured
in -polarization which is expected from electric-dipole selection
rules.
Crystal Field Calculations. A further objective of this study
is to compare the experimental level scheme with that predicted
from crystal field and AOM calculations. In the framework of
conventional ligand field theory the parameters K and K' are
introduced for trigonal symmetry in addition to the cubic ligand
field parameter Dq.15 Considering only diagonal elements of the
perturbation matrix in the strong field approach, the quartet band
splittings are calculated in terms of the low-symmetry parameters
4E -
4A2
=
(3/2)K for 4T2g
4E -
4A, =
(3/2)K- 21/2/C for 4Tlg
From the splitting of the first quartet band K is fitted to be about
300 cm"1. The observed level sequence of the 4Tlg components
requires K' to be much larger and to have a negative sign (K' =
-1500 cm"1). The derived parameter ratio of K'jK == -5 is not
in agreement with an early assumption of comparable magnitudes
for K and K'.16 The relation does not significantly change when
these parameters are obtained from complete ligand field calcu-
lations where all possible (3°) = 120 wave functions are considered
(complete Cl in d3) and spin-orbit coupling is included.
As has been demonstrated for trigonal d3 complexes of rhe-
nium17 and chromium,18 a relation between ligand field parameters
can be used for an estimate of the trigonal distortion of the Cr06
(14) Gouteron, J. J. Inorg. Nucí. Chem. 1975, 38, 55.
(15) Lever, A. B. P. Inorganic Electronic Spectroscopy, 2nd ed.; Elsevier
Science: Amsterdam, 1984.
(16) Sugano, S.; Peter, M. Phys. Reu. 1961, 122, 381.
(17) Schoenen, N.; Schmidtke, H.-H. Mol. Phys. 1986, 57, 983.
(18) Urushiyama, A.; Schdnherr, T.; Schmidtke, H.-H. Ber. Bunsenges.
Phys. Chem. 1986, 90, 1195.
The Journal of Physical Chemistry, Vol. 93, No. 16, 1989 5971
—- —-
Oh 03d d3
Figure 3. Calculated energy splittings of 4A2g and 2Eg for various trigonal
distortions of Cr(ox)33". The AOM, electronic repulsion, and spin-orbit
parameters are (in cm"1): e„ = 6750, e,s = 520, eIC = 0.6e„, B = 700,
C = 3100, f = 200. Notice the different energy scales for the 4A2g and
the 2Eg region.
chromophore under the restriction of fixed metal-ligand distances
and small deviations from cubic symmetry:
(K + XO/Dq =
10/21/2(t?cub
-
*?)7r/180° (2)
in which tZ is the angle between a trigonal axis of the octahedron
and one of the metal-ligand bond vectors. Using the parameter
values given above, i? is increased by about =
t?cub
-
= 6°
leading to significantly compressed Cr06 octahedra of D3d sym-
metry which would explain the strong trigonal contribution to the
ligand field potential. Structural investigations on other [Cr-
(ox)3]3+ salts supplied somewhat smaller values of At?(l°-3°);19,20
however, the larger trigonal compression of the Cr-doped A1
complex with respect to the pure chromium compound could be
due to the misfit of the ionic radii of Cr3+ (64 pm) and Al3+ (57
pm).
The unusually large zero-field 4A2g ground-state splitting of
1.55 cm"1 as derived from EPR measurements8 can be explained
by a complete (all configuration) ligand field calculation using
a spin-orbit coupling parameter in the expected range of 180-250
cm"1. On the other hand, the small energy separation between
(la) the spin-orbit levels arising from the lowest 2Eg excited state could
not be fitted satisfactorily by the ligand field as given above by
(lb) using a unique parameter set which is varied within the wide
limitations of a trigonal field restricted by the measured size of
quartet band splittings. The model so far does, however, not
consider chelate effects and/or additional geometric distortions
of the chromophore. For instance, should a mutual twisting of
the two oppositely coordinated oxygen triangles around the trigonal
axis (by an angle ) be expected as is required also for other
Cr(ox)33" compounds.20 This additional distortion leading to D}
symmetry was shown to have significant influence on the doublet
splittings of K3[Cr(ox)3].5 Since, first of all, angular distortions
are to be considered, the more appropriate model would be the
AOM which uses local bonding parameters independent of angular
variations of the coordination sphere. Eventual bond length
variations are then considered by fitting the AOM parameters
to the experiment. Very recently it has been demonstrated (e.g.,
for chromium tris(acetylacetonate)9·21 and a mixed osmium(IV)
oxalate complex21) that the AOM can appropriately account for
(19) Niekerk, J. N. van; Schoening, F. R. L. Acta Crystallogr. 1952, 5,
499.
(20) Taylor, D. Aust. J. Chem. 1978, 31, 1455.
5972 J. Phys. Chem. 1989, 93, 5972-5974

relations between the electronic spectra and the structure of the
compounds. Since in the case of NaMg[Cr(ox)3]-8H20 the re-
quired structural data are still missing, we started our calculations
using atomic positions which are available for the ammonium and
the potassium salts.19,20
Figure 3a shows from some model calculations, which were
performed by using the perturbation matrices (including Cl) given
by Hoggard,5 the splitting of the 2Eg state being more than 10
times larger than the ground-state splitting for a compfessed Cr06
-effects are generally neglected (cf. Figure 4 of ref 5). Although
much larger 2Eg splittings (about 400 cm"1) have been predicted
from the AOM for Cr(ox)33" in view of a dominant role of -
anisotropy,5 the experimental findings determine this level splitting
to be rather small in the present system which can be rationalized
by the same model using a reasonable trigonal geometric distortion
of the tris-chelated molecule as the basis for the calculation. The
10 times larger 2Eg splitting in the compound with nine crystalline
H20 ( 30 cm"1) can be explained by a further reduction of
~

chromophore (t7 > t?cub = 54.74°) when restricting to Dzd sym-
metry. Deviations from the octahedral value of the twist angle,
i.e., = 60°, are connected to the chelate bite angle a and the
trigonal angle t7 by the relation (cf. Figure 1 of ref 9)
cos ( /2) = sin ¡7 cos ( /2)
(3)
If we take the t7 value of 60.74° which was derived from the
quartet band splittings, and the octahedral angle = 60°, a bite
angle of a = 82° is obtained from eq 3 which is in good agreement
with the oxalate bite in other first-row transition complexes as
well as with the corresponding valence angle of the free anion.
Therefore, we can assume that an additional geometric distortion
lowering the D2d symmetry should not significantly influence the
bite angle that is predominantly determined by the electronic
structure of the oxalate ligand. Figure 3b illustrates the calculated
energy dependence of 5A2g and 2Eg split levels with respect to
4
(=60° ),
-
symmetry moving the two opposite planes of coordinated oxygens
away from parallel position. This tipping of the oxalate ligands
leading to C2 symmetry is actually suggested by X-ray structure
results obtained for the ammonium and the potassium salts.19,20
For this symmetry reduction the calculation predicts larger
splittings for both the ground state and 2Eg in accordance with
EPR and other optical experiments.3,8
A satisfactory fit to the experimental findings is obtained if
the geometric angles are chosen = 55°, t? = 59°, and a = 83°
(±1° in all cases). The twisting of the oxygen triangles around
the trigonal axis does not have a large influence on the quartet
level scheme: the calculated splitting is small compared to the
broadness of the measured absorption bands which could not be
resolved. The AOM calculation, however, can explain the unusual
splittings of the lower octahedral states resulting from the t2g3
electron configuration which give rise to intercombination bands.

when a is fixed at 83°. With growing the splitting
of 2Eg is drastically reduced whereas the ground-state splitting
decreases only moderately. This behavior that is mainly due to
strong contributions of rr-bonding is different from the band
splittings calculated for twisted [Cr(en)3]3+ for which metal-ligand
For a further test of the given description of the Cr(ox)33" molecule,
an identification of higher electronic states would be necessary
which seems to be prevented by the intense vibronic sideband
structure arising from 2Eg in the long-wavelength part and by the
low spectral resolution in the region of 4A2g -* 2T2g transitions.

(21) Schonherr, T. Photochemistry and Photophysics of Coordination Acknowledgment. We are grateful to the Fonds der Chem-
Berlin, 1987; p 31.
Compounds·, Yersin, H., Vogler, A., Eds.; Springer: ischen Industrie, Frankfurt/Main, for financial support.

Ordering in the Framework of a Magnesium Aluminophosphate Molecular Sieve

Patrick J. Barrie and Jacek Klinowski*

Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge CB2 1EW, England
(Received: April 5, 1989)

MgAPO-20 is the magnesium aluminophosphate equivalent of the zeolite sodalite with magnesium, aluminum, and phosphorus
in the tetrahedral framework sites. We have measured 27Al and 31P magic-angle-spinning (MAS) NMR spectra of this material
and demonstrate that (i) all spectral signals can be assigned; (ii) the framework composition can be calculated from the
spectra; (iii) the magnesium in the framework is strictly ordered; (iv) the precise nature of this ordering can be determined.

Introduction
Since 1982 several new families of porous solids have been
synthesized. The A1P04 molecular sieves, with structures built
from alternating A104 and P04 tetrahedra, were the first to be
discovered.1 Some of them have the framework topologies of
known zeolites, but many have novel structures. A1P04 sieves
are synthesized under mild hydrothermal conditions from gels
containing sources of aluminum, phosphorus, and at least one
organic structure-directing template. Incorporation of a silicon
source into an aluminophosphate gel results in the formation of
silicoaluminophosphates, denoted SAPO, and the incorporation
of a metal, Me (such as Mg, Mn, Fe, Co, or Zn), into A1P04 and
SAPO gives the MeAPO and MeAPSO sieves, respectively.2
Some of these have high Bronsted acidities and thus a considerable
potential as catalysts as well as ion exchangers and sieves.
The sodalite cage (a truncated octahedron) is the simplest
space-filling polyhedron apart from the cube and divides space
with minimum partitional area.3 Many natural and synthetic
materials with the sodalite structure and a variety of framework
and enclathrated species have been described. One of these,
ultramarine, was recently shown by MAS NMR4 to be disordered
and thus to violate the Loewenstein rule5 (“the aluminum avoi-
dance principle”) which is universally obeyed in hydrothermally
prepared aluminosilicates. By contrast, the mineral lazurite, the
natural equivalent of ultramarine, is strictly ordered. The sodalite
structure, in which all tetrahedral and all cationic sites are

(3) Thomson, Sir William. London, Edinburgh, Dublin Philos. Mag. J.

(1) Wilson, S. T.; Lok, B. M.; Messina, C. A.; Cannan, T. R.; Flanigen, Sci. 1887, 24 (5th series), 503.
E. M. J. Am. Chem. Soc. 1982, 104, 1146. (4) Klinowski, J.; Carr, S. W.; Tarling, S. E.; Barnes, P. Nature 1987, 330,
(2) Flanigen, E. M.; Lok, B. M.; Patton, R. L.; Wilson, S. T. Pure Appl. 56.
Chem. 1986, 58, 1351. (5) Loewenstein, W. Am. Mineral. 1954, 39, 92.

0022-3654/89/2093-5972S01.50/0 &copy; 1989 American Chemical Society