Controlling the White-Light Generation of [(RSn)4E6]: Effects of Substituent and Chalcogenide Variation

Article abstract of DOI:10.1002/anie.201909981

Adamantane-type organotin chalcogenide clusters of the general composition [(RT)₄S₆] (R=aromatic substituent, T=Si, Ge, Sn) have extreme non-linear optical properties that lead to highly directional white-light generation (WLG) upon irradiation with an IR laser diode. However, the mechanism is not yet understood. Now, a series of compounds [(RSn)₄E₆] (R=phenyl, cyclopentadienyl, cyclohexyl, benzyl, CH₂CH₂(C₆H₄)CO₂Et; E=S, Se), were prepared, characterized, and investigated for their nonlinear optical properties. With the exception of crystalline [(BnSn)₄S₆], all these compounds exhibit WLG with similar emission spectra; slight blue-shifts are observed by introduction of cyclopentadienyl substituents, while the introduction of Se in the inorganic core can provoke a red-shift. These investigations disprove the initial assumption of an aromatic substituent being a necessary precondition; the precondition seems to be the presence of (cyclic) substituents providing enough electron density.

Full text of DOI:10.1002/anie.201909981

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International Edition: DOI: 10.1002/anie.201909981
German Edition: DOI: 10.1002/ange.201909981
Main-Group Chemistry
Controlling the White-Light Generation of [(RSn)4E6]: Effects of
Substituent and Chalcogenide Variation
Eike Dornsiepen, Florian Dobener, Sangam Chatterjee, and Stefanie Dehnen*
Dedicated to Professor Hubert Schmidbaur on the occasion of his 85th birthday
Abstract: Adamantane-type organotin chalcogenide clusters
of the general composition [(RT)4S6] (R = aromatic substitu-
ent, T= Si, Ge, Sn) have extreme non-linear optical properties
that lead to highly directional white-light generation (WLG)
upon irradiation with an IR laser diode. However, the
mechanism is not yet understood. Now, a series of compounds
[(RSn)4E6] (R = phenyl, cyclopentadienyl, cyclohexyl, benzyl,
CH2CH2(C6H4)CO2Et; E = S, Se), were prepared, character-
ized, and investigated for their nonlinear optical properties.
With the exception of crystalline [(BnSn)4S6], all these com-
pounds exhibit WLG with similar emission spectra; slight blue-
shifts are observed by introduction of cyclopentadienyl sub-
stituents, while the introduction of Se in the inorganic core can
provoke a red-shift. These investigations disprove the initial
assumption of an aromatic substituent being a necessary
precondition; the precondition seems to be the presence of
(cyclic) substituents providing enough electron density.
ties such as solubility in organic solvents or reactivity towards
organic molecules, metal salts, or surfaces.[7]
In the context of our investigation of functionalized
organo Group 14 chalcogenide clusters,[8–12] we have recently
found an unprecedented, extreme non-linear optical behavior
of the styryl-decorated cluster [(StySn)4S6] (Sty = 4-vinyl-
phenyl),[13] which belongs to the family of organo Group 14
sesquichalcogenide clusters of the general formula [(RT)4E6]
(R = organic substituent; T= Si, Ge, Sn; E = O, S, Se,
Te).[14–18] [(StySn)4S6] has been obtained as an amorphous
powder, but DFT calculations reveal that the adamantane-
type structure are favored over the double-decker-type
isomer by ca. 30 kJmolꢀ1. While compounds that lack
inversion symmetry are widely known for second-harmonic
generation (SHG), we observed white-light generation
(WLG) upon irradiation with a commercially available
continuous wave (CW) near-infrared laser diode.[13] This
unexpected phenomenon was intuitively attributed to the
amorphous nature of the compound. In the respective
powders, SHG is clearly prohibited by the random orientation
of the molecules, which, at the same time, leads to an extreme
broadening of the SHG emission. Yet, the exact mechanism of
this non-linear response is still unknown. Therefore, we are
currently about to expand the library of related compounds
for getting more insight in the new WLG behavior.
We have furthermore prepared a range of adamantane-
type clusters with different organic substituents and Group 14
elements: [(PhSn)4S6] and [(PhGe)4S6] exhibit WLG, while
[(PhSi)4S6], [(MeSn)4S6] and [(NpSn)4S6] do not emit white
light; yet, these compounds still show non-linear optical
properties by strong SHG instead.[19] For [(PhSi)4S6], this is
easily attributed to the crystallinity of the compound, which
suppresses WLG. In the case of [(MeSn)4S6], the organic
substituent shell does not contain an aromatic p-electron
system; as [(MeSn)4S6] lacks any evidence for long-range
order but shows SHG, the presence of p-aromatic substituent
molecules was intuitively assumed to be a necessary condition
for WLG. The lack of WLG observed for the naphthyl-
substituted [(NpSn)4S6] was attributed to beginning long-
range order in the amorphous powder due to p-stacking.[19]
Although the assumption of an aromatic p-electron
system as a critical parameter seemed plausible, its definite
role has remained unclear so far. So, we intend to further
narrow down the chemical and electronic pre-conditions for
WLG and have designed a new series of compounds that have
cyclic substituents R, hence including non-aromatic ones.
Herein, we report on their synthesis and characterization as
well as on the non-linear optical response that was shown this
Introduction
Organo Group 14 chalcogenide clusters are organic/
inorganic hybrid compounds consisting of an inorganic cage,
which are derived from chalcogenido Group 14 anions[1,2] that
feature an organic substituent shell attached to the core by
covalent Group 14 element–carbon bonds. Chalcogenido
Group 14 anion salts have been actively investigated owing
to their tunable optoelectronic and semiconducting proper-
ties, resulting in diverse applications.[3–6] The decoration of
such cluster anions with organic substituents not only allows
the isolation of compounds with discrete, neutral cluster
molecules, it also enables further tailoring of material proper-
[*] E. Dornsiepen, Prof. Dr. S. Dehnen
FB Chemie and Wissenschaftliches Zentrum fꢀr Materialwissen-
schaften (WZMW), Philipps-Universitꢁt Marburg
Hans-Meerwein-Straße 4, 35043 Marburg (Germany)
E-mail: dehnen@chemie.uni-marburg.de
F. Dobener, Prof. Dr. S. Chatterjee
Institute of Experimental Physics I, Justus Liebig University Gießen
and Center for Materials Research (ZfM)
Heinrich-Buff-Ring 16, 35392 Gießen (Germany)
Supporting information and the ORCID identification number(s) for
the author(s) of this article can be found under:
https://doi.org/10.1002/anie.201909981.
ꢂ 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co.
KGaA. This is an open access article under the terms of the Creative
Commons Attribution License, which permits use, distribution and
reproduction in any medium, provided the original work is properly
cited.
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way to be feasible with cyclic substituents lacking aromaticity,
as well.
Upon reaction of the corresponding organotin trichlorides
and (Me3Si)2E in toluene, the compounds precipitate from
solution and are isolated by filtration. Amorphousness versus
crystallinity is then probed by powder X-ray diffraction
(Supporting Information, Figures S42–S50), and emission
spectra of all new compounds are collected. The emission
spectra of the amorphous compounds 1 and 4–9 are shown
Clusters of the type [(RSn)4E6] (R = Ph, Bn, CH2CH2-
(C6H4)CO2Et, h1-Cp, Cy; E = S, Se) have been prepared
according to Equation (1) and fully characterized.
ðMe3SiÞ2E
toluene
RSnCl3
½ðRSnÞ E ꢁ
ð1Þ
ƒƒƒƒƒ!
4
6
The subtle influence of the substituent was probed by
introducing either non-aromatic cyclic substituents or an
aliphatic linker to further separate the aromatic ring from the
cluster core, or finally additional functionalization of the
aromatic substituent. To gain further insight into the role of
the cluster coreꢀs composition, the series of compounds is
realized for both E = sulfur and selenium, with the latter
being the first selenide clusters of this kind to be examined for
non-linear optical properties. Scheme 1 summarizes all com-
pounds that were synthesized and studied herein.
Results and Discussion
With the chosen series of compounds, we intend to gain
more insight into the prerequisites for WLG[20] by answering
the following questions:
1) Is the emission spectrum affected by replacement of
sulfur with selenium; 2) does the aromatic substituent need to
be bonded directly to the inorganic core, or is WLG also
observed if an aliphatic spacer is inserted between the cluster
core and the p-system; 3) is a p-aromatic substituent neces-
sary at all, or do p-electrons located in isolated double-bonds
also lead to the observation of WLG; and 4) are substituents
with any kind of p-electrons generally needed for WLG, or
can molecules that bear fully saturated organic substituents
also exhibit WLG.
Figure 1. WLG emission spectra of organotin sulfide and selenide
clusters (from top left to bottom right): A and 1 (R=phenyl), 4 and 5
(R=R1 =CH2CH2(C6H4)CO2Et), 6 and 7 (R=h1-cyclopentadienyl), 8
and 9 (R=cyclohexyl). Each spectrum is response-corrected with
a calibrated tungsten halogen lamp. In the cross-hatched area
(>1000 nm) the instrument response of the used silicon charge-
coupled device array detector (cooled down to ꢀ608C) is very weak,
hence inhibiting a reliable spectral intensity correction in this range.
Scheme 1. Synthesis of compounds 1–9 (Ph=phenyl, Bn=benzyl, R1 =CH2CH2(C6H4)CO2Et, h1-Cp=h1-cyclopentadienyl, Cy=cyclohexyl), along
with DFT-optimized molecular structures, shown for the selenide clusters as examples, and photographs of samples of the isolated compounds.
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along with the spectrum of known compound [(PhSn)4S6] (A)
in Figure 1.
spacer group (as found for 2 and 3). Although we did not
expect crystalline compounds 2 and 3 to generate white light,
we investigate their structures, and also their non-linear
optical response.
To address question 1, we compare the emission spectra of
the sulfide clusters with those of the selenide analogues. The
observations will be discussed at each of the homologous pairs
along this report and summarized at the end. In case of
compounds [(PhSn)4S6] (A) and [(PhSn)4Se6] (1), we do not
see a significant change in the shape of the emission, thus
concluding that the WLG is largely independent from the
composition of the inorganic core here. This is similar to what
has been reported for the variation of the Group 14 element
before.[19]
Compound 2 crystallizes in the tetragonal crystal system
¯
in the space group I4 with two formula units per unit cell. The
ꢀ
Sn S bonds show little variation, ranging from 2.3948(18) to
2.4086(19) ꢁ, which is in the usual range for organotinsul-
fides.[9] The same holds for the bond angles within the
inorganic core (103.60(11)–115.71 (6)8), which are all in close
proximity to an ideal tetrahedral angle. The selenide cluster 3
ꢀ
is isostructural to its lighter homologue. The Sn Se bond
Regarding question 2, we investigate the benzyl-substi-
tuted clusters 2 and 3, and also explored compounds 4 and 5.
The latter feature a CH2CH2(C6H4)CO2Et substituent in
which the phenyl moiety is separated from the tin atom by an
CH2 unit. Compounds 2 and 3 show a striking difference from
the previously prepared clusters. While all other compounds
are obtained as amorphous powders, 2 and 3 are isolated in
crystalline form suitable for single-crystal structural analysis.
Apparently, the methylene groups in the benzyl substitu-
ents give the molecules the necessary flexibility to orient in
a way that allows for an efficient packing in a crystal lattice.
Hence, although enhanced flexibility of substituents often
disturbs long-range order, and also leads to the remarkably
amorphous powders of most of the clusters discussed herein,
the benzyl-substituents seem to lead to an opposite effect for
a gain of lattice energy or alternate second-order interaction
energy. So far, we have identified three possible ways to do so
in this class of compounds: 1) beginning long-range order if
the aromatic system is large enough for efficient p-stacking
(as found for naphthyl substituents in [(NpSn)4S6]),[19] 2) a
relatively small size of the cluster core relative to (small)
aromatic substituents, which in the sum allows for a suffi-
ciently close approach of the clusters for efficient p-stacking
(as found for [(PhSi)4S6]),[19] 3) setting apart a (small) aro-
matic group from the cluster core by introducing an organic
lengths are 2.5227(9)–2.5292(10) ꢁ long, thus longer as in 2
and in the expected range for organotinselenides.[21] The
variation in bond angles is slightly greater than in 2, ranging
from 100.82(5) to 117.13(3)8. For both of the compounds, the
packing diagrams indicate the absence of p-stacking in spite
of the presence of terminal phenyl rings (see the Supporting
Information, Figure S33 for 2, and Figure 2 for 3). Instead,
the benzyl substituents are well separated from each other.
However, the packing of the molecules allows for another
type of secondary interactions, which are found between the
chalcogenide atoms in the cluster core and the phenyl rings of
the neighboring molecules (shortest distance 3.5221(79) ꢁ for
2 and 3.5303(81) ꢁ for 3).
The emission spectra of 2 and 3 are shown in Figure 3.
While the sulfide cluster 2 shows SHG, as expected for
a crystalline compound, the selenide compound 3 unexpect-
edly featured WLG. Yet, as WLG in the crystalline state is
very unlikely to happen for the reasons given above, we also
inspect the thermal behavior of both compounds. While 2
starts decomposing in the temperature range of 160–1808C
without melting, 3 already melts at 1418C without decom-
position. So, their different optical behavior might be put
down to compound 3 melting under irradiation with the result
that the order vanishes, which allows for WLG. To our
knowledge, this observation would be the first experimental
Figure 2. Packing of the cluster molecules in the crystal structure of 3 (left) and illustration of the intermolecular interaction of neighboring
clusters (right). Ellipsoids are set at 50% probability; hydrogen atoms are omitted for clarity. The analogue structure of 2 is given in the
Supporting Information, Figure S51.
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clusters 6 and 7. As shown in Figure 1 (bottom right), these
compounds also show WLG, thus rendering the essential need
for aromatic substituents obsolete. However, in both cases, we
observed a steeper drop-off at the high-energy edge of the
spectrum, resulting in a larger blue portion of the emitted
light. As for the other homologous pairs discussed above,
a red-shift is observed upon inclusion of selenium into the
inorganic core of 7 as compared to the spectrum measured for
6.
The last logical step in this study is to completely dispense
with p-electrons in the substituents. As we knew from our
previous studies that simple aliphatic substituents like methyl
or butyl do not lead to WLG, but cause SHG instead, we
probe the effect of a saturated, yet cyclic substituent. The
substituent of choice here is cyclohexyl for its relationship
with the phenyl group regarding the number of C atoms,
which was realized in compounds 8 and 9 (Figure 1, bottom
left). We observe WLG for both of these compounds, so our
conclusion it that the WLG cannot be based on an electronic
excitation of p electrons. In this case, we did not observe
a red-shift between the spectrum of the sulfide cluster 8 and
that of the selenide cluster 9.
All these results together clearly show the explanation for
the observed phenomenon is to be refined as follows: The
WLG process is based upon excitation of electrons near the
Fermi level with photon energies below the HOMO–LUMO
gap. Hence, from all that we have learned in this work, the
crucial requirement with respect to the electronic structure of
potential white-light emitters is a sufficiently large HOMO–
LUMO gap. Otherwise, electronic excitations into states with
much longer lifetimes gain the upper hand, in which case
other relaxation pathways like photoluminescence will be
observed. Additionally, the amorphous nature of the com-
pounds is key in deciding whether WLG or SHG is observed,
because crystallinity allows for a preference of SHG emission.
To confirm the requirement of sufficiently large HOMO–
LUMO gaps, we inspect the electronic absorption properties
Figure 3. Emission spectra of compounds 2 (no WLG) and 3 (WLG).
Two different excitation schemes were employed: a pulsed Ti:sapphire
laser excitation and a 1450 nm continuous wave (CW) laser diode. As
the field strength of the CW laser diode is not sufficient to generate
detectable second harmonic emission from compound 2, we use the
100 fs pulses from the Ti:sapphire laser to generate a detectable
signal. To keep the data comparable to the measurements in Figure 1,
we decided to show the signal excited by the CW laser diode of
compound 3. The excitation at 800 nm shows a very similar signal
owing to the excitation wavelength-independent emission process (see
also the Experimental Section in the Supporting Information).
evidence of WLG to occur in liquids/melts under CW laser
irradiation. This is similar to WLG upon in situ amorphization
in the solid state, which was observed for a series of
unsymmetrically substituted clusters recently.[22]
To allow for the formation of amorphous solids with this
kind of substituents, we explore compounds with a larger
spacer length, namely compounds 4 and 5 comprising an
ethylene group between the cluster core and the phenyl group
(see Scheme 1, bottom). We hoped that the even enhanced
flexibility of the substituents would inhibit crystallization this
time, which indeed was the case. The emission spectra of these
compounds are shown in the top right part of Figure 1. Both
compounds exhibit WLG. The emission spectrum is not
modified significantly in comparison to that of compounds A
and 1 upon inclusion of a longer spacer. As for the quoted
compounds, the emission sets in at energies slightly above
those of the exciting laser, and drops off at the energy where
SHG would be expected. However, by replacement of sulfur
with selenium, we induce a red-shift of the emission spectrum
that was not observed for the phenyl-substituted clusters,
which we cannot explain to date. Yet, to summarize our result
regarding question 2, the final answer to question 2 is that in
the case of amorphous solids, the aromatic substituents may
be separated from the inorganic cluster core. Having learned
that aliphatic spacers do not inhibit WLG in principle, we
investigate if an aromatic p electron system is at all
a necessary prerequisite for WLG. For this purpose, we
prepare compounds with localized p-electrons in a non-
aromatic system, namely the h1-cyclopentadienyl-substituted
Figure 4. Lowest singlet excitation energies for compounds A, and 1–
9, as calculated by means of TD-DFT studies. The nature of the organic
substituent is shown; S versus Se ligands are indicated by yellow or
red bars, respectively.
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Powder X-ray diffraction patterns were measured on a StadiMP
diffractometer by Stoe equipped with a Mythen 1 K silicon strip
detector and a Cu-Ka (l = 1.54056 ꢁ) X-ray source. Samples were
measured in transmission between two layers of Scotch Tape (3M).
Data for the single-crystal X-ray diffraction analyses were
collected on a STOE STADIVARI four-circle diffractometer using
CuKa radiation (l = 1.54186 ꢁ) at 100 K. Reflection data were
processed with X-Area 1.77.[31] Structure solution was performed by
direct methods and full-matrix-least-squares refinement against F2
using SHELXT[32] and SHELXL-2014[33] software. CCDC 1924382 (2)
and 1924383 (3) contain the supplementary crystallographic data for
this paper. These data are provided free of charge by The Cambridge
Crystallographic Data Centre.
of the compounds by means of time-dependent DFT (TD-
DFT) calculations. The lowest singlet excitation energies are
given in Figure 4 and the Supporting Information, Table S7.
Figures S53–S57 show the corresponding absorption spectra.
In all cases, the HOMO–LUMO gaps are larger than the
highest emission energies, in agreement with the statement
above. Furthermore, the gaps of selenide clusters are
calculated to be smaller than those of the corresponding
sulfides. This correlates well with the different colors of the
products, which are colorless or yellow in case of the sulfur
compounds, and darker (yellow to dark orange, see Scheme 1)
in case of the corresponding selenides.
White-light emission and SHG were performed using a confocal
microscopy spectroscopy setup. For excitation, we use either 100-fs
pulses from a titan-sapphire laser oscillator operating at a repetition
rate of 78 MHz tuned to 1.56 eV for SHG experiments and a multi-
mode continuous-wave diode laser at a photon energy of 0.855 eV for
white-light emission. A 0.5 NA Schwarzschild objective focusses and
collects the light onto and from the sample, which is held in vacuum at
room temperature (293 K). A lens focuses the back-reflected light
onto an either an imaging camera or the entrance slit of a quarter
meter Czechy–Turner spectrometer equipped with a thermoelectri-
cally cooled silicon deep-depletion charge-coupled-device camera.
The apparently different overall shape of the emission spectra in
comparison with those reported in former work[14,20] are due to
a detection-based change and not due to the different excitation
wavelength. In the present work, we use a 1450 nm laser diode to
suppress the excitation laser line, which would otherwise appear in
the employed silicon-based detection system. Accordingly, we do not
use any filters in front of our detection system and thus, we are able to
detect in the full response window of the silicon CCD. In the quoted
publications, a 980 nm diode was used, which is filtered from the
spectra, yielding the altered shape of the WL emission. However, the
actual emission is not affected by the change of excitation wavelength
and the different appearance is due to the employed filter set in the
detection.
Yet, this does not explain the red-shift in the emission
spectra observed for compounds 5 and 7, as the emission in
both cases is limited at an energy of about 2.0 eV, which is still
significantly below the lowest excitation energies. Moreover,
to this date, we cannot explain why the substitution of
selenium for sulfur induces a red-shift of the emission in some
cases, while in some cases no such effect occurs. This will be
subject to ongoing studies within the framework of FOR 2824.
Conclusion
We report on a study that provides a big step forward in
the understanding of this class of white-light emitters based
on adamantane-type organotin chalcogenide clusters. While
the previously stated precondition of the materials to be
amorphous was substantiated, our new findings prompted us
to re-phrase some of our former assumptions that were made
based on a much smaller cohort of compounds. Clusters of the
type [(RSn4E6)] are capable of white-light generation (WLG)
if they fulfill the following preconditions: The materials need
to contain electron-rich (cyclic) substituents, which may (but
do not need to) possess p-electrons, and which do not need to
be directly bonded to the inorganic cluster core, as long the
spacer group does not cause crystallization. A point that could
not be clarified so far is the impact of a homologous
replacement of sulfur atoms with its heavier congeners on
the emission properties, while the effect on the absorption
properties is clearly a red-shift. Here, we need to refer to
future comprehensive work into this direction.
Density functional theory (DFT) calculations were carried out
with TURBOMOLE[34] using def2-TZVP basis sets[35] and taking
advantage of the multipole-accelerated resolution-of the-identity
method.[36] Structures were optimized with the functional BP86.[37]
Time-dependent DFT (TD-DFT) calculations were done employing
the B3-LYP functional.[38]
Acknowledgements
This work was supported by the Deutsche Forschungsge-
meinschaft within the frameworks of FOR 2824 and
GRK1782. The Giessen group additionally acknowledges
financial support by the European regional development
fonts (EFRE 2DIBS). S.C. furthermore thanks the Heisen-
berg programme (CH660/2).
Experimental Section
Detailed syntheses, characterization, and details of spectroscopic
techniques are to be found in the Supporting Information.
All synthetic steps were carried out under exclusion of oxygen
and moisture by use of standard Schlenk techniques. Phenyltin
trichloride,[23] bis(trimethylsilyl) sulfide[24] and selenide,[25] sodium
cyclopentadienide,[26] tetracyclohexyltin,[27] benzyltributyltin,[28] 4-vi-
nylethylbenzoate,[29] and tricyclohexylstannane[30] were prepared
according to previously procedures; SnCl4 and AIBN were used as
received from abcr.
Conflict of interest
The authors declare no conflict of interest.
For the synthesis and characterization of BnSnCl3 (A), R1SnCy3
(B), R1SnCl3 (C), CySnCl3 (D), and compounds [(PhSn)4Se6] (1),
[(BnSn)4S6] (2), [(BnSn)4Se6] (3), [(R1Sn)4S6] (4), [(R1Sn)4Se6] (5),
[(CpSn)4S6] (6), [(CpSn)4Se6] (7), [(CySn)4S6] (8), and [(CySn)4Se6]
(9), see the Supporting Information.
Keywords: main-group clusters ·
quantum chemical calculations · second-harmonic generation ·
substituent effects · white-light generation
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[20] We use the term WLG in a broader sense to refer to the similar
process in previous studies. The term, as we understand it, refers
to light composed of multiple wavelengths, that is, spanning
a broad spectral range, which does not necessarily mean that the
emission shows a purely white color. Note that the term
“emission” always refers to this kind of “WL emission” herein.
[21] K. Wraage, T. Pape, R. Herbst-Irmer, M. Noltemeyer, H. G.
Schmidt, H. W. Roesky, Eur. J. Inorg. Chem. 1999, 869 – 872.
[22] E. Dornsiepen, F. Dobener, N. Mengel, O. Lenchuk, C. Dues, S.
Sanna, D. Mollenhauer, S. Chatterjee, S. Dehnen, Adv. Opt.
Mater. 2019, 7, https://doi.org/10.1002/adom.201801793.
[23] H. Zimmer, W. Sparmann, Chem. Ber. 1954, 87, 645 – 651.
[24] J. H. So, P. Boudjouk, Synthesis 1989, 306 – 307.
[25] M. W. DeGroot, N. J. Taylor, J. F. Corrigan, J. Mater. Chem. 2004,
14, 654 – 660.
[1] M. G. Kanatzidis, Adv. Mater. 2007, 19, 1165 – 1181.
[2] W. Schiwy, B. Krebs, Angew. Chem. Int. Ed. Engl. 1975, 14, 436 –
436; Angew. Chem. 1975, 87, 451 – 452.
[3] N. Kamaya, K. Homma, Y. Yamakawa, M. Hirayama, R. Kanno,
M. Yonemura, T. Kamiyama, Y. Kato, S. Hama, K. Kawamoto,
A. Mitsui, Nat. Mater. 2011, 10, 682 – 686.
[4] N. Zheng, X. Bu, B. Wang, P. Feng, Science 2002, 298, 2366 –
2369.
[5] S. Bag, P. N. Trikalitis, P. J. Chupas, G. S. Armatas, M. G.
Kanatzidis, Science 2007, 317, 490 – 493.
[6] R. L. Gitzendanner, F. J. DiSalvo, Inorg. Chem. 1996, 35, 2623 –
2626.
[26] T. K. Panda, M. T. Gamer, P. W. Roesky, Organometallics 2003,
22, 877 – 878.
[7] L. Nicole, C. Laberty-Robert, L. Rozes, C. Sanchez, Nanoscale
2014, 6, 6267 – 6292.
[27] E. Krause, R. Pohland, Ber. Dtsch. Chem. Ges. 1924, 57, 532 –
544.
[28] D. V. Airapetyan, V. S. Petrosyan, S. V. Gruener, K. V. Zaitsev,
D. E. Arkhipov, A. A. Korlyukov, J. Organomet. Chem. 2013,
747, 241 – 248.
[8] Z. Hassanzadeh Fard, C. Mꢂller, T. Harmening, R. Pçttgen, S.
Dehnen, Angew. Chem. Int. Ed. 2009, 48, 4441 – 4444; Angew.
Chem. 2009, 121, 4507 – 4511.
[9] Z. Hassanzadeh Fard, M. Reza Halvagar, S. Dehnen, J. Am.
Chem. Soc. 2010, 132, 2848 – 2849.
[29] S. Cho, B. Ma, S. T. Nguyen, J. T. Hupp, T. E. Albrecht-Schmitt,
Chem. Commun. 2006, 2563 – 2565.
[30] B. Jousseaume, M. Lahcini, M.-C. Rascle, Organometallics 1995,
14, 685 – 689.
[31] Stoe and Cie GmbH, X-Area, Version 1.77, 2016.
[32] G. M. Sheldrick, Acta Crystallogr. Sect. A 2015, 71, 3 – 8.
[33] C. B. Hꢂbschle, G. M. Sheldrick, B. Dittrich, J. Appl. Crystallogr.
2011, 44, 1281 – 1284.
[34] TURBOMOLE Version 7.3, TURBOMOLE GmbH 2018.
TURBOMOLE is a development of University of Karlsruhe
and Forschungszentrum Karlsruhe 1989 – 2007, TURBOMOLE
GmbH since 2007.
[35] K. Eichkorn, F. Weigend, O. Treutler, R. Ahlrichs, Theor. Chem.
Acc. 1997, 97, 119.
[36] M. Sierka, A. Hogekamp, R. Ahlrichs, J. Chem. Phys. 2003, 118,
9136 – 9148.
[37] a) A. Becke, Phys. Rev. A 1988, 38, 3098 – 3100; b) J. Perdew,
Phys. Rev. B 1986, 33, 8822 – 8824.
[38] C. Lee, W. Yang, R. G. Parr, Phys. Rev. B. 1988, 37, 785 – 789.
[10] a) J. P. Eußner, B. E. K. Barth, E. Leusmann, Z. You, N. Rinn, S.
Dehnen, Chem. Eur. J. 2013, 19, 13792 – 13802; b) J. P. Eußner, S.
Dehnen, Chem. Commun. 2014, 50, 11385 – 11388; c) J. P.
Eußner, R. O. Kusche, S. Dehnen, Chem. Eur. J. 2015, 21,
12376 – 12388.
[11] E. Leusmann, F. Schneck, S. Dehnen, Organometallics 2015, 34,
3264 – 3271.
[12] a) N. Rinn, J. P. Eußner, W. Kaschuba, X. Xie, S. Dehnen, Chem.
Eur. J. 2016, 22, 3094 – 3104; b) N. Rinn, L. Guggolz, J. Lange, S.
Chatterjee, T. Block, R. Pçttgen, S. Dehnen, Chem. Eur. J. 2018,
24, 5840 – 5848.
[13] N. W. Rosemann, J. P. Eußner, A. Beyer, S. W. Koch, K. Volz, S.
Dehnen, S. Chatterjee, Science 2016, 352, 1301 – 1304.
[14] P. Pfeiffer, R. Lehnardt, Ber. Dtsch. Chem. Ges. 1903, 36, 3027 –
3030.
[15] C. Dorfelt, A. Janeck, D. Kobelt, E. F. Paulus, H. Scherer, J.
Organomet. Chem. 1968, 14, P22 – P24.
[16] J. C. J. Bart, J. J. Daly, J. Chem. Soc. Dalton Trans. 1975, 2063 –
2068.
[17] H. Berwe, A. Haas, Chem. Ber. 1987, 120, 1175 – 1182.
[18] C. Wagner, C. Raschke, K. Merzweiler, Appl. Organomet. Chem.
2004, 18, 147.
Manuscript received: August 6, 2019
[19] N. W. Rosemann, J. P. Eußner, E. Dornsiepen, S. Chatterjee, S.
Dehnen, J. Am. Chem. Soc. 2016, 138, 16224 – 16227.
Accepted manuscript online: September 11, 2019
Version of record online: && &&
,
&&&&
Angew. Chem. Int. Ed. 2019, 58, 2 – 8
ꢀ 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
&&&&
These are not the final page numbers!

Angewandte
Research Articles
Chemie
Research Articles
Main-Group Chemistry
In search of the preconditions for the
generation of highly directed white-light
by means of amorphous molecular
materials of the general formula [(RT)4E6]
(R=organic group, T/E=Group 14/16
elements), nine new compounds were
studied. Surprisingly, R does not need to
be an aromatic ligand, in striking contrast
to previous assumptions.
E. Dornsiepen, F. Dobener, S. Chatterjee,
S. Dehnen*
&&&& — &&&&
Controlling the White-Light Generation of
[(RSn)4E6]: Effects of Substituent and
Chalcogenide Variation
&&&&
www.angewandte.org
ꢀ 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2019, 58, 2 – 8
These are not the final page numbers!