Aggregation induced emission-emissive stannoles in the solid state

Article abstract of DOI:10.1039/d0cc04525j

The optoelectronic and structural properties of six stannoles are reported. All revealed extremely weak emission in solution at 295 K, but intensive fluorescence in the solid state with quantum yields (ΦF) of up to 11.1% in the crystal, and of up to 24.4% (ΦF) in the thin film.

Full text of DOI:10.1039/d0cc04525j

View Article Online
View Journal
ChemComm
Chemical Communications
Accepted Manuscript
This article can be cited before page numbers have been issued, to do this please use: I. Ramirez y
Medina, M. Rohdenburg, E. Lork and A. Staubitz, Chem. Commun., 2020, DOI: 10.1039/D0CC04525J.
Volume 54
This is an Accepted Manuscript, which has been through the
Number
January 2018
Pages 1-112
1
4
Royal Society of Chemistry peer review process and has been
accepted for publication.
ChemComm
Chemical Communications
rsc.li/chemcomm
Accepted Manuscripts are published online shortly after acceptance,
before technical editing, formatting and proof reading. Using this free
service, authors can make their results available to the community, in
citable form, before we publish the edited article. We will replace this
Accepted Manuscript with the edited and formatted Advance Article as
soon as it is available.
You can find more information about Accepted Manuscripts in the
Information for Authors.
Please note that technical editing may introduce minor changes to the
text and/or graphics, which may alter content. The journal’s standard
Terms & Conditions and the Ethical guidelines still apply. In no event
shall the Royal Society of Chemistry be held responsible for any errors
or omissions in this Accepted Manuscript or any consequences arising
from the use of any information it contains.
ISSN 1359-7345
COMMUNICATION
S. J. Connon, M. O. Senge et al.
Conformational control of nonplanar free base porphyrins:
towards bifunctional catalysts of tunable basicity
rsc.li/chemcomm

Please do not adjust margins
Page 1 of 6
ChemComm
View Article Online
DOI: 10.1039/D0CC04525J
COMMUNICATION
Aggregation Induced Emission – Emissive Stannoles in the Solid
State†
Isabel-Maria Ramirez y Medina,a,b Markus Rohdenburg,c Enno Lork d,b and Anne Staubitz *a, b
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
The optoelectronical and structural properties of six stannoles are heavier element Sn, the emission is weakened to non-existent.
reported. All revealed extremely weak emission in solution at This is most likely due to the heavy element effect of Sn and
295 K, but intensive fluorescence in the solid state with quantum the elongated Sn--C bonds that enhance molecular vibration.2a,
yields (ՓF) of up to 11.1% in the crystal, and in thin film of up to 2c, 8a, 9c, 11 In general, group 14 metalloles (containing Si, Ge, Sn)
24.4% ՓF).
display higher quantum yields (ՓF) in the aggregated state in
dioxane or tetrahydrofuran/water mixtures caused by AIE, but
again, ՓF for the Sn analogues is the lowest (e.g. ՓF, in 90%
water fraction: Silole-Ph6 38%, Germole-Ph6 10%, Stannole-Ph6
1%).2a About the fluorescence behaviour of plumboles little is
known so far.9b
In comparison to classical stannoles, fused-ring systems as
stannafluorenes and dithienostannoles are (highly) emissive in
solution (examples by Yang and co-workers, Tilley and co-
workers, Ohshita and co-workers, ՓF: 0.9-65%).11-12 The
dithienostannoles by Ohshita and co-workers are also efficient
emitters in the crystalline state (ՓF: 21-56%).11a So far, it is not
reported that classical non-fused stannoles show quantum
yields higher than 1% in fluid-phase aggregates and 3.8% in
dispersed phase in glasses of sucrose octaacetate,
respectively.2a
Fluorescent compounds are very useful for biological and
medical applications as well as in materials science. However,
in the literature, many luminescent compounds are described
to exhibit aggregation-caused quenching (ACQ), which reduces
or destroys the fluorescence quantum yields. This makes such
compounds difficult to use in devices, even if they appear
promising in solution. However, for other compound classes
aggregation induced emission (AIE) is observed, which was
described the first time in 2001 by Tang and co-workers.1 One
of these interesting classes consists of the group 14
metalloles.1c, In the past, only siloles have received much
2
attention due to their promising optoelectronic properties in
the fields of materials science,3 biological imaging,4 biological
sensors,5 explosives sensors6 and device applications,7 but
germoles, stannoles and plumboles were little investigated
with respect to their emission properties and applications.1c, 2a,
6b, 8
In this study, we present a set of classical stannoles (Figure 1)
that show unexpected high quantum yields in the crystalline
state of up to 11.1% and in thin films of up to 24.4%.
All of the group 14 metalloles (containing Si, Ge, Sn, Pb) exhibit
narrower highest occupied molecular orbital (HOMO)-lowest
unoccupied molecular orbital (LUMO) energy gaps compared
to their carbon analogues as well as broad red-shifted
absorption maxima.9 The reason for this is a strong σ*−π*
conjugation, also known as hyperconjugation, in the
molecule.9a, 10 However, within group 14, from Si and Ge to the
a. University of Bremen, Institute for Organic and Analytical Chemistry, Leobener
Str. 7, 28359 Bremen, Germany; *E-Mail: staubitz@uni-bremen.de
b. University of Bremen, MAPEX Center for Materials and Processes, Bibliothekstr. 1,
28359 Bremen, Germany
c. University of Bremen, Institute for Applied and Physical Chemistry, Leobener Str.
5, 28359 Bremen, Germany
d. University of Bremen, Institute for Inorganic Chemistry and Crystallography,
Leobener Str. 7, 28359 Bremen, Germany
† Electronic Supplementary Information (ESI) available: [Experimental procedures,
NMR spectra, spectral data (absorption and emission), crystallographic data and
computational data]. See DOI: 10.1039/x0xx00000x
Figure 1. Molecular structures of stannoles ST1-ST6.
Please do not adjust margins

Please do not adjust margins
ChemComm
Page 2 of 6
COMMUNICATION
Journal Name
Herein, we report on the synthesis and crystal structures of 311++G(2d,2p) //PBE1PBE1-GD3BJ/6-311++G(2d,2p)// model
View Article Online
four new stannoles ST1, ST2, ST3, and ST6, the optical chemistry and SDD pseudo potentDiaOlI: 1f0o.1r039S/nD0CfCit045t2h5eJ
properties, in particular the fluorescence properties in fluid experimental data well.14 Main electronic transitions are
solutions, frozen solutions, in water/tetrahydrofuran mixtures, located around 425 nm (ST1) to 456 nm (ST4) and correspond
thin films and crystalline states of in total six stannoles ST1- to a direct HOMO-LUMO transition. Because calculations of
ST6. Theoretical results by DFT and TD-DFT calculations single molecules in the gas phase were used, the absorption
support our experimental results.
maxima are slightly red-shifted about 7 nm to 19 nm
The synthesis of the stannoles analysed in this work was compared to the experimental results (ESI Table S8).
straightforward: Reactions of Rosenthal´s zirconocene with The luminescence of the six stannoles was extremely weak in
alkynes 8, 10, or 13 and di-alkynes 17, 18 or 19 (see alkynes in solution (10-5 M, in chloroform, toluene, tetrahydrofuran) at
the ESI) led to zirconacyclopentadienes, which were used for 295 K with ՓF <0.1% in almost all cases and λem, max in the order
further transmetalation reactions with dichlorodimethyl- 501 nm (ST3)< 507 nm (ST6)< 509 nm (ST5)< 513 nm (ST1)
stannane, dichlorodiphenylstannane and di-(p-hexylphenyl)- < 517 nm (ST2)< 530 nm (ST4). However, two exceptions were
dichlorostannane (22) in the presence of copper(I) chloride to ST4 and ST6 with ՓF = 1.0% and ՓF = 0.4%, respectively, in
furnish ST1-ST6 in yields ranging from 22% to 70% (see all toluene. Similar to the observations for the absorption spectra,
procedures in the ESI).13
The molecular structures of ST1, ST2, ST3 and ST6 are
the polarity of the solvent had little to no effect on ՓF or λem,
max
(ESI Table 5). Stokes shifts ranged from 3706 cm-1 (ST4,
illustrated in figures S1, S5, S9, S13 (ESI) and confirm the toluene) to 4939 cm-1 (ST1, toluene) and all fluorescence half-
identity of the compounds; tables S3 and S4 (ESI) summarise lifes were between τ295 K < 80 ps and 0.13 ns (ESI, Table S5, S6).
the crystal data, selected bond distances and angles. The The luminescence of ST1 and ST5 was also measured in
molecular structures of ST4 and ST5 have already been different solution mixtures of tetrahydrofuran/water at 295 K,
reported by us.9a, 13c The optimised DFT geometries of ST1-ST3 in which these compounds are expected to aggregate. Thus,
and ST6 are in agreement with the molecular structures as this technique can be used to investigate the phenomenon of
derived from crystal data. All compounds show small HOMO- AIE of stannoles in fluid-phase aggregates. The intensity of the
LUMO energy gaps in the range of 3.2-3.4 eV. HOMO and emission maximum increased slowly from 0% (ՓF: <0.1%) to
LUMO are delocalised over the whole backbone and with the 50%/ 60% water fraction for ST1/ ST5, respectively, then
exception of ST6, the Sn atoms are involved in the LUMO at stronger until the water fraction was at 98% (ՓF: 0.4%) for ST1
the displayed isovalue (leading to efficient σ*−π* conjugation), and 85% water fraction (ՓF: 2.5%) for ST5 (Figure 3). Dispersed
while the substituents at the Sn atom are hardly involved particles [µm size] were observed in the solvent mixtures at a
9c
(Figure 2; Figures S111-S116 ESI).9a,
The structure of the water fraction of 70% as indicated by a change from a clear to
LUMO of stannole ST6 appears to have the same a cloudy solution. At 80% water fraction, the mixtures became
characteristics as our previous calculated stannole with 5- homogenous again [nm particles] and with water fractions
nitro-thiophenyl substituents in the 2- and 5-position of the higher than 80%, again visible large aggregates were observed
stannole ring.9a
making the suspension completely inhomogeneous. In the
case of ST5, the emission intensity decreased again at 90%
water fraction (Figure 3). These observations are similar to the
findings of Mullin and co-workers for their group 14
2b
metalloles.2a, Micrographs primarily show needles for ST1
and mixtures of needles and plates for ST5 (ESI, Figures S98-
S104).
Figure 2. FMOs and HOMO-LUMO energy gaps of ST1-ST6.
All stannoles showed absorption in the short-wave region
< 280 nm and a major absorption band with vibrational fine-
structure with λabs,
in the order 412 nm (ST3)< 413 nm
max
(ST1)< 414 nm (ST2) < 418 nm (ST5)< 425 nm (ST6)< 442 nm
(ST4) in solutions of chloroform, toluene and 2-
methyltetrahydrofuran (10-5 M) at 295 K (ESI Table 5). These
휋→휋
휋
bands can be assigned to
* transitions, involving the
-
휋
and *-orbitals of the stannole ring. The polarity of the solvent
had no effect on
λabs, max. All compounds exhibited high extinction coefficients
ranging from 9146 mol∙L-1∙cm-1 (ST2) to 44500 mol∙L-1∙cm-1
(ST4) (ESI Table 5). Our theoretical results from TD-DFT
Figure 3. a) Emission spectra of ST1 and c) of ST5 in tetrahydrofuran/water with
different water fractions at 295 K. b) Plot of maximum intensity against water fraction
(vol %) of ST1 and d) of ST5.
calculations
employing
the
TD-PBE1PBE1-GD3BJ/6-
2 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 3 of 6
ChemComm
Please do not adjust margins
Journal Name
COMMUNICATION
Furthermore, the emission behaviour of ST1-ST6 was 3.9% in the crystalline state and ՓF = 9.3% in thin film
View Article Online
investigated in a solution of 2-methyltetrahydrofurane (10-5 M) (Figure 5). Compared to λem,
in solution at 295 K, the
DOI: 10.1039/D0CC04525J
max
at various temperatures (ST2 Figure 4, ESI Figures S46, S55, maximum was red-shifted by up to 87 nm in the solid state.
S64, S73, S84, S93). While the photoluminescence intensity The compound with the largest shift in the emission maximum
increased slowly from 280 K to 160 K for ST1-ST3, it increased (ST6) showed orange photoluminescence with λem,
=
max
extremely strongly from 140 K to 80 K. The intensity at 280 K 594 nm, ՓF = 11.1% in the crystalline state and even ՓF =
to 80 K was in total increased by a highly significant factor of 24.4% in thin film. In comparison to ST1-ST5, ST6 has thiazolyl-
158 to 620 for ST1-ST3. Compared to 280 K, λem, max was blue- substituents in the 2- and 5-positions. In summary, ՓF are 5 to
shifted about 4 nm to 33 nm, which is consistent with earlier 111 times higher in the crystalline state than in solution at
reports.2a
295 K and even higher in film indicating strong AIE. Except for
ST2, ՓF were 1.8 to 4.2 times higher in thin film than in the
crystalline state and 10 to even 244 times higher than in
solution at 295 K. Going from solution to solid state, λem, max
are red-shifted; this is most probably due to enhanced
conjugation within the molecules in the solid state as
compared to isolated, non-aggregated molecules in solution, in
which the aryl-substituents can rotate with respect to the
stannole core.1c The fluorescence half lifes were between
τ295 K < 0.20 ns and τ295 K = 0.53 ns and all stannoles exhibited
small stokes shifts of Δ휈 = 1094 cm–1 to 1997 cm–1 with regard
to the excitation maximum in the solid state (Table 1). During
our experiments, we never observed long living triplet
emission (phosphorescence), neither at 295 K in solution or
solid state nor at 80 K in frozen solution.
In general, ՓF values are higher for ST4-ST6 with aromatic rings
at the Sn atom than for ST1-ST3 with methyl groups on Sn.
Furthermore, λem, max are red-shifted, which was also observed
by Mullin and co-workers for similar systems.2a The
thiophenyl/thiazolyl rings in the 2- and 5-positions of the
stannole ring make the overall backbone of the structure more
planar, which means better conjugation within the system as
compared to twisted backbones, e.g. for HPSn/ DMTPSn. This
Figure 4. a) Temperature dependent emission spectra of ST2 in 2-
methyltetrahydrofuran. b) Picture of the irradiated frozen solution of ST2 at 80 K. c)
Plot of maximum intensity against the temperature. d) Plot of the maximum
wavelength against the temperature.
Analysing the temperature-intensity dependency for ST4, ST5
and ST6, it could be observed that the intensity increased little
from 280 K to 200 K, then very rapidly from 220 K to 80 K.
Compared to 280 K, the intensity was increased by a very high
factor of 87 to 334 for ST4-ST6 at 80 K. From 280 K to 80 K, all
three compounds (ST4, ST5 and ST6) exhibited a blue-shift of
λem, max about 5 nm to 17 nm. The irradiated frozen solutions of
ST1-ST6 at 80 K are illustrated in Figure 4 and in the ESI, figures
S19, S22, S25, S28, S32, S35 and show intense luminescence.
For all structures, upon cooling, the broad emission band at
280 K split up into at least three larger and one small defined
emission bands. This is most likely caused by suppression of
intramolecular degrees of freedom. Furthermore, the
observed colour of fluorescence of the frozen solution
depended on the intensity ratio of the three main bands. All
were in the range of turquois blue to green. Fluorescence half
lifes were between τ80 K = 0.90 ns (33.4%), 2.77 ns (66.6%) and
τ80 K = 3.83 ns, significant higher than at 295 K (ESI, Table S6).
Most importantly, and the first time described for classical
stannoles, all structures showed visible luminescence in the
solid state (Figure 5). ST1, ST2 and ST5 showed green
emissions from 519 nm to 538 nm with ՓF 1.2% to 10.2% in
the crystalline state and ՓF 1.8% to 18.8% in thin film. ST3
exhibited turquois-green emission with λem, max = 510 nm, ՓF =
0.5% in the crystalline state and ՓF = 1.0% in thin film. ST4
displayed greenish-yellow emission with λem, max = 557 nm, ՓF =
leads to a red-shift in λabs,
and λem,
as compared to
max
max
twisted structures such as HPSn/ DMTPSn and also to an
2a
increased emission intensity.1c, While for ST1-ST3 no
-
휋 휋
interactions between the molecules in the crystal unit cell
휋 휋
were observed, ST6 exhibits
-
stacking between the
thiazolyl-groups of two stannole molecules with an interplanar
distance of 3.493 Å and a slip angle of 76.7 ° (ESI, Figure S17).
Figure 5. a) Steady-state fluorescence spectra in the solid state of ST1-ST6 at 295 K.
b) CIE 1931 chromaticity plot with emission colour coordinates of ST1-ST6; images of
ST1-ST6 under irradiation at 366 nm.
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 3
Please do not adjust margins

Please do not adjust margins
ChemComm
Page 4 of 6
COMMUNICATION
휋 휋
- stacking quenches emission, but in our case, ST6
had the highest ՓF. The substituents in the 3- and 4-positions
are not involved in the HOMO and LUMO and have only a
small effect on the emission; but they are important for the
crystal unit cell packing, therefore causing larger differences in
ՓF between ST1-ST3 (for further discussions see ESI).2b
Journal Name
4. C. Pui-yee Chan, M. Haeussler, B. Zhong Tang, Y. Dong, K.-k.
Sin, W.-c. Mak, D. Trau, M. Seydack anDdORI:. 1R0e.1n0n3Ve9ie/bDwe0ArCrgtiC,clJ0e.4O5n2li5nJe
Immunol. Methods, 2004, 295, 111–118.
5. M. Wang, G. Zhang, D. Zhang, D. Zhu and B. Z. Tang, J. Mater.
Chem., 2010, 20, 1858–1867.
6. (a) S. J. Toal, D. Magde and W. C. Trogler, Chem. Commun.,
2005, DOI: 10.1039/B509404F, 5465-5467; (b) S. J. Toal, J. C.
Sanchez, R. E. Dugan and W. C. Trogler, J. Forensic Sci., 2007,
52, 79-83.
7. (a) Z. Li, Y. Q. Dong, J. W. Y. Lam, J. Sun, A. Qin, M. Häußler,
Y. P. Dong, H. H. Y. Sung, I. D. Williams, H. S. Kwok and B. Z.
Tang, Adv. Funct. Mater., 2009, 19, 905–917; (b) W. Feng, Q.
Su, Y. Ma, Z. Džolić, F. Huang, Z. Wang, S. Chen and B. Z.
Tang, J. Org. Chem., 2020, 85, 158–167.
Normally,
A possible reason for the phenomenon of AIE can be the
restricted intramolecular rotation (RIR) in these molecules.
Therefore, the non-radiative pathways are reduced, while the
emissive
pathway
becomes
dominant
and
the
photoluminescence increases dramatically.1a, 1d, 2a, 2b
In conclusion, we experimentally and computationally
investigated the optical properties and crystal structures of six
stannoles ST1-ST6. Specifically, their fluorescence properties in
fluid and frozen solutions and solid state were investigated.
With this work, classical stannoles with ՓF up to 11.1% in the
crystalline state and 24.4% in thin film were reported for the
first time. We also observed different colours of emissions
ranging from blue turquois to green in frozen solutions at 80 K
and turquois green to orange in the solid state. Future work
will see an in-depth analysis of structure-property
relationships to further increase the emission in the solid state
and eventually the application in organic light-emitting diodes.
8. (a) A. J. Boydston and B. L. Pagenkopf, Angew. Chem. Int. Ed.,
2004, 43, 6336–6338; (b) S. H. Lee, B.-B. Jang and Z. H. Kafafi,
J. Am. Chem. Soc., 2005, 127, 9071–9078.
9. (a) I.-M. Ramirez y Medina, M. Rohdenburg, F. Mostaghimi,
S. Grabowsky, P. Swiderek, J. Beckmann, J. Hoffmann, V.
Dorcet, M. Hissler and A. Staubitz, Inorg. Chem., 2018, 57,
12562–12575; (b) M. Saito, M. Sakaguchi, T. Tajima, K.
Ishimura and S. Nagase, Phosphorus, Sulfur, and Silicon and
the Related Elements, 2010, 185, 1068–1076; (c) S.
Yamaguchi, Y. Itami and K. Tamao, Organometallics, 1998,
17, 4910–4916.
10. S. Yamaguchi and K. Tamao, Bull. Chem. Soc. Jpn., 1996, 69,
2327–2334.
11. (a) D. Tanaka, J. Ohshita, Y. Ooyama, N. Kobayashi, H.
Higashimura, T. Nakanishi and Y. Hasegawa,
Organometallics, 2013, 32, 4136–4141; (b) C. Gu, D. Zhu, M.
Qiu, L. Han, S. Wen, Y. Li and R. Yang, New J. Chem., 2016,
40, 7787–7794.
Acknowledgement
The authors are grateful to Dr. J. Warneke for supplying
computational resources for this work. We thank Prof. Dr. N.-
C. Bigall, Dr. D. Dorfs and P. Rusch for supporting the
fluorescence measurements. We also thank Dr. T. Dülcks, D.
Kemken, Dr. M. Olaru and Dr. M. Kleemeier for their help and
great discussions.
12. K. Geramita, J. McBee and T. D. Tilley, J. Org. Chem., 2009,
74, 820–829.
13. (a) U. Rosenthal, A. Ohff, W. Baumann, A. Tillack, H. Görls, V.
V. Burlakov and V. B. Shur, Z. Anorg. Allg. Chem., 1995, 621,
77–83; (b) S. Urrego-Riveros, I.-M. Ramirez y Medina, D.
Duvinage, E. Lork, F. D. Sönnichsen and A. Staubitz, Chem.
Eur. J., 2019, 25, 13318–13328; (c) J. Linshoeft, E. J. Baum, A.
Hussain, P. J. Gates, C. Näther and A. Staubitz, Angew. Chem.
Int. Ed., 2014, 53, 12916–12920; (d) V. Weingand, T. Wurm,
V. Vethacke, M. C. Dietl, D. Ehjeij, M. Rudolph, F. Rominger,
J. Xie and A. S. K. Hashmi, Chem. Eur. J., 2018, 24, 3725–
3728; (e) D. Lasányi, Á. Mészáros, Z. Novák and G. L. Tolnai, J.
Org. Chem., 2018, 83, 8281–8291; (f) Y. Wei, H. Zhao, J. Kan,
W. Su and M. Hong, J. Am. Chem. Soc., 2010, 132, 2522–
2523; (g) V. Y. Lu and T. D. Tilley, Macromolecules, 2000, 33,
2403–2412; (h) P. J. Fagan, W. A. Nugent and J. C. Calabrese,
Journal of the American Chemical Society, 1994, 116, 1880–
1889.
14. (a) C. Adamo and V. Barone, J. Chem. Phys., 1999, 110,
6158–6170; (b) A. D. McLean and G. S. Chandler, J. Chem.
Phys., 1980, 72, 5639–5648; (c) R. Krishnan, J. S. Binkley, R.
Seeger and J. A. Pople, J. Chem. Phys., 1980, 72, 650–654; (d)
R. C. Binning Jr. and L. A. Curtiss, J. Comput. Chem., 1990, 11,
1206–1216; (e) M. P. McGrath and L. Radom, J. Chem. Phys.,
1991, 94, 511–516; (f) L. A. Curtiss, M. P. McGrath, J.
Blaudeau, N. E. Davis, R. C. Binning and L. Radom, J. Chem.
Phys., 1995, 103, 6104–6113; (g) S. Grimme, J. Antony, S.
Ehrlich and H. Krieg, J. Chem. Phys., 2010, 132, 154104; (h) S.
Grimme, S. Ehrlich and L. Goerigk, J. Comput. Chem., 2011,
32, 1456–1465; (i) G. Igel-Mann, H. Stoll and H. Preuss, Mol.
Phys., 1988, 65, 1321–1328; (j) A. Bergner, M. Dolg, W.
Küchle, H. Stoll and H. Preuß, Mol. Phys., 1993, 80, 1431–
1441.
Conflicts of interest
There are no conflicts to declare.
Notes and references
1. (a) J. Mei, N. L. C. Leung, R. T. K. Kwok, J. W. Y. Lam and B. Z.
Tang, Chem. Rev., 2015, 115, 11718–11940; (b) X. Ma, R.
Sun, J. Cheng, J. Liu, F. Gou, H. Xiang and X. Zhou, J. Chem.
Educ., 2016, 93, 345–350; (c) J. Luo, Z. Xie, J. W. Y. Lam, L.
Cheng, H. Chen, C. Qiu, H. S. Kwok, X. Zhan, Y. Liu, D. Zhu and
B. Z. Tang, Chem. Comm., 2001, 1740–1741; (d) Y. Hong, J.
W. Y. Lam and B. Z. Tang, Chem. Soc. Rev., 2011, 40, 5361-
5388.
2. (a) H. J. Tracy, J. L. Mullin, W. T. Klooster, J. A. Martin, J.
Haug, S. Wallace, I. Rudloe and K. Watts, Inorg. Chem., 2005,
44, 2003–2011; (b) J. L. Mullin and H. J. Tracy, in
Aggregation-Induced Emission: Fundamentals and
Applications, Volumes 1 and 2, John Wiley and Sons Ltd,
2013, DOI: 10.1002/9781118735183.ch02, pp. 39–60; (c) J.
Ferman, J. P. Kakareka, W. T. Klooster, J. L. Mullin, J.
Quattrucci, J. S. Ricci, H. J. Tracy, W. J. Vining and S. Wallace,
Inorg. Chem., 1999, 38, 2464–2472.
3. J. Chen, Z. Xie, J. W. Y. Lam, C. C. W. Law and B. Z. Tang,
Macromolecules, 2003, 36, 1108–1117.
4 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 5 of 6
ChemComm
View Article Online
DOI: 10.1039/D0CC04525J
TOC
For the first time, six classical stannoles with photoluminescence quantum yields up to 11.1% in the
crystalline state and 24.4% in thin film are presented.

ChemComm
Page 6 of 6
View Article Online
DOI: 10.1039/D0CC04525J
600x400mm (96 x 96 DPI)