Full text of DOI:10.1002/chem.201704572

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Accepted Article
Title: Optical Properties and Sequence Information of Tin-Centered
Conjugated Microporous Polymers
Authors: Uwe Heiko Bunz, Andrea Uptmoor, Sven Elbert, Irene
Wacker, Rasmus Schröder, Michael Masterlerz, Jan
Freudenberg, and Ruben Ilyas
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To be cited as: Chem. Eur. J. 10.1002/chem.201704572
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Optical Properties and Sequence Information of Tin-Centered
Conjugated Microporous Polymers
Andrea C. Uptmoor, Ruben Ilyas, Sven M. Elbert, Irene Wacker, Rasmus R. Schröder,[b,c]
[
a]
[a]
[a]
[b,c]
[
a]
[a,d]
and Uwe H. F. Bunz*[a,b]
Michael Mastalerz, Jan Freudenberg
Dedication ((optional))
Abstract: We synthesized conjugated microporous polymers (CMPs)
based on tetrakis(4-ethynylphenyl)stannane and diiodobenzene as
tectons, employing Sonogashira couplings under different conditions.
Through variation of the reaction conditions (catalysts, bases and
solvents), appearance, surface area and emission properties of the
formed CMPs were significantly altered. Wet-chemical, acid-mediated
digestion and analysis of the resulting struts of these otherwise
insoluble networks give insight into the molecular setup.
materials as a direct consequence of the network-forming organic
connectors. An aspect virtually not understood is the fluorescence
of such CMPs. A seminal paper was published by Scherf et al.
who prepared microemulsions of
a
tetraphenylmethane-
diethynylbenzene-based network and demonstrated emission of
the emulsions in water (Scheme 1). [
3]
Introduction
Conjugated microporous polymers (CMPs) containing tetrahedral
building blocks are a class of materials with attractive applications,
including gas separation, catalyst scaffolding or energy storage.[1]
The stability of these materials in combination with their ease of
preparation and functionalization make them enticing, though it
comes at the cost of absolute insolubility and therefore relies on -
in most cases - indirect methods to assign their internal structure.
Useful techniques as IR-, solid-state NMR-spectroscopy, but also
microscopy and gas sorption measurements, assess only bulk
materials’ properties - they do not probe fine details such as
defect structures that must be present in such materials.
Yet, CMPs have been investigated fairly thoroughly and Thomas
et al. have recently emphasized the importance of monomer purity
and reaction conditions, both influencing surface area as well as
appearance of the formed CMPs.[2] Nevertheless, important
questions remain, including the characterization and
rationalization of optical properties of these partially conjugated
Scheme 1. Scherf’s fluorescent CMP microparticles.
They reported that CMP 3 displays green fluorescence
(em,max = 485-510 nm) as dispersion in water. This is surprising,
as the main chromophore in this system is bis(phenylethynyl)-
benzene, with em,max of around 311 nm and shoulders around
[4]
3
60 nm. The authors speculate about the dramatic red shift in
emission and invoke a mix of aggregate formation, but also that
bis(phenylethynyl)benzenes are prone towards red-shifted
emission upon attachment of polar substituents to the
chromophore. Yet, the cause for this dramatic red shift is not fully
understood. Other structures, similar to CMP 3, have been
prepared but their fluorescence was either not mentioned or not
investigated.[5] CMPs with a bis(phenylethynyl)benzene “strut”
connecting tetrahedral carbon, silicon or tin centers should be
colorless and deep-blue emissive. However, most of the reported
materials are yellow, deep beige brown, dark brown or orange or
their color is simply not mentioned. Most are described as non-
fluorescent.[
[
a]
M Sc. A. C. Uptmoor, B. Sc. R. Ilyas, M. Sc. S. M. Elbert, Prof. Dr.
M. Mastalerz, Dr. J. Freudenberg, Prof. Dr. U. H. F. Bunz
Organisch-Chemisches Institut, Ruprecht-Karls-Universität
Heidelberg
6-7]
We work on poly(para-phenyleneethynylene)s (PPEs), having
investigated their optical and structural properties in depth.
[8]
Im Neuenheimer Feld 270, 69120 Heidelberg (Germany)
E-mail: freudenberg@oci.uni-heidelberg.de
uwe.bunz@oci.uni-heidelberg.de
From our experience, the appearance of the PPEs (color,
brilliancy) gives a qualitative idea of the purity of the materials,
which appear either as lemon yellow or bright orange-yellow
solids. Colors such as brown, violet, grey, purplish etc. always
indicated the presence of defects in PPEs. This is probably also
the case for the CMPs with phenyleneethynylene (PE) trimers as
their chromophore.
[
b]
Dr. I. Wacker, Prof. Dr. R. R. Schröder, Prof. Dr. U. H. F. Bunz
Centre for Advanced Materials, Ruprecht-Karls-Universität
Heidelberg
Im Neuenheimer Feld 225, 69120 Heidelberg (Germany)
Dr. I. Wacker, Prof. Dr. R.R. Schröder
CellNetworks, Bioquant, Ruprecht-Karls-Universität Heidelberg
Im Neuenheimer Feld 267, 69120 Heidelberg (Germany)
Dr. J. Freudenberg
[
[
c]
d]
CMPs containing PE units as struts connected by tetrahedral
centers can be digested by chloroacetic acid if a tin atom is the
central unit.[ Insoluble and infusible CMPs are digested into their
building blocks, which then are analyzed by conventional solution
phase NMR and GC-MS to detect defect structures and end
groups. In this contribution, we investigate the effect of different
Innovation Lab GmbH
Speyerer Straße 4, 69115 Heidelberg (Germany)
9]
Supporting information for this article is given via a link at the end of
the document.
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reaction conditions for network formation on composition and
optical properties of digestible tin-centered CMPs 6.
a protocol developed by our group for the synthesis of PPEs
(Table 1, CMP 6h).[9]
Results and Discussion
We prepared the porous polymers 6a-k via Sonogashira coupling
of the tin-based tetrahedral monomer 4 with diiodobenzene 5
(
Scheme 2). Table 1 lists the different reaction conditions and
catalyst systems employed. Synthesis was either based on the
procedure for CMPs by Thomas et al. (Table 1, CMP 6a)[2] or on
Scheme 2. Synthetic procedure to tin-centered CMPs 6.
Table 1: Synthetic conditions, optical properties, nitrogen content, BET surface areas and GCMS yield after wet-chemical digestion of CMPs 6a-k.
Elemental
Analysis
Synthesis
Emission Maximaa
BETb
Digestionc
Reaction
temperature
and time
Solid state
Suspension in THF
(c = 1 mg/mL)
Nitrogen
content
[%]
Ratio organic
linker 11:12
2
CMP
Catalyst
Solvent
Base
λ
max, em
m /g
[nm]
λmax, em [nm]
6
6
6
6
6
a
b
c
d
e
Pd(PPh
3
)
4
(2 mol%)
DMF
DMF
NEt
NEt
NEt
NEt
NEt
3
3
3
3
3
21 h, 100 °C
21 h, 100 °C
21 h, 100 °C
21 h, 100 °C
21 h, 100 °C
524
524
532
539
541
522 (shoulder 460)
520 (shoulder 460)
522, 478
-
-
-
-
-
426
32
7
only 11
6:1
3 4
Pd(PPh ) (0.2 mol%)
Toluene/
DMF 1:1
Pd(PPh
3
)
4
(2 mol%)
(2 mol%)
384:1
62:1
4:1
Pd(PPh
3
)
4
Toluene
Toluene
533
10
753
Pd(PPh
3
)
2
Cl
Cl
2
2
(2 mol%)
(2 mol%)
540
5
29
(shoulder
80)
6
f
Pd(PPh
3
)
2
Toluene
Toluene
Toluene
Piperidine
Piperidine
Piperidine
21 h, 100 °C
3 d, 75 °C
3 d, 75 °C
518, 477
469, 510
-
116
27
6:1
9:1
4
6
g
h
3 2
Pd(PPh ) Cl
2
(0.2 mol%)
(0.2 mol%),
512, 477
470, 503
0.23
3 2 2
Pd(PPh ) Cl
6
462, 503
461, 503
0.55
0.10
25
6
11:1
11:1
CuI (0.4 mol%)
3 2 2
Pd(PPh ) Cl (0.1 mol%),
6
i
Toluene
Piperidine
3 d, 75 °C
511, 473
CuI (0.4 mol%)
5
22
(shoulder
80)
Pd(PPh
3 2 2
) Cl (0.2 mol%),
6
j
THF
Piperidine
Piperidine
3 d, 75 °C
3 d, 75 °C
466, 509
464, 511
0.23
0.73
2
6
10:1
CuI (0.4 mol%)
4
3 2 2
Pd(PPh ) Cl (0.2 mol%),
6k
DMF
522, 471
9:1
CuI (0.4 mol%)
[
a]: Excitation wavelength: λexc = 376 nm. [b] Determined through nitrogen sorption experiments at 77 K. [c] After treatment with chloroacetic acid (20 eq) in
toluene at 90 °C for 20 h.
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6
a
6b
6c
6d
6e
6f
6g
6h
6i
6j
6k
Figure 1: Photographs of the solid polymers (top) and suspensions in THF (bottom, c = 1 mg/mL) under daylight and under UV-light (λ = 365 nm).
Both synthetic procedures were systematically varied to yield
CMPs 6b-e and 6f,g,i-k, which were purified by Soxhlet extraction
from methanol and dried under vacuum. The yields ranged from
and 518 nm in suspensions) and another maximum between
471 nm and 480 nm (461 nm and 477 nm in suspensions).
To compare the structure of the polymers and set it into relation
to the emission properties we synthesized a model compound
consisting of the PE strut that should also be present in the
polymers (Scheme 3). 10 shows an intense blue fluorescence in
the solid state and in solution (see supporting information). While
93% to “112%” which we attribute to encapsulated
palladium/ligand residues rather than unreacted halides (vide
supra).The color of the resulting powders ranges from pale yellow
to dark orange under daylight (Figure 1, top). In general, CMPs
prepared employing PPE conditions (or slightly varied, 6f-k) were
pale yellow in the solid state, whereas the polymers prepared after
Thomas’ protocol were dark orange. All of the CMPs are
fluorescent in the solid state and in suspension of the finely
ground powders in THF. Whereas polymers 6g-k appear similar,
the emission color of 6a-f ranges from greenish to bright yellow in
the solid state, and from blue to yellowish-green in their
suspensions.
Emission spectra reveal two groups of emission types in
dependence of the base employed, reaction time and
temperature (Figure 2). CMPs from triethylamine and/or high
catalyst loading (top) show red shifted emission maxima
compared to those prepared in piperidine (bottom). Catalyst and
solvent choice do not have a great influence on emission
properties but catalyst loading has. The emission maxima for 6a-
e in the solid state do not differ notably, as they are between 524
nm and 541 nm. Noticeably, there are shoulders in the blue
shifted area which are even more distinct when the emission
spectra are recorded in suspensions of THF. If compared to
polymers 6f-k, the shoulders become apparently well-resolved
peaks. There are now two maxima present in the emission
spectra of the solid state - between 503 nm and 529 nm (503 nm
10 exhibits
a well-resolved vibronic finestructure in THF
(λem,max = 407 nm), its emission spectrum is bathochromically
shifted in the solid state (λem,max = 452 nm) and less well-resolved.
Although its maximum is close to those of the CMPs synthesized
from piperidine, fluorescence from the networks is slightly red-
shifted. Comparing spectral features with those received from the
polymers from triethylamine, the red shift becomes even more
apparent (Figure 2). These differences between the emission
properties of the polymers 6a-k and also the model compound 10
can be explained by additional effects arising from the deviant
spatial orientation of the optically active bis(phenylethynyl)-
benzene units within the polymeric structure compared to an
arrangement of single molecules as formed in 10. The formation
of CMPs from tetrahedral monomers could lead to a variety of
possible alignments of the chromophores to each other. Current
investigations in this field confirm this assumption and hint at the
existence of further coupled excitonic states and different decay
channels arising from changes in packing, orientation and
distances concerning the chromophores.[10] Fluorescence lifetime
measurements were conducted for 10, 6b and 6f in the solid state
at their emission maxima (see Supporting Information). In general,
multi-exponential decays were observed, common in thin-films
due to different orientations. However, lifetime depends on the
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Solid state
Suspension in THF
Figure 2: Emission spectra of polymers 6a-e (top) and 6f-k (bottom) in the solid state (left) and in suspensions of THF (right, c = 1 mg/mL) in comparison with the
model compound 10.
of Thomas et al. utilizing a relatively high amount of palladium
catalyst (2 mol%) and triethylamine as base. Pore size distribution
analysis revealed pores of 1.6 nm and 2.8 nm in size, showing a
small mesoporous distribution (see Supporting Information). We
observed a strong solvent effect concerning the surface area
2
when changing from DMF to toluene (6a to 6d, 426 m /g to
2
1
0 m /g). Although there are no other literature known tin-
centered CMPs, our results correspond to earlier reports where
solvent choice influences morphology and porosity of similar
materials.[11,12] Surprisingly, a catalyst change from Pd(PPh
)
to
3 2 2
Pd(PPh ) Cl leads to the highest observed surface area (6d to
3
4
2
2
6
e, 10 m /g to 753 m /g). When piperidine as a base is employed,
2
2
the surface area decreases (6e to 6f, 753 m /g to 116 m /g).
Reducing the catalyst loading to PPE-based conditions produces
materials with very low surface areas (CMP 6g-k). Even though
different solvents were tested, the low catalyst loading (0.2 mol%)
always resulted in a non-porous network (CMP 6b, 6g-k). One
explanation could be that in some cases the pores within the
polymers are too small for interdiffusion of nitrogen. SEM images
were taken exemplarily of 6e, 6f and 6g to reveal differences in
the morphology of the materials (see Supporting Information for
SEM data). For the reasonably porous CMP 6f and non-porous
Scheme 3: Synthesis of model compound 10.
emission maximum for 6b and 6f and is longer for the red-shifted
maximum. Thus, aggregation and rigidification of the
electronically independent struts of the microporous polymers
cannot solely account for the emission but further effects, e.g.
excimers, or defects influence spectral features of the networks.
Porosity was determined by nitrogen sorption measurements at
77K and calculation of the Brunauer-Emmet-Teller (BET) surface
2
2
6
g (surface areas: 116 m /g (6f); 27 m /g (6g)) the sharp-edged
areas of the CMPs. Noticeably, some of the polymers exhibit a
high surface area while others are non-porous (Table 1). The
highest surface areas were achieved for CMPs 6a and 6e (426
2
particles severely vary in size whereas for 6e (753 m /g) the
material forms well-defined spherical conglomerates of similar
size and shape as observed for nanoparticular CMPs previously
2
2
m /g and 753 m /g) - both synthesized according to the protocol
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resulted in less mono-reacted compound 12 and thus a higher
degree of polymerization.
Scheme 4: Conditions for digestion of the polymers 6a-k.
Except for linkers 11, 12 and phenylacetylene no other organic
compounds were detected in the GC-MS traces or during
purification of the digest via column chromatography (see
Supporting Information for all spectra). If one looks into PPEs, the
use of a high catalyst loading is discouraged, as it leads invariably
to the formation of butadiyne defects.[8] This is apparently different
for CMPs, where the growing polymer support suppresses diyne
formation, as no diphenylbutadiyne was detected in the
chromatograms.
Elemental analyses of the networks indicate incorporation of
nitrogen defect structures employing piperidine as a base (PPE
conditions). Nitrogen content ranges from 0.10% to 0.73% for
CMPs 6g-k. Whereas nitrogen is absent using tertiary
triethylamine (bathochromically shifted emission), prolonged
reaction times might lead to Buchwald-Hartwig amination with
secondary amines,[
14]
resulting in CMPs with blue-shifted
Figure 3: SEM images of CMP 6e. Top: overview. Bottom: Detail of the highly
porous preparations of 6e. Clearly visible are the roundish clumped together
spherical species sized around 500 nm.
emission features. Nitrogen containing moieties blocking the
pores within the CMPs could also be the reason for the non-
porosity of the materials. However, our GC-MS analyses of the
digests did not reveal the presence of nitrogen containing organic
compounds, despite neutralization of the formerly acidic reaction
mixtures. The explanation for the observed optical properties and
behavior concerning the porosity remains difficult, but our
approach led to an insight into the inner structure of completely
insoluble networks.
synthesized (Figure 3).[3,5b,13] The structures are fairly uniform and
interestingly enough very dependent upon the synthetic
conditions. To further elucidate the inner structure of the CMPs
and to investigate a correlation between porosity/morphology and
reactivity we cleaved their tin-carbon-bonds by heating
suspensions with chloroacetic acid in toluene overnight
(
Scheme 4). After neutralization with sodium bicarbonate and
washing with water to remove the acid residues or even simple
stirring over solid K CO , we performed GC-MS analyses. Spectra
2
3
Conclusions
show prominent signals of the expected organic linker 11 and
mono-reacted 12 (see Supporting Information for GCMS data). In
some cases, unreacted phenylacetylene was detected in
negligible amounts. The recorded IR-spectra of the polymers
support a low residue of phenylacetylene as they show only very
The CMPs 6a-k with tin as the central connecting atom were
systematically synthesized via Sonogashira-Hagihara coupling,
employing different reaction conditions, catalyst loadings,
solvents etc. The habitus i.e. the color and the emission
characteristics of the CMP 6 is dependent upon the reaction
conditions and selected solvents. All of the - in a formal sense
identical - materials are fluorescent, yet show emission colors and
porosities that are dependent upon the use of the base, the
solvent and the catalyst loading. Typically, triethylamine gives
more red-emitting CMPs, while piperidine leads to bright yellow or
greenish emitting solids. As a consequence, an important and still
unsolved question is the nature of the active chromophore and
fluorophore in the CMPs, as the synthesized model compound 10
with the two triphenylstannyl substituents has a very intense blue-
shifted emission as against any of the investigated CMPs (for
-1
weak signals at 3300 cm , the typical band for alkyne C-H
vibration, compared to the monomer (see Supporting
4
Information). For linker 11 and 12, the GC-MS intensity ratios are
listed in table 1. Our digestion experiments show that from 6a only
organic linker 11 is formed. For 6b, a much smaller catalyst
loading is employed resulting in incomplete polymerization,
evident from the detection of compound 12. Conditions optimized
for the coupling of aromatic iodides with alkynes 6g-k for PPEs
do give higher amounts of the expected trimeric PE-strut 11, but
also some corresponding iodinated dimer is left in the polymeric
structure. In contrast, conditions for preparation of 6c and 6d
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detailed information see Supporting Information). The reason for
the difference could be a weak but persistent 3D conjugation
through the tin centers or the fact that the fluorophores in the CMP
show increased excimeric or aggregative behavior compared to
that of the model compound.
mixture was stirred at 100 °C for 21 h. After collection of the crude product
via filtration, washing with methanol and prestling it was purified via
Soxhlet extraction with methanol over 1 d. The polymer was obtained as a
dark orange powder (200 mg, “112%”). Elemental Analysis (%): calculated
C
78.72,
decomposition: > 370 °C. IR: 휈̃ = 3060, 3010, 2960, 1655, 1583, 1536,
508, 1439, 1387, 1306, 1258, 1189, 1099, 1064, 1012, 830, 810, 759,
712, 658, 642, 589, 522, 457 cm-1
H 3.60, Sn 17.68. Found C 68.22, H 4.73. Thermal
Piperidine-made materials exhibit lower BET surface areas than
their triethylamine analogues. Digestion of the polymers with
chloroacetic acid reveals the fine structure of the CMPs yielding
subtle differences. When using triethylamine as base and high
catalyst loadings, we find higher crosslinking densities as
expressed by the presence of a high amount of PE-trimer strut 11
compared to mono-reacted compound 12 in the digests of our
CMPs; however, it is not clear if there is still Pd and/or solvent
encapsulated – a reasonable assumption, as our materials are in
some cases not porous and the formal yield can exceed 100%.
While even the digestion of the CMPs is not able to solve the
whole puzzle of the structure-property correlation we can identify
the connecting linker within the polymeric network and exclude
the formation of diynes or other defect structures - which gives us
a significant insight into the inner workings of insoluble CMPs
assembled from tetrahedral building blocks.
1
.
CMP 6d: Tetrakis(4-ethynylphenyl)stannane (99.0 mg, 189 μmol, 1.00 eq)
and 1,4-diiodobenzene (125 mg, 379 μmol, 2.00 eq) were dissolved in a
degassed mixture of toluene (900 μL) and NEt
3 3 4
(600 μL). Pd(PPh )
(4.38 mg, 3.79 μmol, 2 mol%) was added and the reaction mixture was
stirred at 100 °C for 21 h. The crude product was collected via filtration and
washed with methanol. After pestling the crude product was purified by
Soxhlet extraction with methanol over 1 d. The polymer was obtained as
dark brown powder (119 mg, 93%). Elemental Analysis (%): calculated C
78.72, H 3.60, Sn 17.68. Found C 72.88, H 4.26. Decomposition: > 370 °C.
IR: 휈̃ = 3285, 3059, 2959, 1909, 1658, 1584, 1536, 1508, 1438, 1388,
1306, 1259, 1190, 1100, 1065, 1013, 949, 832, 812, 754, 719, 693, 659,
-
1
6
38, 592, 524, 466, 456, 426 cm .
CMP 6e: Tetrakis(4-ethynylphenyl)stannane (200 mg, 382 μmol, 1.00 eq)
and 1,4-diiodobenzene (252 mg, 764 μmol, 2.00 eq) were dissolved in a
degassed mixture of toluene (1.80 mL) and NEt
3 3 2 2
(1.20 mL). Pd(PPh ) Cl
(5.37 mg, 7.64 μmol, 2 mol%) was added and the reaction mixture was
stirred at 100 °C for 21 h. The crude product was collected via filtration and
washed with methanol. After pestling, it was purified by Soxhlet extraction
with methanol over 1 d. The polymer was obtained as bright yellow powder
Experimental Section
(
248 mg, 97%). Elemental Analysis (%): calculated C 78.72, H 3.60, Sn
1
3
1
6
7.68. Found C 65.07, H 4.73. Decomposition: > 370 °C. IR: 휈̃ = 3734,
671, 3629, 3061, 2960, 2898, 2360, 2340, 2164, 1735, 1653, 1585, 1539,
508, 1438, 1389, 1372, 1306, 1258, 1190, 1065, 1043, 1007, 863, 809,
Syntheses of the polymers
CMP 6a: Tetrakis(4-ethynylphenyl)stannane (99.0 mg, 189 μmol, 1.00 eq)
and 1,4-diiodobenzene (125 mg, 379 μmol, 2.00 eq) were dissolved in a
-
1
92, 659, 637, 607, 524, 467 cm .
degassed mixture of DMF (900 μL) and NEt
3
1
After pestling, the crude product was purified by Soxhlet extraction with
methanol over 1 d. The polymer was obtained as dark brown powder
3
(600 μL). Pd(PPh
.79 μmol, 2 mol%) was added and the reaction mixture was stirred at
00 °C for 21 h. The precipitate was filtered and washed with methanol.
3 4
) (4.38 mg,
CMP 6f: Tetrakis(4-ethynylphenyl)stannane (200 mg, 382 μmol, 1.00 eq)
and 1,4-diiodobenzene (252 mg, 764 μmol, 2.00 eq) were dissolved in a
degassed mixture of toluene (1.30 mL) and piperidine (1.12 mL).
3 2 2
Pd(PPh ) Cl (5.37 mg, 7.64 μmol, 2 mol%) was added and the reaction
mixture was stirred at 100 °C for 21 h. The crude product was collected via
filtration and washed with methanol. After pestling, it was purified by
Soxhlet extraction with methanol over 1 d. The polymer was obtained as
dark yellow powder (258 mg, “101%”). Elemental Analysis (%): calculated
C 78.72, H 3.60, Sn 17.68. Found C 71.06, H 3.80. Decomposition: >
(
124 mg, 97%). Elemental Analysis (%): calculated C 78.72, H 3.60, Sn
1
3
1
4
7.68. Found C 71.94, H 4.29. Decomposition: > 370 °C. IR: 휈̃ = 3285,
053, 2960, 1913, 1674, 1584, 1536, 1508, 1438, 1387, 1306, 1259, 1188,
090, 1065, 02, 861, 831, 809, 754, 735, 712, 689, 658, 638, 591, 521,
-
1
66, 456, 425 cm .
3
1
5
70 °C. IR: 휈̃ = 3059, 2320, 1905, 1792, 1631, 1582, 1536, 1502, 1389,
301, 1257, 1099, 1062, 1005, 948, 829, 807, 750, 715, 696, 659, 639,
CMP 6b: Tetrakis(4-ethynylphenyl)stannane (150 mg, 287 μmol, 1.00 eq)
and 1,4-diiodobenzene (189 mg, 573 μmol, 2.00 eq) were dissolved in a
-
1
98, 518, 461, 453 cm .
degassed mixture of DMF (1.36 mL) and NEt
3
(910 μL). Pd(PPh
3 4
) (663 μg,
CMP 6g: Tetrakis(4-ethynylphenyl)stannane (150 mg, 287 μmol, 1.00 eq)
and 1,4-diiodobenzene (189 mg, 537 μmol, 2.00 eq) were dissolved in a
degassed mixture of toluene (950 μL) and piperidine (340 μL).
0.2 mol%) was added after prepartation of a stock solution of 6.63 mg
3
catalyst in 5.00 mL degassed NEt and adding 500 μL of it to the reaction
mixture. After stirring for 21 h at 100 °C the crude product was collected
via filtration and washed with methanol and pestled. Soxhlet extraction with
methanol over 1 d yielded the product as a dark yellow powder (198 mg,
3 2 2
Pd(PPh ) Cl (402 μg, 0.574 μmol, 0.2 mol%) was added by preparing a
stock solution of 5 mL degassed piperidine, 4.02 mg palladium catalyst
and adding 500 μL via syringe into the reaction vessel. The reaction
mixture was stirred at 75 °C for 3 d. The crude product was collected via
filtration and washed with methanol. After pestling, it was purified by
Soxhlet extraction with methanol over 1 d. The polymer was obtained as
yellow powder (195 mg, “102%”). Elemental Analysis (%): calculated C
“103%”). Elemental Analysis (%): calculated C 78.72, H 3.60, Sn 17.68.
Found C 69.79, H 3.70. Thermal decomposition: > 370 °C. IR: 휈̃ = 3289,
3
1
5
061, 6007, 2958, 2363, 2341, 2160, 1901, 1582, 1536, 1507, 1494, 1388,
305, 1258, 1189, 1099, 1064, 1013, 1006, 948, 831, 811, 712, 657, 637,
-
1
90, 533, 523, 514, 462, 449 cm .
78.72, H 3.60, Sn 17.68. Found C 70.87, H 3.73, N 0.23. Thermal
decomposition: > 370 °C. IR: 휈̃ = 3298, 3059, 3010, 2961, 1907, 1629,
CMP 6c: Tetrakis(4-ethynylphenyl)stannane (139 mg, 265 μmol, 1.00 eq)
and 1,4-diiodobenzene (175 mg, 530 μmol, 2.00 eq) were dissolved in a
1
582, 1536, 1508, 1387, 1305, 1258, 1185, 1095, 1064, 1006, 948, 831,
-
1
810, 712, 657, 637, 593, 521, 459 cm .
mixture of degassed toluene/DMF (1.25 mL, 1:1 v:v) and NEt
3
(830 μL).
Then Pd(PPh (6.13 mg, 5.30 μmol, 2 mol%) was added and the reaction
3 4
)
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Chemistry - A European Journal
10.1002/chem.201704572
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CMP 6h: Tetrakis(4-ethynylphenyl)stannane (200 mg, 382 μmol, 1.00 eq)
and 1,4-diiodobenzene (252 mg, 764 μmol, 2.00 eq) were dissolved in a
degassed mixture of toluene (1.30 mL) and piperidine (620 μL).
The polymer CMP 6 (30.0 mg, 1.00 eq) was suspended in 3 mL of
anhydrous toluene and chloroacetic acid (84.5 mg, 894 μmol, 20.0 eq) was
added. The reaction mixture was stirred overnight at 90 °C. Afterwards, it
was diluted with dichloromethane (50 mL) and the organic layer was
Pd(PPh
3 2 2
) Cl (537 μg, 764 nmol, 0.2 mol%) and CuI (291 μg, 1.53 μmol,
0.4 mol%) were added by preparing a stock solution of 5 mL degassed
4
washed with deionized water (4 x 50 mL). After drying over MgSO the
piperidine, 5.37 mg palladium catalyst and 2.91 mg CuI and adding 500 μL
via syringe into the reaction vessel. The reaction mixture was stirred at
solvents were evaporated under reduced pressure and the crude product
purified via column chromatography (PE/DCM 20:1) to yield organic linker
11 and 12.
75 °C for 3 d. The crude product was collected via filtration and washed
with methanol. After pestling, it was purified by Soxhlet extraction with
methanol over 1 d. The polymer was obtained as pale yellow powder
For further analytical data see supplementary information.
(
250 mg, 97%). Elemental Analysis (%): calculated C 78.72, H 3.60, Sn
7.68. Found C 71.81, H 3.97, N 0.55. Thermal decomposition: > 370 °C.
IR: 휈̃ = 3289, 3059, 2932, 2853, 1911, 1700, 1665, 1629, 1583, 1535,
1
1
508, 1495, 1441, 1387, 1305, 1258, 1207, 1187, 1099, 1064, 1013, 1006,
-
1
948, 831, 811, 754, 712, 688, 658, 637, 592, 522, 466, 455 cm .
Keywords: conjugated microporous polymers • structure
elucidation • fluorescence • network analysis • defects
CMP 6i: Tetrakis(4-ethynylphenyl)stannane (150 mg, 287 μmol, 1.00 eq)
and 1,4-diiodobenzene (189 mg, 537 μmol, 2.00 eq) were dissolved in a
degassed mixture of toluene (950 μL) and piperidine (340 μL).
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3 2 2
) Cl (201 μg, 287 nmol, 0.1 mol%) and CuI (218 μg, 1.15 μmol,
0.4 mol%) were added by preparing a stock solution of 5 mL degassed
piperidine and 2.01 mg palladium catalyst, 2.18 mg CuI and adding 500 μL
via syringe into the reaction vessel. The reaction mixture was stirred at
75 °C for 3 d. The crude product was collected via filtration and washed
with methanol. After pestling, it was purified by Soxhlet extraction with
methanol over 1 d. The polymer was obtained as pale yellow powder
30, 221–236.
[
2]
M. Trunk, A. Herrmann, H. Bildirir, A. Yassin, J. Schmidt, A. Thomas,
(
1
191 mg, 99%). Elemental Analysis (%): calculated C 78.72, H 3.60, Sn
7.68. Found C 70.83, H 4.05, N 0.10. Thermal decomposition: > 370 °C.
IR: 휈̃ = 3302, 3286, 059, 3006, 2961, 2931, 1907, 1629, 1583, 1536, 1508,
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1
387, 1305, 1259, 1186, 1098, 1064, 1006, 944, 831, 810, 759, 713, 657,
-
1
637, 593, 522, 465 cm .
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a) B. Kim, N. Park, S. M. Lee, H. J. Kim, S. U. Son, Polym. Chem. 2015,
6, 7363-7367. b) H. Ma, H. Ren, X. Zou, S. Meng, F. Sun, G. Zhu, Polym.
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CMP 6j: Tetrakis(4-ethynylphenyl)stannane (150 mg, 287 μmol, 1.00 eq)
and 1,4-diiodobenzene (189 mg, 537 μmol, 2.00 eq) were dissolved in a
degassed mixture of THF (960 μL) and piperidine (340 μL). Pd(PPh
402 μg, 574 nmol, 0.2 mol%) and CuI (218 μg, 1.13 μmol, 0.4 mol%)
were added by preparing a stock solution of 5 mL degassed piperidine,
.02 mg palladium catalyst and 2.18 mg CuI and adding 500 μL via syringe
3
)
2
Cl
2
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a) E. Stöckel, X. Wu, A. Trewin, C. D. Wood, R. Clowes, N. L. Campbell,
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(
4
into the reaction vessel. The reaction mixture was stirred at 75 °C for 3 d.
The crude product was collected via filtration and washed with methanol.
After pestling, it was purified by Soxhlet extraction with methanol over 1 d.
The polymer was obtained as yellow powder (204 mg, “106%”). Elemental
Analysis (%): calculated C 78.72, H 3.60, Sn 17.68. Found C 72.23, H 4.18,
N 0.23. Thermal decomposition: > 370 °C. IR: 휈̃ = 3290, 3056, 2960, 1903,
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1
629, 1583, 1536, 1508, 1442, 1387, 1305, 1258, 1186, 1064, 1006, 863,
-
1
831, 809, 712, 658, 637, 592, 522, 466 cm .
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CMP 6k: Tetrakis(4-ethynylphenyl)stannane (150 mg, 287 μmol, 1.00 eq)
and 1,4-diiodobenzene (189 mg, 537 μmol, 2.00 eq) were dissolved in a
[
10] a) R. Haldar, A. Mazel, R. Joseph, M. Adams, I. A. Howard, B. S.
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degassed mixture of DMF (960 μL) and piperidine (340 μL). Pd(PPh
402 μg, 574 nmol, 0.2 mol%) and CuI (218 μg, 1.13 μmol, 0.4 mol%)
were added by preparing a stock solution of 5 mL degassed piperidine,
.02 mg palladium catalyst and 2.18 mg CuI and adding 500 μL via syringe
3 2 2
) Cl
(
4
into the reaction vessel. The reaction mixture was stirred at 75 °C for 3 d.
The crude product was collected via filtration and washed methanol. After
grinding, it was purified by Soxhlet extraction with methanol over 1 d. The
polymer was obtained as yellow powder (193 mg, 100%). Elemental
Analysis (%): calculated C 78.72, H 3.60, Sn 17.68. Found C 68.98, H 4.14,
N 0.73. Thermal decomposition: > 370 °C. IR: 휈̃ = 3060, 2956, 1905, 1632,
[
11] a) F. Markl, I. Braun, E. Smarsly, U. Lemmer, N. Mechau, G. Hernandez-
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1
8
4
583, 1508, 1495, 1387, 1305, 1258, 1188, 1092, 1064, 1013, 1006, 949,
31, 810, 754, 712, 689, 657, 638, 592, 532, 522, 464, 454, 534, 428, 418,
-
1
09 cm .
General procedure for the cleavage reaction
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Chemistry - A European Journal
10.1002/chem.201704572
FULL PAPER
[
14] a) F. Paul, J. Patt, J. F. Hartwig, J. Am. Chem. Soc. 1994, 116, 5969-
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7901-7902.
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Entry for the Table of Contents
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Andrea C. Uptmoor, Ruben Ilyas, Sven
M. Elbert, Michael Mastalerz, Jan
Freudenberg, and Uwe H. F. Bunz*
((Insert TOC Graphic here; max. width: 11.5 cm; max. height: 2.5 cm))
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Optical Properties and Sequence
Information of Tin-centered
Conjugated Microporous Polymers
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