A C-Pyrenyl Poly(methylenephosphine): Oxidation "turns On" Blue Photoluminescence in Solution and the Solid State

Article abstract of DOI:10.1021/acs.organomet.6b00880

A C-pyrenyl poly(methylenephosphine) (M_n = 4800, D = 1.56) was synthesized from the anionic polymerization of a P-mesityl phosphaalkene. The phosphine oxide polymer exhibits blue fluorescence in solution (λ_max 379, 400 nm, λ_onse

Full text of DOI:10.1021/acs.organomet.6b00880

Article
pubs.acs.org/Organometallics
A C‑Pyrenyl Poly(methylenephosphine): Oxidation “Turns On” Blue
Photoluminescence in Solution and the Solid State
†
†
‡
†
Benjamin W. Rawe, Christopher M. Brown, Marc R. MacKinnon, Brian O. Patrick,
‡
,†
Graham J. Bodwell, and Derek P. Gates*
†
Department of Chemistry, University of British Columbia, 2036 Main Mall, Vancouver, British Columbia, Canada V6T 1Z1
‡
Department of Chemistry, Memorial University of Newfoundland, St. John’s, Newfoundland and Labrador, Canada A1B 3X7
*
S Supporting Information
ABSTRACT: A C-pyrenyl poly(methylenephosphine) (M =
n
4
800, Đ = 1.56) was synthesized from the anionic polymerization
of a P-mesityl phosphaalkene. The phosphine oxide polymer
exhibits blue fluorescence in solution (λmax 379, 400 nm, λonset
5
60 nm; Φ = 0.05) and blue-green fluorescence in the solid state
at room temperature (λ 460 nm, Φ = 0.07). In contrast,
max
unoxidized polymer displays only a weak emission in solution and
no emission in the solid state. Fluorescence studies of partially
oxidized polymers (50, 75, 83% oxidation) indicate that “turn on”
emission occurs only at very high degrees of oxidation (near
100%). We conclude that even a small number of unoxidized
phosphine moieties within the partially oxidized polymer
intramolecularly quench the fluorescence.
INTRODUCTION
optoelectronic applications from π-conjugated molecular P-
containing compounds.
A particular interest within our group involves investigating
the striking analogy between the polymer chemistry of olefins
and that of phosphaalkenes. In 2003, we reported the addition
■
7
,8
The development of polymers featuring main-group elements
in the backbone is a rapidly growing interdisciplinary area of
1
research. The unique oxidation states and coordination
numbers of heteroatoms in the main chain impart chemical
functionality, semiconducting, optoelectronic, and physical
properties that are often quite different from their organic
counterparts. Specifically, phosphorus-containing π-conjugated
polymers have garnered widespread attention due to the fact
that their electronic properties are dependent on the readily
modifiable chemical environment at phosphorus. Important
classes of π-conjugated phosphorus polymers include (Chart 1)
polymerization of MesPCPh as a route to poly(methylene-
2
phosphines) (PMPs), a new class of chemically functional P-
9
polymers. Living anionic methods of initiation may be
employed to afford homopolymers and block copolymers
10,11
with controlled architectures.
Additionally, the P moieties
within PMPs can be functionalized to give materials that
12,13
undergo self-assembly in block-selective solvents.
Radical-
initiated copolymerization of phosphaalkenes with styrene can
be achieved to access random copolymers that are effective
ligands for Pd-catalyzed Suzuki−Miyaura cross-coupling
2
3
poly(phospholes) (A), poly(arylene phosphines) (B),
4
5
phospha - and diphospha-PPVs (C and D), and poly(p-
6
14
phenylenediethynylenephosphines) (E). The exciting pros-
reactions. Recently, we have shown that PMP copolymers
derived from an enantiomerically pure phosphaalkene and
styrene can be used as chiral macromolecular ligands for
pects for P-containing hybrid organic−inorganic materials are
illustrated by the fact that devices have been fabricated for
15
rhodium(I).
The photophysical properties of phosphaalkenes and
16
Chart 1. General Depiction of the Main Structural Motifs
within π-Conjugated Phosphorus-Containing Polymers
17
PMPs have been explored. We recently reported the synthesis
of a C-naphthyl-substituted PMP that exhibited “turn on”
emission upon oxidation of the phosphorus atoms in the
polymer. Remarkably, other P-functionalized derivatives (e.g.,
Special Issue: Tailoring the Optoelectronic Properties of Organo-
metallic Compounds with Main Group Elements
Received: November 24, 2016
©
XXXX American Chemical Society
A
DOI: 10.1021/acs.organomet.6b00880
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Article
S, BH , and AuCl) were nonemissive. Despite the observed
3
selectivity toward oxygen, a limitation of the aforementioned
systems is that the emission occurs in the UV region and
therefore cannot be seen with the naked eye. For this reason, a
C-pyrenyl PMP was envisaged. We hypothesized that the
incorporation of pyrene units would provide access to a
chemically functional hybrid organic−inorganic material that
emits in the visible region.
Herein, we report a C-pyrenyl PMP that displays blue
fluorescence upon oxidation. Remarkably, strong emission is
only observed upon complete oxidation of the phosphine
moieties. We speculate that there is a communicative effect
where even traces of unoxidized phosphine moieties lead to
long-range intramolecular fluorescence quenching (inverse
amplification of fluorescence).
RESULTS AND DISCUSSION
Monomer Synthesis. Phosphalkene 1 was synthesized by
■
utilizing the well-established phospha-Peterson reaction
1
8
(
Scheme 1). MesP(SiMe3)2 was treated with MeLi (1
Scheme 1. Synthesis of E/Z-1
Figure 1. Molecular structure of Z-1 (thermal ellipsoids are displayed
at the 50% probability level). Hydrogen atoms are omitted for clarity.
phenanthryl) the angles are quite different (Phtrans 20°, Phencis
6
3°) and intermolecular π stacking is observed for the Phen
equiv) and heated to reflux for 2 h to afford MesP(SiMe )Li
17
3
moieties. Inspection of the crystal packing of 1 (Figure 2)
3
1
quantitatively as determined by P NMR spectroscopy. The
dropwise addition of a THF solution of 1-benzoylpyrene to the
phosphide at −78 °C resulted in the quantitative formation of a
3
1
diastereometric mixture of 1 ( P NMR: 252 ppm, 80% (Z-1);
2
42 ppm, 20% (E-1)). Me SiCl was added at −78 °C to quench
3
lithates (e.g., LiOSiMe ). After removal of volatiles in vacuo, Z-
3
1
was recrystallized selectively from toluene or THF to afford a
bright yellow crystalline solid. Like many phosphaalkenes, when
crystals of Z-1 were dissolved in CDCl , an E/Z-1 mixture
3
formed in the presence of ambient light at room temperature
over a few hours. Minimizing exposure to light slows this
19
process considerably.
Crystals suitable for analysis by X-ray crystallography of Z-1
were grown from a solution of hexanes and dichloromethane.
The molecular structure is shown in Figure 1 (see the
Supporting Information for data collection parameters, cell
constants, and refinement details). The PC bond length
Figure 2. Portion of the crystal structure of Z-1 showing
intermolecular packing of pyrene moieties.
(
1.69 Å) is on the longer side of that expected for C-aryl
phosphaalkenes but is typical of P-Mes-bearing phosphaalke-
suggests a considerable intermolecular interaction between
adjacent pyrene substituents. The molecules of 1 adopt a
dimeric structure with the distance between the planes of the
pyrene substituents being consistently ca. 3.6 Å. For
comparison, the distance between planes of Phen substituents
1
9a,20,21
nes.
The angle between the P-Mes and the PC bond (ca. 70°)
2
0
is typical for P-Mes phosphaalkenes (cf. MesPCPh = 71°
2
2
1
or 72° ). Interestingly, the trans-configured phenyl moiety is
only slightly twisted with respect to the PC bond (34°). In
contrast, the angle between the cis-1-pyrenyl group and the P
C bond is far greater (ca. 66°). Previously, it has been suggested
that intermolecular π-stacking of a cis-aryl substituent can
account for large differences in plane angles between the PC
bond and the cis and trans substituents. Specifically, MesP
17
in Z-MesPCPh(Phen) is ca. 3.4 Å. It should also be noted
that π stacking in pyrene and between pyrenyl substituents in a
variety of compounds is well-established within the liter-
22,23
ature.
Polymer Synthesis. The polymer derived from 1 is of
interest for its potentially novel photophysical properties.
CPh has been obtained in two crystallographic forms. One has
Following procedures developed for the anionic polymerization
2
20
10,11
similar plane angles (Phtrans 37°, Ph 43°) and no π stacking,
whereas the other has different plane angles (Ph
of MesPCPh and derivatives,
Monomer 1 was treated
cis
2
21°, Phcis
with 10 mol % n-BuLi in a glovebox at room temperature
(Scheme 2). Upon addition of initiator the reaction mixture
turned dark blue immediately. The reaction mixture was stirred
trans
2
1
59°) and intermolecular dimers are observed via π-stacking of
the cis-Ph. Likewise, for Z-MesPCPh(Phen) (Phen = 9-
B
DOI: 10.1021/acs.organomet.6b00880
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Scheme 2. Synthesis of Poly(methylenephosphine) 2
47 ppm but, analogous to previously reported PMP-oxide
9
,17
polymers, has a narrower line width than 2.
The highly
fluorescent nature of 2·O appears to interfere with the GPC
analysis of 2·O using MALS detection. Thus, molecular weights
were determined by conventional GPC (vs polystyrene
standards). Similar molecular weight estimates for 2·O (M =
n
−1
−1
2
100 g mol ; Đ = 1.4) and 2 (M = 2400 g mol ; Đ = 1.4)
n
were obtained. Presumably, the apparent decrease in molecular
weight for the oxidized polymer results from the increased
polarity of phosphine oxide 2·O, which might lead to a tighter
coil size in solution (vs polystyrene). It should also be noted
that the molecular weight of 2 is underestimated when
polystyrene is used as a standard, which is expected since the
repeating unit for the former is much higher than that of
polystyrene of an equal chain length.
at room temperature for 7 days in a sealed vessel within a
glovebox under an N atmosphere. The reaction progress was
2
monitored by 31P NMR spectroscopy, which revealed the
depletion of the signals corresponding to E/Z-1 (252 and 241
ppm) and their replacement by a broad signal at −11 ppm,
which was assigned to PMP 2. The polymerization was
terminated by the addition of degassed methanol (2 drops),
upon which the reaction mixture turned yellow. The reaction
mixture was added to a vigorously stirred ice-cold hexanes
solution, from which the polymer precipitated as an off-white
solid. The material was purified by two further precipitations
and dried in vacuo (yield 51%).
Photophysical Properties. The absorption spectra (Figure
4
) recorded show that 1, 2, and 2·O have large extinction
Analysis of C-1-pyrenyl-substituted PMP by gel permeation
chromatography featuring a multiangle light scattering detector
(
GPC-MALS) revealed 2 to be a polymer with M = 4800 g
n
−1
mol and Đ = 1.56. The molecular weight is close to the
expected value for the monomer to initiator ratio used
−1
(
M (calcd) = 4400 g mol ). Recently, we reported that the
n
microstructure of the PMP made from the polymerization of
MesPCPh with a radical initiator featured an Ar−CH −P−
2
2
2
4
CHPh linkage. Multinuclear NMR spectroscopy using a 600
2
MHz spectrometer with a cryoprobe was used to investigate the
1
microstructure of 2. H NMR spectroscopic analysis of 2
revealed two broad signals from 5.4 to 9.3 and from 0.5 to 4.0
ppm with two broad shoulders at 5.4−6.5 and 2.6−4.0 ppm
,
which are assigned to the Pyr-CHPh and Mes-CH protons,
2
1
3
respectively, with the aid of HSQC and C-APT experiments
see the Supporting Information). These assignments are in
(
1
Figure 4. Absorption spectra of 1, 2, and 2·O (solvent THF, c = 1.0 ×
good agreement with the H NMR spectra of the model
compounds Bn(Mes)P-CH(Pyr)Ph (see Figure 3a) and
−6
1
0
M in phosphorus).
5
−1
−1
coefficients (ε ≈ 10 M cm ) and contain several maxima
typical for polyaromatics. Each spectrum displays three sets of
overlapping signals (λmax 248, 281, and 351 nm for 2) assigned
to vibronic spacing of the π−π* transition of the pyrene
substituent. The observed spectra are analogous to those of 1-
25
methylpyrene and similar derivatives. In addition to these
three sets of signals, a higher wavelength broad absorption is
observed (ca. 390 nm) for 1 only. This low-energy band has
tentatively been assigned to π−π* transition involving the P
C bond. A DFT calculation (see the Supporting Information)
revealed that the HOMO is primarily π type with contributions
from phosphorus and the pyrene. The LUMO is π* with a
major contribution from the PC moiety and a minor
contribution from pyrene.
1
Figure 3. H NMR spectra of (a) Bn(Mes)P-CH(Pyr)Ph and (b) 2.
2
4
Bn(Mes)P-CHPh2. The obtained NMR spectra for 2 exhibit
similarities to the previously reported C-naphthyl PMP
synthesized by anionic initiation. The mechanism to explain
the microstructure of PMPs synthesized by anion initiation is
the subject of ongoing study within our group and will be
reported separately.
Investigation of the emission properties of 2·O in THF
solution revealed three emission maxima (λmax 379, 389, and
400 nm) and a shoulder (423 nm) tailing into the blue region
(>450 nm; Figure 5). The appearance of the spectrum shares
similarities to those of 1-methylpyrene and other substituted
17
26
derivatives of pyrene, albeit with a lower quantum yield (Φ =
The oxidized polymer 2·O was prepared by the addition of
an aqueous hydrogen peroxide solution (30% w/w) to a
solution of 2 in dichloromethane. The resultant polymer, 2·O,
0.05 for 2·O). These observations potentially reflect the heavy-
27,28
atom quenching effect of the phosphorus atoms.
The phosphine oxide polymer 2·O also exhibits blue
emission in the solid state. In this case, the emission band is
3
1
displays a broad resonance in its P NMR spectra in CDCl at
3
C
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and 83% oxidation are shown in Figure 6. As the degree of
oxidation is increased, an increase in fluorescence is expected. It
Figure 5. Emission and excitation spectra of 2·O in solution (solvent
−6
THF, c = 1.0 × 10 M in phosphorus) and the solid state. Inset (left):
THF solutions of 2 (left) and 2·O (right) under a UV lamp (c ≈ 1
Figure 6. Emission spectra of 2, 2·O, and partially oxidized derivatives
−
6
(
solvent CH Cl , c = 1.0 × 10 M in phosphorus, λex 351 nm).
2 2
mg/mL, λ 365 nm). Inset (right): solid sample of 2·O irradiated with
ex
a UV lamp (λex 365 nm).
was therefore remarkable to observe that the partially oxidized
polymers showed an emission intensity similar to that of
unoxidized 2. By comparison, the fully oxidized 2·O was
substantially more emissive, thereby indicating that “turn on”
emission occurs only at very high degrees of oxidation. The
increase of emission upon oxidation is possibly due to the
absence of photoinduced electron transfer of the phosphorus
much broader, lacks fine structure, and is bathochromically
shifted (λmax 460 nm, Φ = 0.07) from that observed in the
solution spectrum of 2·O. The breadth and wavelength of this
emission band are typical of those observed for pyrene excimers
2
9
in the solid state. Similar behavior has been noted for pyrene-
30
31,32
containing polymers and dendrimers.
3
6
The lifetimes of emission from both solution and solid states
were measured. Each state has three distinct short-lived
fluorescence emissions (τsoln = 3.1, 6.2, 12.3 ns; τsld = 1.2,
lone pair as a quenching mechanism and has been
documented previously for molecular P-containing chromo-
37
phores.
Molecular phosphines bearing pyrene moieties are used
5.7, 25.6 ns). The excitation spectra of 2·O (Figure 5) indicate
38
that both solid- and solution-state emission originates mainly
from the lowest energy set of absorption signals (i.e., λmax 351
nm in the absorption spectrum described above). The other
absorption bands are far less emissive.
extensively for solution-based peroxide sensing applications.
In contrast to polymeric 2, the emission of molecular systems
increases linearly with oxide concentration. In partially oxidized
2·O, there appears to be an unexpected cooperative or
communicative effect where the fluorescence of the oxide
units within a chain is quenched, presumably by phosphines,
until extremely high degrees of oxidation. For comparison, the
fluorescence intensity of a mixture of 2 (0.5 μM) and 2·O (0.5
μM) (i.e., 50% oxidized) was greater than that of partially
oxidized 2·O (50% oxidized, 1.0 μM) and comparable to that of
fully oxidized 2·O (0.5 μM). Furthermore, the same
observations were made with more concentrated solutions of
2 (10 μM), 2·O (10 μM), and a 50:50 mixture (10 μM).
Therefore, we conclude that the amplification of quenching
observed for partially oxidized PMPs is intramolecular (i.e.,
within the chain) rather than intermolecular (i.e., between
chains). Given the proliferation of applications for oxygen
It should be noted that THF solutions of 1 and 2 were far
less emissive than solutions of oxidized 2·O. This phenomenon
can be observed by spectroscopy and also visually by irradiation
with a UV lamp, which reveals a strong blue emission for 2·O
(
Figure 5, inset). Blue emission is quite desirable, since it is one
of the primary colors but is rarely observed for organic
conjugated polymers. For example, a few derivatives of PPV
exhibit blue photoluminescence but require exotic substituents
or bulky groups to limit the extent of π conjugation. It should
be noted that there are examples of conjugated B-containing
polymers that are blue emitting but have limited stability
33
3
4,35
toward air.
Another fascinating property of PMP 2 is its “turn on”
fluorescence when the P centers are oxidized. A series of
experiments were performed to probe the relationship between
the degree of oxidation of the polymer and its emission
properties. Specifically, substoichiometric amounts of hydrogen
peroxide were added to a solution of 2 in order to afford
polymers where the phosphorus centers are partially oxidized.
39
sensors, the potential for sensor applications for these unique
materials based on PMP 2 is of interest.
SUMMARY
■
We have synthesized and polymerized a new phosphaalkene
bearing a C-pyrenyl substituent. The resultant poly-
(methylenephosphine) possesses intriguing photophysical
properties in solution and in the solid state. The solid-state
emission spectrum suggests that the broad emission is due to
pyrene eximer formation. In solution, a weak blue fluorescence
is observed that is greatly enhanced when the phosphorus
3
1
1
P{ H} NMR spectroscopic analysis of each isolated polymer
reveals signals assigned to either phosphine (−11 ppm) or
phosphine oxide (47 ppm) units. The degree of oxidation was
estimated by integration of these signals. The emission spectra
of unoxidized 2, fully oxidized 2·O, and samples with 50%, 75%,
D
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centers are oxidized using H O . Notably, this fluorescence
calculations were performed using the SHELXL-2014 crystallographic
2
2
4
3
software package from Bruker AXS. Compound Z-1 crystallized with
three inequivalent molecules of Z-1 in the asymmetric unit. Additional
crystal data and details of data collection and structure refinement are
given in the Supporting Information. Crystallographic data for Z-1
have been deposited with the Cambridge Structural Database (CCDC
enhancement is only observed upon complete oxidation of the
phosphorus atoms within the chain. It appears as though a
small number of phosphine moieties within a chain intra-
molecularly quench the fluorescence of all the pyrene units in
the chain. To our knowledge, this cooperative or amplified
quenching of fluorescence is quite unusual. Thus, future studies
on these and related phosphorus polymers will investigate their
potential use as novel sensory or switching materials.
1
530414).
Preparation of MesPC(Pyr)(Ph) (1). To a stirred solution at
room temperature of MesP(SiMe ) (1.0 g, 3.4 mmol) dissolved in
3
2
THF (30 mL) was added MeLi (2.1 mL, 3.5 mmol, 1.60 M) in ether.
The reaction mixture was heated under reflux overnight. An aliquot
removed for analysis by 31P spectroscopy revealed a signal resonance
EXPERIMENTAL SECTION
■
at −187 ppm, which was assigned to MesP(SiMe )Li. The reaction
3
Materials and Methods. All manipulations of air- and/or water-
sensitive compounds were performed under a nitrogen atmosphere by
using standard Schlenk or glovebox techniques. Hexanes and
dichloromethane were deoxygenated with nitrogen and dried by
passing through a column containing activated alumina. Tetrahy-
drofuran (THF) was dried over sodium and benzophenone and was
distilled prior to use. Hydrogen peroxide was purchased as a 30%
solution with water from Aldrich and was used as received and titrated
mixture was cooled to −78 °C, after which a solution of 1-
benzoylpyrene (1.05 g, 3.4 mmol) was added dropwise. After 5 min,
the reaction mixture was warmed to room temperature and was stirred
for a further 25 min. An aliquot was taken for 31P NMR spectroscopy
which indicated that an E/Z mixture of phosphaalkene 1 had been
formed quantitatively (252 ppm, Z-1, 80%; 241 ppm, E-1). The
solvent was removed in vacuo, leaving an orange residue. To the
residue was added ether (3 × 30 mL), and the suspension was filtered
and the solvent removed in vacuo. The residue was heated (55 °C)
under reduced pressure for 4 h to remove other volatiles from the
reaction mixture. From the resulting residue, bright yellow crystals
suitable for X-ray diffraction were formed from the slow evaporation of
solvent from a dichloromethane/hexanes mixture. Crystals can also be
grown from a saturated solution of toluene or THF. In all cases Z-1
crystallized preferentially. Yield: 1.15 g, 76%. This compound was pure
as measured by NMR spectroscopy and elemental analysis but was not
of the grade required for living polymerization.
against KMnO . Methyllithium and n-butyllithium were purchased
4
from Aldrich and used as received and titrated by using N-
40
41
benzylbenzamide. MesP(SiMe3)2 was made following literature
procedures. Details for the preparation of 1-benzoylpyrene are given in
the Supporting Information.
1
31
1
13
1
Equipment. H, P{ H}, and C{ H} NMR spectra were
recorded at 25 °C on Bruker Avance 300, 400, and 600 MHz
spectrometers. H PO (85%) was used as an external standard (δ 0 for
3
4
3
1
1
P). H NMR spectra were referenced to residual protonated solvent
signal, and 13C{ H} NMR spectra were referenced to the deuterated
solvent signal. Elemental analyses were performed in the University of
British Columbia Chemistry Microanalysis Facility. Mass spectra were
recorded on a Kratos MS 50 instrument in EI mode (70 eV). Polymer
molecular weights were determined by triple-detection gel permeation
chromatography (GPC-LLS) using an Agilent liquid chromatograph
equipped with an Agilent 1200 series isocratic pump, Agilent 1200
series standard autosampler, Phenomenex Phenogel 5 μm narrow bore
1
31
1
P NMR (C D , 121 MHz): δ 252 (Z-1), 241(E-1). H NMR
6
6
(C D 300 MHz, Z-1 only): 8.2−7.0 (m, 14H, Ar), 6.9−5.8 (br, 2H,
6
6,
1
3
1
Mes-H), 3.0−1.8 (br, 6H, Mes, o-CH ), 1.7 (s, 3H, p-CH ). C{ H}
3
3
1
NMR (CDCl , 101 MHz, Z-1 only): δ 194.0 (d, J = 44 Hz, PC),
3
CP
1
145.1 (d, JCP = 24 Hz), 138.1, 137.9, 135.6 (d, J = 41.5 Hz C -P),
CP
ipso
131.1, 130.7, 130.6, 128.8 (d, JCP = 5.1 Hz), 128.5, 128.1, 127.4, 127.1,
126.8, 126.1, 126.0, 125.9, 125.1, 125.0 124.9 (d), 124.0, 22.3 (br, o-
+
CH ), 20.5 (s, p-CH ). MS (EI, 70 eV): 441, 440 [7, 100; M ]; 426,
3
3
4
+
+
columns (4.6 × 300 mm) 10 Å (5000−500000), 500 Å (1000−
425 [3, 75; M − CH ]; 78, 77 [2, 11; Ph ]. Anal. Calcd for C H P:
3
32 25
3
1
5000), and 10 Å (1000−75000), a Wyatt OptilabrEx differential
C, 87.25; H, 5.72. Found: C, 87.15; H, 5.80.
refractometer (λ 658 nm, 40 °C), a Wyatt TriStar miniDAWN laser
Preparation of Bu(MesP-C(Pyr)(Ph)) H (2). The polymerization
n
light scattering detector (λ 690 nm), and a Wyatt ViscoStar
viscometer. A flow rate of 0.5 mL min was used, and samples
of 1 was performed in a glovebox. To a stirred solution of 1 (1.20 g,
2.7 mmol) in THF was added n-BuLi (85 μL, 5 mol %). Upon the
addition of initiator the reaction mixture turned dark blue immediately.
The reaction mixture was stirred at room temperature for 7 days. At
this time an aliquot was taken for 31P{ H} NMR spectroscopy, which
revealed the replacement of phosphaalkene signals with a very broad
signal centered at −11 ppm, indicative of polymer formation. The
reaction mixture was removed from the glovebox and quenched with
degassed methanol (3 drops), upon which a yellow solution was
formed. The polymer was purified by precipitation from minimal THF
into ice-cold hexanes (3 × 25 mL) and dried in a vacuum oven
overnight. Yield: 0.61 g, 51%. This material was of acceptable purity
−1
−1
were dissolved in THF (ca. 2 mg mL ). The molecular weights were
determined using 100% mass recovery methods from Astra version 5
software. Solution absorption spectra were obtained in THF on a
Varian Cary 5000 UV−vis−near-IR spectrophotometer using a 1 cm
quartz cuvette. Fluorescence and excitation spectra were obtained in
THF on a Horiba Scientific Fluoromax-4 fluorospectrometer using a 1
cm quartz cuvette. The solution-state quantum yield of 2·O was
determined using anthracene as a standard (Φ = 0.27 in ethanol).
Solid-state emission spectra and quantum yield measurements were
recorded on a Photon Technology International QuantaMaster 50
fluorimeter fitted with an integrating sphere and double mono-
chromator and utilizing a 75 W Xe arc lamp as the source. Emission
lifetime data were collected using a Horiba Yvon Fluorocube TCSPC
apparatus. A 370 nm NanoLED source pulsing at a repetition rate of
1
1
for a polymer, with only a few spurious small signals in its H NMR
spectrum. Elemental microanalysis was satisfactory for a polymer
which often is slightly low in carbon due to inefficient combustion.
3
1
1
1
P { H} NMR (CDCl , 121 MHz): δ −11 (br). H NMR (CDCl ,
3
3
5
0 100 kHz was used for excitation. Broad-band emission was
600 MHz): 9.6−7.6 (br, 9H, Ar-H), 7.6−6.2 (br, 7H, Ar-H), 6.2−5.3
(br, 1H, P-CHAr ), 4.2−3.0 (br, 2H Mes-CH ) 2.7−0.3 (br, 6H, Mes-
monitored by a CCD detector at wavelengths >400 nm using a low-
pass filter. Data were fitted using the DAS6 Data Analysis software
package. Computational details are given in the Supporting
Information.
2
2
13
1
CH ). C{ H} NMR (CDCl 202 MHz): δ 149.2−134.7 (br m, Ar-
3
3,
C), 132.8−121.6 (br m, Ar-C 49.9−41.5 (br, P-CH(Ar) ), 36.2−27.4
2
(br, Mes-CH ), 26.9−15.7 (br, Mes o-CH ), 14.6−13.1 (br, Mes p-
2
3
X-ray Crystallographic Studies. All single crystals were
immersed in oil and mounted on glass fibers. Data were collected
on a Bruker X8 APEX II diffractometer with graphite-monochromated
Mo Kα radiation. All structures were solved by direct methods and
subsequent difference Fourier techniques. All non-hydrogen atoms
were refined anisotropically with hydrogen atoms being included in
calculated positions but not refined. All data sets were corrected for
CH ). Assignments were made with the assistance of APT and 2D
3
correlation NMR experiments. GPC (THF, MALS): M = 4800 g
n
−
1
−1
mol , M = 7500 g mol , Đ = 1.56; d /d = 0.276. Anal. Calcd for
w
n
c
C H P: C, 87.25; H, 5.72. Found: C, 84.57; H, 5.63.
32
25
Preparation of Bu(MesP(O)-C(Pyr)(Ph)) H (2·O). To a rapidly
n
stirred solution of 2 (100 mg, 0.23 mmol) in CH Cl (2 mL) was
2
2
added H O (1.5 mL, 30% in H O) dropwise at room temperature.
2
2
2
4
2
31
absorption effects (SADABS), Lorentz, and polarization effects. All
The reaction mixture was stirred vigorously for 1 h, at which time a P
E
DOI: 10.1021/acs.organomet.6b00880
Organometallics XXXX, XXX, XXX−XXX

Organometallics
Article
NMR spectrum of the reaction mixture revealed quantitative
conversion to a new product. An additional 5 mL of CH Cl was
Notes
2
2
The authors declare no competing financial interest.
added, and the organic layer was taken to give an off-white solid, which
was dried in a vacuum oven overnight. Yield: 81 mg, 78%. Purity was
determined as for 2; however, microanalysis was not performed.
ACKNOWLEDGMENTS
■
3
1
1
1
P{ H} NMR (CDCl , 121 MHz): δ 47 (br). H NMR (CDCl ,
D.P.G. and G.J.B. thank the Natural Sciences and Engineering
Research Council of Canada (NSERC) for support of this work
in the form of Discovery and Research Tools and Instruments
Grants. The authors also thank Dr. S. C. Serin for collecting the
crystal structure data for Z-1.
3
3
3
00 MHz): δ 9.6−7.7 (br, 11H, Ar-H), 7.7−6.8 (br, 3H, Ar-H), 6.8−
5
.6 (br, P-CHAr ), 4.0−2.5 (br, 2H, Mes-CH ), 2.5−0.3 (br, 6H, Mes-
2
2
CH ). Assignments are tentative. GPC (vs polystyrene): M = 2100 g
3
n
−
1
mol ; Đ = 1.40.
Preparation of Bn(Mes)PC(Pyr)PhH. A stirred solution of
PhCH Li (11.5 mL, 0.166 M, 1.91 mmol) in THF was prepared
2
ABBREVIATIONS
and cooled to −78 °C. To this solution was added 1 (0.70 g, 1.59
mmol), upon which the reaction mixture turned dark blue. After it was
warmed to room temperature, the reaction mixture was stirred for a
further 1 h. A 31P NMR spectra of the reaction mixture revealed the
consumption of starting material to two new signals at −10 ppm,
assigned to Bn(Mes)P-C(Pyr)PhLi. Degassed water (1 mL) was
added to quench the reaction. The solvent was removed in vacuo to
leave an orange residue. To this residue was added dichloromethane (2
■
Pyr = 1-pyrenyl; PMP = poly(methylenephosphine); Mes =
mesityl
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ASSOCIATED CONTENT
Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.organo-
met.6b00880.
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*
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Additional figures, X-ray crystallographic data, and
computational details (PDF)
Crystallographic data (CIF)
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AUTHOR INFORMATION
Corresponding Author
E-mail for D.P.G.: dgates@chem.ubc.ca.
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■
*
ORCID
Derek P. Gates: 0000-0002-0025-0486
F
DOI: 10.1021/acs.organomet.6b00880
Organometallics XXXX, XXX, XXX−XXX

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DOI: 10.1021/acs.organomet.6b00880
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