Visible-Light Photocatalysis of Aerobic Oxidation Reactions Using Carbazolic Conjugated Microporous Polymers

Article abstract of DOI:10.1021/acscatal.6b00443

Carbazolic conjugated microporous polymer (C-CMP) is obtained via straightforward carbazole-based oxidative coupling polymerization. C-CMP exhibits high porosity and a specific surface area of 1137 m² g^-1, and it is thermally stable to 600 °C in nitrogen. C-CMP is shown to be a highly effective heterogeneous photocatalyst for a wide range of reactions, including the oxidative coupling of primary amines, aerobic dehydrogenation of nonactive secondary amine substrates such as pharmaceutically relevant nitrogen heterocycles, and selective oxidation of sulfide using molecular oxygen and visible light. This work highlights the potential of developing photoactive N-containing CMPs as a highly stable, molecularly tunable, reusable, and metal-free visible light photocatalysts for a wide variety of organic transformations.

Full text of DOI:10.1021/acscatal.6b00443

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Article
Visible-light Photocatalysis of Aerobic Oxidation Reactions
Using Carbazolic Conjugated Microporous Polymers
Chenliang Su, Rika Tandiana, Bingbing Tian, Ananya Sengupta, WEI TANG, Jie Su, and Kian Ping Loh
ACS Catal., Just Accepted Manuscript • DOI: 10.1021/acscatal.6b00443 • Publication Date (Web): 26 Apr 2016
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Visibleꢀlight Photocatalysis of Aerobic Oxidation
Reactions Using Carbazolic Conjugated
Microporous Polymers
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Chenliang Sua,b§, Rika Tandianab§, Bingbing Tiana,b, Ananya Senguptaa,b, Wei Tangb, Jie Sub,
Kian Ping Lohb*
a SZUꢀNUS Collaborative Innovation Center for Optoelectronic Science & Technology, Key
Laboratory of Optoelectronic Devices and Systems of Ministry of Education and Guangdong
Province, College of Optoelectronic Engineering, Shenzhen University, Shenzhen 518060, China
b Department of Chemistry, Centre for 2D Advanced Materials, National University of
Singapore, 3 Science Drive 3, 117543, Singapore
Abstract: Carbazolic conjugated microporous polymer (CꢀCMP) is obtained via straightforward
carbazoleꢀbased oxidative coupling polymerization. CꢀCMP exhibits high porosity and a specific
o
surface area of 1137 m2g−1 and it is thermally stable to 600 C in nitrogen. CꢀCMP is shown to
be a highly effective heterogeneous photocatalyst for a wide range of reactions, including the
oxidative coupling of primary amines, aerobic dehydrogenation of nonꢀactive secondary amine
substrates such as pharmaceutically relevant nitrogen heterocycles, and selective oxidation of
sulfide using molecular oxygen and visible light. This work highlights the potential of
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developing photoactive Nꢀcontaining CMPs as a highly stable, molecularly tunable, reusable and
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metalꢀfree visible light photocatalysts for a wide variety of organic transformations.
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Keywords: Visibleꢀlight photocatalysis, conjugated microporous polymers, metal free, selective
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oxidations, heterogeneous catalysis
Introduction
The utilization of solar energy as a clean and renewable energy resource for driving synthetic
transformations has become an important thrust in green chemistry.1 During the last decades,
transitionꢀmetal complexes1a and organic dyes1c which absorb mainly in the visible spectrum had
been widely employed as photoredox catalysts to trigger synthetic transformations. However the
poor stability of the organic dye, the inclusion of precious metal in transitionꢀmetal complexes
and the difficulty to remove and reuse these homogeneous photocatalysts restrict their practical
applications. Metalꢀfree heterogeneous visibleꢀlight photocatalysts that are highly stable, easily
handled, recoverable and reusable are needed to address the aforementioned concerns. Carbon
nitride polymers1d, 2 have been explored for a series of metalꢀfree photocatalytic selective
oxidations such as oxidation of alcohols,2dꢀe amines,2f and crossꢀdehydrogenativeꢀcoupling
reactions.2g Engineering the morphology of carbon nitride polymers to obtain a higher surface
area and porosity, and incorporating organic moieties in the CN frameworks to enhance
functionalities, are effective ways to enhance their catalytic efficiency.2
Conjugated microporous polymer (CMPs),3 a class of πꢀconjugated organic polymers with
photoꢀactive structure, high surface area, permanent nanopores, thermal stability and high
flexibility, provides another type of valuable platform for the design of photoredox catalysts.4
The optoelectronic properties of CMPs can be fineꢀtuned at the molecular level, thus allowing
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flexible design and structureꢀproperty correlation to be investigated.4aꢀc Nitrogen containing πꢀ
conjugated microporous polymers (NꢀCMPs) derived from oxidative polymerization of
triarylamines and their derivatives such as carbazoles have recently emerged as an important
class of photoꢀactive NꢀCMPs.5, 6 The nitrogenꢀcontaining conjugated structure allow the
electron rich NꢀCMPs to be applied as redoxꢀactive materials in a wide variety of optoelectronic
applications such as electric energy storage,5bꢀc light harvesting3a, 6f and optical sensing.6dꢀe
Despite these remarkable advantages, there are scant reports on the use of these NꢀCMPs as a
visibleꢀlight photocatalyst for synthetic transformations,4c in particular there are no reports of
selective aerobic oxidations. In this work, we synthesized carbazolic conjugated microporous
polymer (CꢀCMP)6 and applied it as catalysts for three classes or representation reactions,
namely: visibleꢀlight driven oxidative coupling of primary amines, aerobic dehydrogenation of
nonꢀactive secondary amine substrates and selective oxidation of sulfides under mild condition.
Since CꢀCMP is a metalꢀfree heterogeneous photocatalyst that shows good recyclability and can
be reused efficiently in multiꢀruns, it can be considered as a green catalyst.
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Experimental
Preparation of CꢀCMP:6b A preheated 250 mL flask (with a stirrer bar) was charged with FeCl3
inside the glove box and sealed with rubber stopper before taking out of the glove box. 200 mg
(0.37 mmol) of 1,3,5ꢀtri(9ꢀcarbazolyl)ꢀbenzene (TCB) was dissolved in 60 mL of anhydrous
chloroform and then injected into the flask. The solution was stirred at room temperature for 3
days under argon protection. After that, 100 mL of methanol was added into the reaction mixture
and the solution was stirred for another hour. The precipitate was collected using filtration and
washed with 250 mL methanol. The collected solids were added into a 250 mL flask with 150
mL of 37% HCl and the suspension was stirred for 2 hours. The suspension was then filtered and
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washed with deionized water and methanol. All solids were further purified through Soxhlet
extraction with boiling methanol for 24 hours and then tetrahydrofuran for 48 hours. The
collected polymer was dried and kept in vacuum desiccators.
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Results and discussion
Carbazole derivatives with excellent electronꢀdonating capabilities are good candidates for the
production of photoꢀactive NꢀCMPs as these monomers have been used as photocatalysts in
several UV lightꢀpromoted organic reactions.7 It is wellꢀknown that polymerization of these
carbazole derivatives to produce CꢀCMPs6 could result in enhanced visible light absorption
crossꢀsection because of the extended πꢀconjugation, which probably allows the CꢀCMPs to be
efficient visible light photocatalysts. A commercial available 1,3,5ꢀtri(9ꢀcarbazolyl)ꢀbenzene
(TCB)6b is selected as the candidate monomer to demonstrate our hypothesis. Oxidative coupling
polymerization of TCB was readily performed by using anhydrous FeCl3 in chloroform under
nitrogen protection at room temperature (Figure 1a).6aꢀb To demonstrate the successful formation
of CꢀCMP, extensive characterizations using TGA, UV, FTIR, SEM etc. are performed. After
polymerization, the thermal stability of CꢀCMP is greatly improved as shown in Figure 1b. The
bandgap of the CꢀCMP, as compared to its monomer, is smaller due to the significant increase in
conjugation length. This is supported by the redꢀshift of the absorption spectrum (Figure 1c) to
the visible region. From the FTIR spectrum, most of the fingerprint peaks of the monomer are
retained in its polymer (Figure S1). The BrunauerꢀEmmettꢀTeller (BET) surface areas of TCB
and CꢀCMP are measured to be 2.28 m2g−1, and 1137 m2g−1, with pore volumes of 0.00058
cm3g−1, and 0.68 cm3g−1, respectively (Table S3). The scanning electron microscopy (SEM)
images of CꢀCMP and its monomer are shown in Figure 1dꢀe. TCB forms rodꢀlike crystal with
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lengths of several micrometers. The SEM image of CꢀCMP indicates agglomerated micrometer
particles with highly curved surface. The superior surface area and high pore volumes can be
assigned to the rigid structure of carbazole units, the inherent permanent porosity and the interꢀ
particle porosity between the agglomerated particles.
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Figure 1. a) Oxidative polymerization of TCB monomer catalyzed by FeCl3 to produce CꢀCMP,
which could serve as a photoꢀredox catalyst. b) Thermal gravimetry of CꢀCMP and its monomer
TCB. c) UVꢀvisible absorption spectra of CꢀCMP and its monomer TCB. d) SEM image of TCB
monomer, scale bar 1 ꢁm. e) SEM image of CꢀCMP, scale bar 1 ꢁm.
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We first performed the oxidative coupling of benzylamine to investigate the photocatalytic
effectiveness of CꢀCMP.8 As evident in Figure 2, the conversion rate is negligible in the absence
of the catalyst. Since the monomer TCB only absorbs UV light and the lamp have a UV filter, it
shows no photocatalytic reactivity. In contrast, CꢀCMP shows remarkably enhanced visible light
absorption (> 400 nm), better stability, higher porosity and higher surface area than the monomer
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and allows >99% conversion with 95% selectivity (determined by H NMR). It is clear from
Figure 2 that CꢀCMP provides the best performance among all the tested heterogeneous
photocatalysts including the wellꢀexplored gꢀC3N4, TiO2 as well as other NꢀCMPs (TPAꢀCMP
6a
and TDPABꢀCMP)5c,
prepared from the monomers like triphenylamine (TPA), 1,3,5ꢀ
tris(diphenylamino)benzene (TDPAB) (Table S1ꢀ3). The photoactiveꢀcarbazole units in CꢀCMP
form a rigid conjugated network. CMP also has an open 3D network with much higher porosity
(Table S1ꢀ3) than the other classes of NꢀCMPs. All these factors may contribute to its superior
performance. To avoid the formation of the overꢀoxidized product benzaldehyde (4ꢀ5% as
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determined by H NMR) which occurred when a high intensity lamp was used, a 150 W lamp
was used for the photochemical reaction, in which a selectivity >98% can be attained with a
slightly prolonged reaction time (Table S1).
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Figure 2. Optimization the conditions of photocatalytic oxidative conversion of benzyl amine
into imine: The reaction was carried out by using 1.0 mmol of primary amine, oxygen (1 atm),
a
20 mg of catalyst and 2 mL CH3CN at specified conditions. Conditions: as made CꢀCMP, 300
W, 2 h; b annealed CꢀCMP, 150 W, 4 h.
In this section, substrate scope and synthetic applications are systemically studied. Firstly, a
series of primary amines 1 could be readily oxidized to produce imines 2 in excellent yields
(Table 1). Electron withdrawing group such as ꢀCF3 require a longer time to achieve complete
conversion while electron donating group like –OMe reduces the reaction time. Orthoꢀ and paraꢀ
methyl substituents have little impact on the coupling process but the metaꢀsubstituted methyl
benzylamine increases the rate of reaction and shortens the reaction time. 2ꢀ
thiophenemethylamine, a representative of the heterocyclic amines is well tolerated.
Table 1. Photocatalytic oxidative conversion of primary amines into imines.a
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Entry
Product
t (h)
Conv. (%)b
Yield
(%)c
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X = H (2a)
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>99
>99
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>99
>99
>99
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X = pꢀCl (2b)
X = pꢀMe (2c)
X = oꢀMe (2d)
X = mꢀM (2e)
X= pꢀCF3 (2f)
X= pꢀOMe (2g)
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(2h)
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Unless specified the reaction was carried out by using 1.0 mmol of primary amines, and 20
mg of CꢀCMP and 2 mL CH3CN at RT under visible light (150 W Xe lamp). Determined by
GCꢀMS. c Isolated yields.
b
Next we examine the efficiency of the photocatalytic aerobic dehydrogenation of nonꢀactive
secondary amine substrates. Diꢀbenzyl amine, a representative of the secondary amines is
converted to the corresponding imine in 76% yield (Table 2, entry 1). Selective oxidation of 1, 2,
3, 4ꢀtetrahydroisoquinone furnishes the 3, 4ꢀdihydroisoquinoline in good yield (Table 2, entry 2).
Utilizing this protocol, we successfully demonstrate the efficient transformation of substituted
tetrahydroquinazolines to the corresponding quinazolines, which are important pharmaceuticals
compounds (Table 2, entries 3ꢀ6).
Table 2. Photocatalytic aerobic dehydrogenation of nonꢀactive secondary amine substrates.a
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Entry
Substrate
Product
t (h)
Yield (%)b
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1c
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2d
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R = H
R = H
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R = PhꢀpꢀF
R= PhꢀpꢀNO2
R = PhꢀpꢀF
R= PhꢀpꢀNO2
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a Unless specified the reaction was carried out by using 0.5 mmol of secondary amines, and 20
mg of CꢀCMP and 2 mL CH3CN at RT under visible light (150 W Xe lamp). Isolated yields. c
b
The reaction was carried out by using 1.0 mmol of diphenyl amine, and 20 mg of CꢀCMP and 2
mL CH3CN at 10 C. The reaction was carried out by using 1.0 mmol of 1,2,3,4ꢀtetrahydro
isoquinoline, and 30 mg of CꢀCMP and 2 mL CH3CN at 10 C. GCꢀYield with anisole as the
internal standard.
o
d
o
e
Table 3. Photocatalytic selective oxidation of sulfides.a
Entry
Substrate
Visible
Light (W)
T (h) Conv.
(%)b
Select.
(%)c
Yield
(%)d
1
R1 = Ph
250
300
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>99
93:7
92
R2 = CH3(3a)
R1 = pꢀBrꢀPh
R2 = CH3 (3b)
2
10.5
>99
93:7
95
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R1 = pꢀOMeꢀPh
R2 = CH3 (3c)
R1 = pꢀMeꢀPh
R2 = CH3 (3d)
R1 = Ph
300
300
300
300
4.5
7
>99
>99
>99
>99
95:5
93:7
93:7
93:7
90
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R2 = CH2CH3 (3e)
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(3f)
a Unless specified the reaction was carried out by using 1.0 mmol of sulfides, and 20 mg of Cꢀ
CMP and 2 mL CH3CN at RT under 1 atm of oxygen. b Determined by GCꢀMS. c Determined by
1H NMR. d Total isolated yield of 4 and 5.
Metalꢀfree photocatalysis using CꢀCMP has also been applied to the synthesis of substituted
sulfoxides from sulfides. As summarized in Table 3, CꢀCMP catalyzed conversions furnish the
corresponding sulfoxides with high levels of efficiency and selectivity. Having electron donating
substituent on thioanisole (pꢀmethoxythianisole, entry 3) reduces the reaction time significantly
and furnishes the oxidized products in 90% with good selectivity (95:5). In contrast, having the
electronꢀwithdrawing substituent (pꢀbromothianisole, entry 2) on the substrate takes a much
longer time to reach completion. One advantage of our approach is the mild reaction conditions,
which allows the cyclopropane moiety to be intact, as these can be easily destroyed by harsh
catalysis conditions. We have recycled and reused the CꢀCMP catalyst by simple filtration and
rinsing in acetonitrile. The catalyst maintains its high photocatalytic activity up to the seventh
cycle when applied in the selective oxidation of thioanisole, as shown in Figure 3.
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Figure 3. Recyclability of CꢀCMP in sulfide oxidation reaction. Conditions: room temperature,
oxygen (1 atm), 1.0 mmol PhSMe, 20 mg catalyst, 8 h, 250 W Xe lamp.
A probable reaction mechanism is proposed in Figure 4. First, excited CꢀCMP (CB, ꢀ1.42 V
vs. SCE, see Table S4 and Figure S7ꢀ8) reduces molecular oxygen to give CꢀCMP+ and a
superoxide radical (E
= ꢀ0.86 V vs. SCE). Amines and sulfides are oxidized by CꢀCMP+ to
red
form radical cations and regenerate neutral CꢀCMP in a photoredox cycle. The superoxide
radical then abstracts protons from the activated amine substrate, from which an imine
product/intermediate and hydrogen peroxide are produced. When using primary amines as the
substrates (R = H), imine intermediates or hydrolysed benzaldehydes can further react with the
free amines to furnish the coupling products.8 In the case of the oxidation of sulfides, the
activated substrates are probably nucleophilic attacked by water from the solvent and further
oxidized by superoxide radical to give corresponding sulfoxides (Figure 4a). The ability of Cꢀ
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CMP to mediate electron transfer from electronꢀdonating substrates (amines or sulfides) to
oxygen to generate superoxide radical is confirmed by employing 1,4ꢀ
bis(dimethylamino)benzene as the indicator (Figure 4b). The generation of H2O2 in the
photoredox aerobic oxidation reactions is also captured by using by Horseradish peroxidase
(POD) catalyzed oxidation of N, Nꢀdiethylꢀ1, 4ꢀphenylenediammonium sulfate (DPD) (Figure
4c).
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Figure 4. a) Mechanism of CꢀCMP catalyzed photoredox oxidations; b) UV/Vis absorption
spectra and photograph of the cationic radical species of 1,4ꢀbis(diꢀmethylamino)benzene
generated by CꢀCMP in the presence of visible light and oxygen; c) UV/Vis absorption spectra
of reaction system (benzylamine oxidation) with or without catalyst after adding DPD and POD.
Conclusions
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We have demonstrated that carbazoleꢀbased conjugated microporous polymer (CꢀCMP) shows
superior photocatalytic efficiency compared to many classes of NꢀCMPs, and also gꢀC3N4 and
TiO2. CꢀCMP can be used for the visible light photocatalysed oxidation of primary and
secondary amines, aerobic dehydrogenation of nitrogen heterocycles, and oxidation of sulfides,
all attained with high efficiency. Furthermore, CꢀCMP photocatalyst can be recycled and reused
for multiꢀruns without obvious decrease in catalytic efficiency. The strategy disclosed here will
be helpful for the development of the function of CꢀCMPs. Since the catalytic efficiency of Cꢀ
CMPs, as well as its applicability to other catalytic reactions, can be tuned at a molecular level
by altering the substituents or the backbone structure, it is envisaged that CꢀCMPs will emerge as
powerful photoꢀcatalysts for mediating synthetic transformations.
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Associated content. This material is available free of charge via the Internet at
http://pubs.acs.org.
Supporting Information. The following file is available free of charge on the ACS
Publications website at DOI: xxx. General procedures, synthesis, FTIR spectra, UVꢀVis spectra,
and NMR spectra.
Author information
Corresponding author: chmlohkp@nus.edu.sg;
§These authors contributed equally.
Acknowledgements
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Singapore National Research Foundation through the Singapore–Berkeley Research Initiative
for Sustainable Energy (SinBeRISE) CREATE Program. National Natural Science Foundation of
China (Grant No. 51502174 and 21506126). The Science and Technology Project of Shenzhen
(Grant No. JCYJ20150324141711616, JCYJ20150324141711645) and Natural Science
Foundation of SZU 827ꢀ000059.)
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