Silylium cation initiated sergeants-and-soldiers type chiral amplification of helical aryl isocyanide copolymers
A series of silylium cations [(R 1 R 2 R 3 Si) 2 H] + [B(C 6 F 5 ) 4 ] − ( 1-6 ) ( 1 : R 1 = R 2 = R 3 = Et; 2 : R 1 = R 3 = H, R 2 = Ph; 3 : R 1 = R 3 = Me, R 2 = Ph; 4 : R 1 = R 2 = R 3 = Ph; 5 : R 1 = R 2 = R 3 = i Pr; 6 : R 1 = R 2 = R 3 = OEt) serve as highly efficient metal-free single-compone...
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| Veröffentlicht in: | Polymer chemistry 2020-10, Vol.11 (37), p.617-628 |
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| container_title | Polymer chemistry |
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| creator | Liu, Hao Zhang, Shaowen Yan, Xiangqian Song, Chuang Chen, Jupeng Dong, Yuping Li, Xiaofang |
| description | A series of silylium cations [(R
1
R
2
R
3
Si)
2
H]
+
[B(C
6
F
5
)
4
]
−
(
1-6
) (
1
: R
1
= R
2
= R
3
= Et;
2
: R
1
= R
3
= H, R
2
= Ph;
3
: R
1
= R
3
= Me, R
2
= Ph;
4
: R
1
= R
2
= R
3
= Ph;
5
: R
1
= R
2
= R
3
=
i
Pr;
6
: R
1
= R
2
= R
3
= OEt) serve as highly efficient metal-free single-component cationic initiators for the cationic polymerization and copolymerization of chiral and achiral aryl isocyanides R-N&z.tbd;C (
a-k
) (
a
: R = 2-C
10
H
7
(NI);
b
: R = 4-(COOEt)-C
6
H
4
(EPI);
c
: R = 3-[COO
i
Pr]-C
6
H
4
(IPI);
d
: R = 4-{COO-[(1
S
,2
R
,5
S
)-(2-
i
Pr-5-Me-C
6
H
6
)]}-C
6
H
4
(
d
-IMCI);
e
: R = 4-{COO-[(1
R
,2
S
,5
R
)-(2-
i
Pr-5-Me-C
6
H
6
)]}-C
6
H
4
(
l
-IMCI);
f
: R = 4-[4-(Ph)C&z.dbd;C(Ph)
2
-C
6
H
4
]-C
6
H
4
(ITPB);
g
: R = 4-{COO-(CH
2
)
9
-O-[4-(4-Ph-2-C
9
H
5
N)-C
6
H
4
]}-C
6
H
4
(BNB);
h
: R = 4-{COO-[4-(4-Ph-2-C
9
H
5
N)-C
6
H
4
]}-C
6
H
4
(PQPI);
i
: R = 4-(4-Ph-2-C
9
H
5
N)-C
6
H
4
(IPQ);
j
: R = 4-{COO-(CH
2
)
9
-O-[4-(Ph)C&z.dbd;C(4-N(C
2
H
5
)
2
-C
6
H
4
)
2
-C
6
H
4
]}-C
6
H
4
(PPNI);
k
: R = 4-(N&z.dbd;N-Ph)-C
6
H
4
(IPD)). Nine homopoly(aryl isocyanide)s are prepared, in which optically active poly(
d
) and poly(
e
) exhibit obvious negative and positive Cotton effects at 364 nm and adopt one-handed helical conformations, the poly(
f
) containing tetraphenylethylene (TPE) substituent shows an aggregation-induced emission (AIE) nature, and the poly(
g
) containing 2,4-diphenylquinoline (DPQ) substituent serves as a new fluorescent probe for the detection of Fe
3+
or Fe
2+
ions. By fine-tuning the types of chiral and achiral aryl isocyanides, different degrees of chiral amplification of copolymer helicity can be achieved in the copolymerization of chiral aryl isocyanides
d
and
e
with achiral aryl isocyanides
b
,
c
,
f
, and
k
. Such chiral amplifications of the helical poly(
e
-
co
-
b
)s, poly(
d
/
e
-
co
-
c
)s, poly(
d
/
e
-
co
-
f
)s, and poly(
d
/
e
-
co
-
k
)s with the same helical sense as the corresponding poly(
d
) and poly(
e
) obey the "sergeants-and-soldiers" rule. Determination of reactivity ratios of these copolymerizations demonstrates that the different nonlinear relationship between the intensity of CD signals at 364 nm and the
d
/
l
-IMCI contents of these copolymers depends on the sequence distribution of chiral aryl isocyanide monomers in these copolymers. Based on the
in situ
1
H NMR, FT-IR, and high resolution ESI-MS spectra, a possible cationic (co)polymerization mechanism is proposed.
Silylium cati |
| doi_str_mv | 10.1039/d0py00808g |
| format | Article |
| fullrecord | <record><control><sourceid>proquest_cross</sourceid><recordid>TN_cdi_proquest_journals_2446945031</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>2446945031</sourcerecordid><originalsourceid>FETCH-LOGICAL-c307t-bceb021d1a6ee34796d0ee51650e4c4a7c44e33f6ff94023462322dd3c42e96f3</originalsourceid><addsrcrecordid>eNp9kE1LAzEQhhdRsNRevAsRb8JqvjbbPUrVKhQU1IOnJU0mbUp2sybbw_57Uyv15lxmhnlm3uHNsnOCbwhm1a3G3YDxFE9XR9mIlEWVV5Wgx4e64KfZJMYNTsEIp0yMsu7NusHZbYOU7K1vkW1tb2UPGkUIK5BtH3PZ6jx6py2EiPqhA6TWNkiHZNM5a-zvqjdoDS51aRAGh2z0apCt1Yn3nXdDk_bPshMjXYTJbx5nH48P77OnfPEyf57dLXLFcNnnSwVLTIkmUgAwXlZCY4CCiAIDV1yWinNgzAhjKo4p44IySrVmilOohGHj7Gp_twv-awuxrzd-G9okWVPORcWL5EGirveUCj7GAKbugm3S9zXB9c7U-h6_fv6YOk_w5R4OUR24P9PrTu9kL_5j2Df894Fj</addsrcrecordid><sourcetype>Aggregation Database</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype><pqid>2446945031</pqid></control><display><type>article</type><title>Silylium cation initiated sergeants-and-soldiers type chiral amplification of helical aryl isocyanide copolymers</title><source>Royal Society Of Chemistry Journals</source><creator>Liu, Hao ; Zhang, Shaowen ; Yan, Xiangqian ; Song, Chuang ; Chen, Jupeng ; Dong, Yuping ; Li, Xiaofang</creator><creatorcontrib>Liu, Hao ; Zhang, Shaowen ; Yan, Xiangqian ; Song, Chuang ; Chen, Jupeng ; Dong, Yuping ; Li, Xiaofang</creatorcontrib><description>A series of silylium cations [(R
1
R
2
R
3
Si)
2
H]
+
[B(C
6
F
5
)
4
]
−
(
1-6
) (
1
: R
1
= R
2
= R
3
= Et;
2
: R
1
= R
3
= H, R
2
= Ph;
3
: R
1
= R
3
= Me, R
2
= Ph;
4
: R
1
= R
2
= R
3
= Ph;
5
: R
1
= R
2
= R
3
=
i
Pr;
6
: R
1
= R
2
= R
3
= OEt) serve as highly efficient metal-free single-component cationic initiators for the cationic polymerization and copolymerization of chiral and achiral aryl isocyanides R-N&z.tbd;C (
a-k
) (
a
: R = 2-C
10
H
7
(NI);
b
: R = 4-(COOEt)-C
6
H
4
(EPI);
c
: R = 3-[COO
i
Pr]-C
6
H
4
(IPI);
d
: R = 4-{COO-[(1
S
,2
R
,5
S
)-(2-
i
Pr-5-Me-C
6
H
6
)]}-C
6
H
4
(
d
-IMCI);
e
: R = 4-{COO-[(1
R
,2
S
,5
R
)-(2-
i
Pr-5-Me-C
6
H
6
)]}-C
6
H
4
(
l
-IMCI);
f
: R = 4-[4-(Ph)C&z.dbd;C(Ph)
2
-C
6
H
4
]-C
6
H
4
(ITPB);
g
: R = 4-{COO-(CH
2
)
9
-O-[4-(4-Ph-2-C
9
H
5
N)-C
6
H
4
]}-C
6
H
4
(BNB);
h
: R = 4-{COO-[4-(4-Ph-2-C
9
H
5
N)-C
6
H
4
]}-C
6
H
4
(PQPI);
i
: R = 4-(4-Ph-2-C
9
H
5
N)-C
6
H
4
(IPQ);
j
: R = 4-{COO-(CH
2
)
9
-O-[4-(Ph)C&z.dbd;C(4-N(C
2
H
5
)
2
-C
6
H
4
)
2
-C
6
H
4
]}-C
6
H
4
(PPNI);
k
: R = 4-(N&z.dbd;N-Ph)-C
6
H
4
(IPD)). Nine homopoly(aryl isocyanide)s are prepared, in which optically active poly(
d
) and poly(
e
) exhibit obvious negative and positive Cotton effects at 364 nm and adopt one-handed helical conformations, the poly(
f
) containing tetraphenylethylene (TPE) substituent shows an aggregation-induced emission (AIE) nature, and the poly(
g
) containing 2,4-diphenylquinoline (DPQ) substituent serves as a new fluorescent probe for the detection of Fe
3+
or Fe
2+
ions. By fine-tuning the types of chiral and achiral aryl isocyanides, different degrees of chiral amplification of copolymer helicity can be achieved in the copolymerization of chiral aryl isocyanides
d
and
e
with achiral aryl isocyanides
b
,
c
,
f
, and
k
. Such chiral amplifications of the helical poly(
e
-
co
-
b
)s, poly(
d
/
e
-
co
-
c
)s, poly(
d
/
e
-
co
-
f
)s, and poly(
d
/
e
-
co
-
k
)s with the same helical sense as the corresponding poly(
d
) and poly(
e
) obey the "sergeants-and-soldiers" rule. Determination of reactivity ratios of these copolymerizations demonstrates that the different nonlinear relationship between the intensity of CD signals at 364 nm and the
d
/
l
-IMCI contents of these copolymers depends on the sequence distribution of chiral aryl isocyanide monomers in these copolymers. Based on the
in situ
1
H NMR, FT-IR, and high resolution ESI-MS spectra, a possible cationic (co)polymerization mechanism is proposed.
Silylium cations act as new highly efficient metal-free single-component cationic initiators for the cationic polymerization and copolymerization of chiral or achiral aryl isocyanides, preparing optically active polymers and copolymers obeying "sergeants-and-soldiers" rule.</description><identifier>ISSN: 1759-9954</identifier><identifier>EISSN: 1759-9962</identifier><identifier>DOI: 10.1039/d0py00808g</identifier><language>eng</language><publisher>Cambridge: Royal Society of Chemistry</publisher><subject>Absorption spectra ; Amplification ; Aromatic compounds ; Cationic polymerization ; Copolymerization ; Copolymers ; Fluorescent indicators ; Helicity ; Infrared spectroscopy ; NMR ; Nuclear magnetic resonance ; Optical activity ; Photoluminescence ; Photon correlation spectroscopy ; Polymer chemistry ; Polymerization</subject><ispartof>Polymer chemistry, 2020-10, Vol.11 (37), p.617-628</ispartof><rights>Copyright Royal Society of Chemistry 2020</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c307t-bceb021d1a6ee34796d0ee51650e4c4a7c44e33f6ff94023462322dd3c42e96f3</citedby><cites>FETCH-LOGICAL-c307t-bceb021d1a6ee34796d0ee51650e4c4a7c44e33f6ff94023462322dd3c42e96f3</cites><orcidid>0000-0001-7437-0678 ; 0000-0003-0677-6689 ; 0000-0003-2415-3872</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>314,780,784,27924,27925</link.rule.ids></links><search><creatorcontrib>Liu, Hao</creatorcontrib><creatorcontrib>Zhang, Shaowen</creatorcontrib><creatorcontrib>Yan, Xiangqian</creatorcontrib><creatorcontrib>Song, Chuang</creatorcontrib><creatorcontrib>Chen, Jupeng</creatorcontrib><creatorcontrib>Dong, Yuping</creatorcontrib><creatorcontrib>Li, Xiaofang</creatorcontrib><title>Silylium cation initiated sergeants-and-soldiers type chiral amplification of helical aryl isocyanide copolymers</title><title>Polymer chemistry</title><description>A series of silylium cations [(R
1
R
2
R
3
Si)
2
H]
+
[B(C
6
F
5
)
4
]
−
(
1-6
) (
1
: R
1
= R
2
= R
3
= Et;
2
: R
1
= R
3
= H, R
2
= Ph;
3
: R
1
= R
3
= Me, R
2
= Ph;
4
: R
1
= R
2
= R
3
= Ph;
5
: R
1
= R
2
= R
3
=
i
Pr;
6
: R
1
= R
2
= R
3
= OEt) serve as highly efficient metal-free single-component cationic initiators for the cationic polymerization and copolymerization of chiral and achiral aryl isocyanides R-N&z.tbd;C (
a-k
) (
a
: R = 2-C
10
H
7
(NI);
b
: R = 4-(COOEt)-C
6
H
4
(EPI);
c
: R = 3-[COO
i
Pr]-C
6
H
4
(IPI);
d
: R = 4-{COO-[(1
S
,2
R
,5
S
)-(2-
i
Pr-5-Me-C
6
H
6
)]}-C
6
H
4
(
d
-IMCI);
e
: R = 4-{COO-[(1
R
,2
S
,5
R
)-(2-
i
Pr-5-Me-C
6
H
6
)]}-C
6
H
4
(
l
-IMCI);
f
: R = 4-[4-(Ph)C&z.dbd;C(Ph)
2
-C
6
H
4
]-C
6
H
4
(ITPB);
g
: R = 4-{COO-(CH
2
)
9
-O-[4-(4-Ph-2-C
9
H
5
N)-C
6
H
4
]}-C
6
H
4
(BNB);
h
: R = 4-{COO-[4-(4-Ph-2-C
9
H
5
N)-C
6
H
4
]}-C
6
H
4
(PQPI);
i
: R = 4-(4-Ph-2-C
9
H
5
N)-C
6
H
4
(IPQ);
j
: R = 4-{COO-(CH
2
)
9
-O-[4-(Ph)C&z.dbd;C(4-N(C
2
H
5
)
2
-C
6
H
4
)
2
-C
6
H
4
]}-C
6
H
4
(PPNI);
k
: R = 4-(N&z.dbd;N-Ph)-C
6
H
4
(IPD)). Nine homopoly(aryl isocyanide)s are prepared, in which optically active poly(
d
) and poly(
e
) exhibit obvious negative and positive Cotton effects at 364 nm and adopt one-handed helical conformations, the poly(
f
) containing tetraphenylethylene (TPE) substituent shows an aggregation-induced emission (AIE) nature, and the poly(
g
) containing 2,4-diphenylquinoline (DPQ) substituent serves as a new fluorescent probe for the detection of Fe
3+
or Fe
2+
ions. By fine-tuning the types of chiral and achiral aryl isocyanides, different degrees of chiral amplification of copolymer helicity can be achieved in the copolymerization of chiral aryl isocyanides
d
and
e
with achiral aryl isocyanides
b
,
c
,
f
, and
k
. Such chiral amplifications of the helical poly(
e
-
co
-
b
)s, poly(
d
/
e
-
co
-
c
)s, poly(
d
/
e
-
co
-
f
)s, and poly(
d
/
e
-
co
-
k
)s with the same helical sense as the corresponding poly(
d
) and poly(
e
) obey the "sergeants-and-soldiers" rule. Determination of reactivity ratios of these copolymerizations demonstrates that the different nonlinear relationship between the intensity of CD signals at 364 nm and the
d
/
l
-IMCI contents of these copolymers depends on the sequence distribution of chiral aryl isocyanide monomers in these copolymers. Based on the
in situ
1
H NMR, FT-IR, and high resolution ESI-MS spectra, a possible cationic (co)polymerization mechanism is proposed.
Silylium cations act as new highly efficient metal-free single-component cationic initiators for the cationic polymerization and copolymerization of chiral or achiral aryl isocyanides, preparing optically active polymers and copolymers obeying "sergeants-and-soldiers" rule.</description><subject>Absorption spectra</subject><subject>Amplification</subject><subject>Aromatic compounds</subject><subject>Cationic polymerization</subject><subject>Copolymerization</subject><subject>Copolymers</subject><subject>Fluorescent indicators</subject><subject>Helicity</subject><subject>Infrared spectroscopy</subject><subject>NMR</subject><subject>Nuclear magnetic resonance</subject><subject>Optical activity</subject><subject>Photoluminescence</subject><subject>Photon correlation spectroscopy</subject><subject>Polymer chemistry</subject><subject>Polymerization</subject><issn>1759-9954</issn><issn>1759-9962</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2020</creationdate><recordtype>article</recordtype><recordid>eNp9kE1LAzEQhhdRsNRevAsRb8JqvjbbPUrVKhQU1IOnJU0mbUp2sybbw_57Uyv15lxmhnlm3uHNsnOCbwhm1a3G3YDxFE9XR9mIlEWVV5Wgx4e64KfZJMYNTsEIp0yMsu7NusHZbYOU7K1vkW1tb2UPGkUIK5BtH3PZ6jx6py2EiPqhA6TWNkiHZNM5a-zvqjdoDS51aRAGh2z0apCt1Yn3nXdDk_bPshMjXYTJbx5nH48P77OnfPEyf57dLXLFcNnnSwVLTIkmUgAwXlZCY4CCiAIDV1yWinNgzAhjKo4p44IySrVmilOohGHj7Gp_twv-awuxrzd-G9okWVPORcWL5EGirveUCj7GAKbugm3S9zXB9c7U-h6_fv6YOk_w5R4OUR24P9PrTu9kL_5j2Df894Fj</recordid><startdate>20201007</startdate><enddate>20201007</enddate><creator>Liu, Hao</creator><creator>Zhang, Shaowen</creator><creator>Yan, Xiangqian</creator><creator>Song, Chuang</creator><creator>Chen, Jupeng</creator><creator>Dong, Yuping</creator><creator>Li, Xiaofang</creator><general>Royal Society of Chemistry</general><scope>AAYXX</scope><scope>CITATION</scope><scope>7SR</scope><scope>8FD</scope><scope>JG9</scope><orcidid>https://orcid.org/0000-0001-7437-0678</orcidid><orcidid>https://orcid.org/0000-0003-0677-6689</orcidid><orcidid>https://orcid.org/0000-0003-2415-3872</orcidid></search><sort><creationdate>20201007</creationdate><title>Silylium cation initiated sergeants-and-soldiers type chiral amplification of helical aryl isocyanide copolymers</title><author>Liu, Hao ; Zhang, Shaowen ; Yan, Xiangqian ; Song, Chuang ; Chen, Jupeng ; Dong, Yuping ; Li, Xiaofang</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c307t-bceb021d1a6ee34796d0ee51650e4c4a7c44e33f6ff94023462322dd3c42e96f3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2020</creationdate><topic>Absorption spectra</topic><topic>Amplification</topic><topic>Aromatic compounds</topic><topic>Cationic polymerization</topic><topic>Copolymerization</topic><topic>Copolymers</topic><topic>Fluorescent indicators</topic><topic>Helicity</topic><topic>Infrared spectroscopy</topic><topic>NMR</topic><topic>Nuclear magnetic resonance</topic><topic>Optical activity</topic><topic>Photoluminescence</topic><topic>Photon correlation spectroscopy</topic><topic>Polymer chemistry</topic><topic>Polymerization</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Liu, Hao</creatorcontrib><creatorcontrib>Zhang, Shaowen</creatorcontrib><creatorcontrib>Yan, Xiangqian</creatorcontrib><creatorcontrib>Song, Chuang</creatorcontrib><creatorcontrib>Chen, Jupeng</creatorcontrib><creatorcontrib>Dong, Yuping</creatorcontrib><creatorcontrib>Li, Xiaofang</creatorcontrib><collection>CrossRef</collection><collection>Engineered Materials Abstracts</collection><collection>Technology Research Database</collection><collection>Materials Research Database</collection><jtitle>Polymer chemistry</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Liu, Hao</au><au>Zhang, Shaowen</au><au>Yan, Xiangqian</au><au>Song, Chuang</au><au>Chen, Jupeng</au><au>Dong, Yuping</au><au>Li, Xiaofang</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Silylium cation initiated sergeants-and-soldiers type chiral amplification of helical aryl isocyanide copolymers</atitle><jtitle>Polymer chemistry</jtitle><date>2020-10-07</date><risdate>2020</risdate><volume>11</volume><issue>37</issue><spage>617</spage><epage>628</epage><pages>617-628</pages><issn>1759-9954</issn><eissn>1759-9962</eissn><abstract>A series of silylium cations [(R
1
R
2
R
3
Si)
2
H]
+
[B(C
6
F
5
)
4
]
−
(
1-6
) (
1
: R
1
= R
2
= R
3
= Et;
2
: R
1
= R
3
= H, R
2
= Ph;
3
: R
1
= R
3
= Me, R
2
= Ph;
4
: R
1
= R
2
= R
3
= Ph;
5
: R
1
= R
2
= R
3
=
i
Pr;
6
: R
1
= R
2
= R
3
= OEt) serve as highly efficient metal-free single-component cationic initiators for the cationic polymerization and copolymerization of chiral and achiral aryl isocyanides R-N&z.tbd;C (
a-k
) (
a
: R = 2-C
10
H
7
(NI);
b
: R = 4-(COOEt)-C
6
H
4
(EPI);
c
: R = 3-[COO
i
Pr]-C
6
H
4
(IPI);
d
: R = 4-{COO-[(1
S
,2
R
,5
S
)-(2-
i
Pr-5-Me-C
6
H
6
)]}-C
6
H
4
(
d
-IMCI);
e
: R = 4-{COO-[(1
R
,2
S
,5
R
)-(2-
i
Pr-5-Me-C
6
H
6
)]}-C
6
H
4
(
l
-IMCI);
f
: R = 4-[4-(Ph)C&z.dbd;C(Ph)
2
-C
6
H
4
]-C
6
H
4
(ITPB);
g
: R = 4-{COO-(CH
2
)
9
-O-[4-(4-Ph-2-C
9
H
5
N)-C
6
H
4
]}-C
6
H
4
(BNB);
h
: R = 4-{COO-[4-(4-Ph-2-C
9
H
5
N)-C
6
H
4
]}-C
6
H
4
(PQPI);
i
: R = 4-(4-Ph-2-C
9
H
5
N)-C
6
H
4
(IPQ);
j
: R = 4-{COO-(CH
2
)
9
-O-[4-(Ph)C&z.dbd;C(4-N(C
2
H
5
)
2
-C
6
H
4
)
2
-C
6
H
4
]}-C
6
H
4
(PPNI);
k
: R = 4-(N&z.dbd;N-Ph)-C
6
H
4
(IPD)). Nine homopoly(aryl isocyanide)s are prepared, in which optically active poly(
d
) and poly(
e
) exhibit obvious negative and positive Cotton effects at 364 nm and adopt one-handed helical conformations, the poly(
f
) containing tetraphenylethylene (TPE) substituent shows an aggregation-induced emission (AIE) nature, and the poly(
g
) containing 2,4-diphenylquinoline (DPQ) substituent serves as a new fluorescent probe for the detection of Fe
3+
or Fe
2+
ions. By fine-tuning the types of chiral and achiral aryl isocyanides, different degrees of chiral amplification of copolymer helicity can be achieved in the copolymerization of chiral aryl isocyanides
d
and
e
with achiral aryl isocyanides
b
,
c
,
f
, and
k
. Such chiral amplifications of the helical poly(
e
-
co
-
b
)s, poly(
d
/
e
-
co
-
c
)s, poly(
d
/
e
-
co
-
f
)s, and poly(
d
/
e
-
co
-
k
)s with the same helical sense as the corresponding poly(
d
) and poly(
e
) obey the "sergeants-and-soldiers" rule. Determination of reactivity ratios of these copolymerizations demonstrates that the different nonlinear relationship between the intensity of CD signals at 364 nm and the
d
/
l
-IMCI contents of these copolymers depends on the sequence distribution of chiral aryl isocyanide monomers in these copolymers. Based on the
in situ
1
H NMR, FT-IR, and high resolution ESI-MS spectra, a possible cationic (co)polymerization mechanism is proposed.
Silylium cations act as new highly efficient metal-free single-component cationic initiators for the cationic polymerization and copolymerization of chiral or achiral aryl isocyanides, preparing optically active polymers and copolymers obeying "sergeants-and-soldiers" rule.</abstract><cop>Cambridge</cop><pub>Royal Society of Chemistry</pub><doi>10.1039/d0py00808g</doi><tpages>12</tpages><orcidid>https://orcid.org/0000-0001-7437-0678</orcidid><orcidid>https://orcid.org/0000-0003-0677-6689</orcidid><orcidid>https://orcid.org/0000-0003-2415-3872</orcidid></addata></record> |
| fulltext | fulltext |
| identifier | ISSN: 1759-9954 |
| ispartof | Polymer chemistry, 2020-10, Vol.11 (37), p.617-628 |
| issn | 1759-9954 1759-9962 |
| language | eng |
| recordid | cdi_proquest_journals_2446945031 |
| source | Royal Society Of Chemistry Journals |
| subjects | Absorption spectra Amplification Aromatic compounds Cationic polymerization Copolymerization Copolymers Fluorescent indicators Helicity Infrared spectroscopy NMR Nuclear magnetic resonance Optical activity Photoluminescence Photon correlation spectroscopy Polymer chemistry Polymerization |
| title | Silylium cation initiated sergeants-and-soldiers type chiral amplification of helical aryl isocyanide copolymers |
| url | https://sfx.bib-bvb.de/sfx_tum?ctx_ver=Z39.88-2004&ctx_enc=info:ofi/enc:UTF-8&ctx_tim=2024-12-26T05%3A25%3A00IST&url_ver=Z39.88-2004&url_ctx_fmt=infofi/fmt:kev:mtx:ctx&rfr_id=info:sid/primo.exlibrisgroup.com:primo3-Article-proquest_cross&rft_val_fmt=info:ofi/fmt:kev:mtx:journal&rft.genre=article&rft.atitle=Silylium%20cation%20initiated%20sergeants-and-soldiers%20type%20chiral%20amplification%20of%20helical%20aryl%20isocyanide%20copolymers&rft.jtitle=Polymer%20chemistry&rft.au=Liu,%20Hao&rft.date=2020-10-07&rft.volume=11&rft.issue=37&rft.spage=617&rft.epage=628&rft.pages=617-628&rft.issn=1759-9954&rft.eissn=1759-9962&rft_id=info:doi/10.1039/d0py00808g&rft_dat=%3Cproquest_cross%3E2446945031%3C/proquest_cross%3E%3Curl%3E%3C/url%3E&disable_directlink=true&sfx.directlink=off&sfx.report_link=0&rft_id=info:oai/&rft_pqid=2446945031&rft_id=info:pmid/&rfr_iscdi=true |