Phosphorus–nitrogen compounds: part 75—design, synthesis, stereogenic and conformational properties of chiral dispiro(N/N)cyclotriphosphazenes: structural analysis and photophysical and bioactivity studies
Multiheterocyclic inorganic–organic hybrid phosphazenes have robust inorganic ring systems with the stabilities of the phosphorus nitrogen skeleton and many different substituents bonded to the P atoms. In present study, unsymmetrical dispirocyclotriphosphazenes were prepared due to their potential...
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| creator | Cemaloğlu, Reşit Asmafiliz, Nuran Kılıç, Zeynel Topaloğlu Aksoy, Burcu Sabah, Büşra Nur Açık, Leyla Hökelek, Tuncer |
| description | Multiheterocyclic inorganic–organic hybrid phosphazenes have robust inorganic ring systems with the stabilities of the phosphorus nitrogen skeleton and many different substituents bonded to the P atoms. In present study, unsymmetrical dispirocyclotriphosphazenes were prepared due to their potential to depict steric hindrance and electronic rearrangement in creating permanent chirality for certain conformational and configurational isomers. These isomers may have an effect on DNA bindings and activitiy against selected fungi and bacteria, remarkably. Herein, tetrachlorocyclotriphosphazenes (
1
and
2
) were reacted with 9-ethyl-N-methyl-3-carbazolyl-1,2-diaminoethane (
3
), 9-ethyl-N-ethyl-3-carbazolyl-1,2-diaminoethane (
4
) and 9-ethyl-N-methyl-3-carbazolyl-1,3-diaminopropane (
5
) to give the new unsymmetrical cis/trans-dispirocyclotriphosphazenes, [(ClBz/BzSpiro-6)R
1
(N
3
P
3
)(CzSpiro-n)R
2
]Cl
2
(Cz: Carbazolyl; R
1
:Me R
2
:Me or Et; n = 5 or 6; trans
6a
–
11a
and cis
6b
–
11b
). Characterizations, chiralities, and photophysical and biological properties of the new compounds were examined. The molecular and crystal structures of cis-
6b
, cis-
7b
, trans-
9a
, cis-
9b
, trans-
10a
and cis-
10b
were determined by single crystal X-ray crystallography. The chiralities of these compounds with unsymmetrical spiro-architectures were confirmed by X-ray crystallography. These results were further proven by
31
P NMR data recorded with the addition of a chiral solvent (CSA). Additionally, circular dichroism (CD) spectra also supported the results. Photophysical measurements indicate that these compounds show emission with lifetimes of approximately 5.6–5.9 ns. In addition, the bioactivities of some isomers were found to be different and quite high against some bacterial and yeast strains. Trans-
8a
was very active against
B. cereus
(MBC = 78.1 µM), while cis-
6b
, trans-
9a
and cis-
9b
were very active against the pathogenic yeast
C. albicans
(MFC = 156.3 µM).
Graphical abstract |
| doi_str_mv | 10.1007/s11164-024-05285-7 |
| format | Article |
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1
and
2
) were reacted with 9-ethyl-N-methyl-3-carbazolyl-1,2-diaminoethane (
3
), 9-ethyl-N-ethyl-3-carbazolyl-1,2-diaminoethane (
4
) and 9-ethyl-N-methyl-3-carbazolyl-1,3-diaminopropane (
5
) to give the new unsymmetrical cis/trans-dispirocyclotriphosphazenes, [(ClBz/BzSpiro-6)R
1
(N
3
P
3
)(CzSpiro-n)R
2
]Cl
2
(Cz: Carbazolyl; R
1
:Me R
2
:Me or Et; n = 5 or 6; trans
6a
–
11a
and cis
6b
–
11b
). Characterizations, chiralities, and photophysical and biological properties of the new compounds were examined. The molecular and crystal structures of cis-
6b
, cis-
7b
, trans-
9a
, cis-
9b
, trans-
10a
and cis-
10b
were determined by single crystal X-ray crystallography. The chiralities of these compounds with unsymmetrical spiro-architectures were confirmed by X-ray crystallography. These results were further proven by
31
P NMR data recorded with the addition of a chiral solvent (CSA). Additionally, circular dichroism (CD) spectra also supported the results. Photophysical measurements indicate that these compounds show emission with lifetimes of approximately 5.6–5.9 ns. In addition, the bioactivities of some isomers were found to be different and quite high against some bacterial and yeast strains. Trans-
8a
was very active against
B. cereus
(MBC = 78.1 µM), while cis-
6b
, trans-
9a
and cis-
9b
were very active against the pathogenic yeast
C. albicans
(MFC = 156.3 µM).
Graphical abstract</description><identifier>ISSN: 0922-6168</identifier><identifier>EISSN: 1568-5675</identifier><identifier>DOI: 10.1007/s11164-024-05285-7</identifier><language>eng</language><publisher>Dordrecht: Springer Netherlands</publisher><subject>Atomic properties ; Bacteria ; Biological activity ; Biological properties ; Catalysis ; Chemistry ; Chemistry and Materials Science ; Chirality ; Crystallography ; Dichroism ; Inorganic Chemistry ; Isomers ; Nitrogen compounds ; NMR ; Nuclear magnetic resonance ; Phosphorus ; Physical Chemistry ; Single crystals ; Steric hindrance ; Structural analysis ; Yeast</subject><ispartof>Research on chemical intermediates, 2024, Vol.50 (6), p.2603-2628</ispartof><rights>The Author(s) 2024</rights><rights>The Author(s) 2024. This work is published under http://creativecommons.org/licenses/by/4.0/ (the “License”). Notwithstanding the ProQuest Terms and Conditions, you may use this content in accordance with the terms of the License.</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><cites>FETCH-LOGICAL-c314t-c3d468eb2e161dfe56e961139df4fa9730d8fffe24c11387076ab8c337e4827c3</cites><orcidid>0000-0002-2802-0754 ; 0000-0002-8602-4382 ; 0000-0003-1061-8122 ; 0000-0002-9335-4101 ; 0000-0003-1678-843X ; 0000-0001-5380-692X ; 0000-0002-3672-8429</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://link.springer.com/content/pdf/10.1007/s11164-024-05285-7$$EPDF$$P50$$Gspringer$$Hfree_for_read</linktopdf><linktohtml>$$Uhttps://link.springer.com/10.1007/s11164-024-05285-7$$EHTML$$P50$$Gspringer$$Hfree_for_read</linktohtml><link.rule.ids>314,776,780,27901,27902,41464,42533,51294</link.rule.ids></links><search><creatorcontrib>Cemaloğlu, Reşit</creatorcontrib><creatorcontrib>Asmafiliz, Nuran</creatorcontrib><creatorcontrib>Kılıç, Zeynel</creatorcontrib><creatorcontrib>Topaloğlu Aksoy, Burcu</creatorcontrib><creatorcontrib>Sabah, Büşra Nur</creatorcontrib><creatorcontrib>Açık, Leyla</creatorcontrib><creatorcontrib>Hökelek, Tuncer</creatorcontrib><title>Phosphorus–nitrogen compounds: part 75—design, synthesis, stereogenic and conformational properties of chiral dispiro(N/N)cyclotriphosphazenes: structural analysis and photophysical and bioactivity studies</title><title>Research on chemical intermediates</title><addtitle>Res Chem Intermed</addtitle><description>Multiheterocyclic inorganic–organic hybrid phosphazenes have robust inorganic ring systems with the stabilities of the phosphorus nitrogen skeleton and many different substituents bonded to the P atoms. In present study, unsymmetrical dispirocyclotriphosphazenes were prepared due to their potential to depict steric hindrance and electronic rearrangement in creating permanent chirality for certain conformational and configurational isomers. These isomers may have an effect on DNA bindings and activitiy against selected fungi and bacteria, remarkably. Herein, tetrachlorocyclotriphosphazenes (
1
and
2
) were reacted with 9-ethyl-N-methyl-3-carbazolyl-1,2-diaminoethane (
3
), 9-ethyl-N-ethyl-3-carbazolyl-1,2-diaminoethane (
4
) and 9-ethyl-N-methyl-3-carbazolyl-1,3-diaminopropane (
5
) to give the new unsymmetrical cis/trans-dispirocyclotriphosphazenes, [(ClBz/BzSpiro-6)R
1
(N
3
P
3
)(CzSpiro-n)R
2
]Cl
2
(Cz: Carbazolyl; R
1
:Me R
2
:Me or Et; n = 5 or 6; trans
6a
–
11a
and cis
6b
–
11b
). Characterizations, chiralities, and photophysical and biological properties of the new compounds were examined. The molecular and crystal structures of cis-
6b
, cis-
7b
, trans-
9a
, cis-
9b
, trans-
10a
and cis-
10b
were determined by single crystal X-ray crystallography. The chiralities of these compounds with unsymmetrical spiro-architectures were confirmed by X-ray crystallography. These results were further proven by
31
P NMR data recorded with the addition of a chiral solvent (CSA). Additionally, circular dichroism (CD) spectra also supported the results. Photophysical measurements indicate that these compounds show emission with lifetimes of approximately 5.6–5.9 ns. In addition, the bioactivities of some isomers were found to be different and quite high against some bacterial and yeast strains. Trans-
8a
was very active against
B. cereus
(MBC = 78.1 µM), while cis-
6b
, trans-
9a
and cis-
9b
were very active against the pathogenic yeast
C. albicans
(MFC = 156.3 µM).
Graphical abstract</description><subject>Atomic properties</subject><subject>Bacteria</subject><subject>Biological activity</subject><subject>Biological properties</subject><subject>Catalysis</subject><subject>Chemistry</subject><subject>Chemistry and Materials Science</subject><subject>Chirality</subject><subject>Crystallography</subject><subject>Dichroism</subject><subject>Inorganic Chemistry</subject><subject>Isomers</subject><subject>Nitrogen compounds</subject><subject>NMR</subject><subject>Nuclear magnetic resonance</subject><subject>Phosphorus</subject><subject>Physical Chemistry</subject><subject>Single crystals</subject><subject>Steric hindrance</subject><subject>Structural analysis</subject><subject>Yeast</subject><issn>0922-6168</issn><issn>1568-5675</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2024</creationdate><recordtype>article</recordtype><sourceid>C6C</sourceid><recordid>eNp9UcuOFCEUrRhNbEd_wBWJG00sh0cV0O7MxFcyGV3omtA8uph0AwJlUq7mH5wfm1-YL_F2t4k7F8Dlch6XnK57TvAbgrE4r4QQPvSYwhqpHHvxoFuRkct-5GJ82K3wmtKeEy4fd09qvcaYjFLiVXf3dUo1T6nM9f7mdwytpK2LyKR9TnO09S3KujQkxvubW-tq2MbXqC6xTVBXKJsr7sAIBulogRd9KnvdQop6h3JJ2ZUWXEXJIzOFAk0bag4lvbw6v3plFrNLrYR8nEL_ctGBZW1lNm0-gDXILGB1VAdUS3mCuzk-WbQJSZsWfoa2AGu24PS0e-T1rrpnf8-z7vuH998uPvWXXz5-vnh32RtGhga7Hbh0G-oIJ9a7kbs1J4StrR-8XguGrfTeOzoY6EqBBdcbaRgTbpBUGHbWvTjpwid_zK42dZ3mAuNWxTCnXDImCaDoCWVKqrU4r3IJe10WRbA6RKdO0SmITh2jUwJI7ESqAI5bV_5J_4f1B2Kmpa8</recordid><startdate>2024</startdate><enddate>2024</enddate><creator>Cemaloğlu, Reşit</creator><creator>Asmafiliz, Nuran</creator><creator>Kılıç, Zeynel</creator><creator>Topaloğlu Aksoy, Burcu</creator><creator>Sabah, Büşra Nur</creator><creator>Açık, Leyla</creator><creator>Hökelek, Tuncer</creator><general>Springer Netherlands</general><general>Springer Nature B.V</general><scope>C6C</scope><scope>AAYXX</scope><scope>CITATION</scope><orcidid>https://orcid.org/0000-0002-2802-0754</orcidid><orcidid>https://orcid.org/0000-0002-8602-4382</orcidid><orcidid>https://orcid.org/0000-0003-1061-8122</orcidid><orcidid>https://orcid.org/0000-0002-9335-4101</orcidid><orcidid>https://orcid.org/0000-0003-1678-843X</orcidid><orcidid>https://orcid.org/0000-0001-5380-692X</orcidid><orcidid>https://orcid.org/0000-0002-3672-8429</orcidid></search><sort><creationdate>2024</creationdate><title>Phosphorus–nitrogen compounds: part 75—design, synthesis, stereogenic and conformational properties of chiral dispiro(N/N)cyclotriphosphazenes: structural analysis and photophysical and bioactivity studies</title><author>Cemaloğlu, Reşit ; Asmafiliz, Nuran ; Kılıç, Zeynel ; Topaloğlu Aksoy, Burcu ; Sabah, Büşra Nur ; Açık, Leyla ; Hökelek, Tuncer</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c314t-c3d468eb2e161dfe56e961139df4fa9730d8fffe24c11387076ab8c337e4827c3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2024</creationdate><topic>Atomic properties</topic><topic>Bacteria</topic><topic>Biological activity</topic><topic>Biological properties</topic><topic>Catalysis</topic><topic>Chemistry</topic><topic>Chemistry and Materials Science</topic><topic>Chirality</topic><topic>Crystallography</topic><topic>Dichroism</topic><topic>Inorganic Chemistry</topic><topic>Isomers</topic><topic>Nitrogen compounds</topic><topic>NMR</topic><topic>Nuclear magnetic resonance</topic><topic>Phosphorus</topic><topic>Physical Chemistry</topic><topic>Single crystals</topic><topic>Steric hindrance</topic><topic>Structural analysis</topic><topic>Yeast</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Cemaloğlu, Reşit</creatorcontrib><creatorcontrib>Asmafiliz, Nuran</creatorcontrib><creatorcontrib>Kılıç, Zeynel</creatorcontrib><creatorcontrib>Topaloğlu Aksoy, Burcu</creatorcontrib><creatorcontrib>Sabah, Büşra Nur</creatorcontrib><creatorcontrib>Açık, Leyla</creatorcontrib><creatorcontrib>Hökelek, Tuncer</creatorcontrib><collection>Springer Nature OA Free Journals</collection><collection>CrossRef</collection><jtitle>Research on chemical intermediates</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Cemaloğlu, Reşit</au><au>Asmafiliz, Nuran</au><au>Kılıç, Zeynel</au><au>Topaloğlu Aksoy, Burcu</au><au>Sabah, Büşra Nur</au><au>Açık, Leyla</au><au>Hökelek, Tuncer</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Phosphorus–nitrogen compounds: part 75—design, synthesis, stereogenic and conformational properties of chiral dispiro(N/N)cyclotriphosphazenes: structural analysis and photophysical and bioactivity studies</atitle><jtitle>Research on chemical intermediates</jtitle><stitle>Res Chem Intermed</stitle><date>2024</date><risdate>2024</risdate><volume>50</volume><issue>6</issue><spage>2603</spage><epage>2628</epage><pages>2603-2628</pages><issn>0922-6168</issn><eissn>1568-5675</eissn><abstract>Multiheterocyclic inorganic–organic hybrid phosphazenes have robust inorganic ring systems with the stabilities of the phosphorus nitrogen skeleton and many different substituents bonded to the P atoms. In present study, unsymmetrical dispirocyclotriphosphazenes were prepared due to their potential to depict steric hindrance and electronic rearrangement in creating permanent chirality for certain conformational and configurational isomers. These isomers may have an effect on DNA bindings and activitiy against selected fungi and bacteria, remarkably. Herein, tetrachlorocyclotriphosphazenes (
1
and
2
) were reacted with 9-ethyl-N-methyl-3-carbazolyl-1,2-diaminoethane (
3
), 9-ethyl-N-ethyl-3-carbazolyl-1,2-diaminoethane (
4
) and 9-ethyl-N-methyl-3-carbazolyl-1,3-diaminopropane (
5
) to give the new unsymmetrical cis/trans-dispirocyclotriphosphazenes, [(ClBz/BzSpiro-6)R
1
(N
3
P
3
)(CzSpiro-n)R
2
]Cl
2
(Cz: Carbazolyl; R
1
:Me R
2
:Me or Et; n = 5 or 6; trans
6a
–
11a
and cis
6b
–
11b
). Characterizations, chiralities, and photophysical and biological properties of the new compounds were examined. The molecular and crystal structures of cis-
6b
, cis-
7b
, trans-
9a
, cis-
9b
, trans-
10a
and cis-
10b
were determined by single crystal X-ray crystallography. The chiralities of these compounds with unsymmetrical spiro-architectures were confirmed by X-ray crystallography. These results were further proven by
31
P NMR data recorded with the addition of a chiral solvent (CSA). Additionally, circular dichroism (CD) spectra also supported the results. Photophysical measurements indicate that these compounds show emission with lifetimes of approximately 5.6–5.9 ns. In addition, the bioactivities of some isomers were found to be different and quite high against some bacterial and yeast strains. Trans-
8a
was very active against
B. cereus
(MBC = 78.1 µM), while cis-
6b
, trans-
9a
and cis-
9b
were very active against the pathogenic yeast
C. albicans
(MFC = 156.3 µM).
Graphical abstract</abstract><cop>Dordrecht</cop><pub>Springer Netherlands</pub><doi>10.1007/s11164-024-05285-7</doi><tpages>26</tpages><orcidid>https://orcid.org/0000-0002-2802-0754</orcidid><orcidid>https://orcid.org/0000-0002-8602-4382</orcidid><orcidid>https://orcid.org/0000-0003-1061-8122</orcidid><orcidid>https://orcid.org/0000-0002-9335-4101</orcidid><orcidid>https://orcid.org/0000-0003-1678-843X</orcidid><orcidid>https://orcid.org/0000-0001-5380-692X</orcidid><orcidid>https://orcid.org/0000-0002-3672-8429</orcidid><oa>free_for_read</oa></addata></record> |
| fulltext | fulltext |
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| ispartof | Research on chemical intermediates, 2024, Vol.50 (6), p.2603-2628 |
| issn | 0922-6168 1568-5675 |
| language | eng |
| recordid | cdi_proquest_journals_3062683381 |
| source | SpringerLink Journals |
| subjects | Atomic properties Bacteria Biological activity Biological properties Catalysis Chemistry Chemistry and Materials Science Chirality Crystallography Dichroism Inorganic Chemistry Isomers Nitrogen compounds NMR Nuclear magnetic resonance Phosphorus Physical Chemistry Single crystals Steric hindrance Structural analysis Yeast |
| title | Phosphorus–nitrogen compounds: part 75—design, synthesis, stereogenic and conformational properties of chiral dispiro(N/N)cyclotriphosphazenes: structural analysis and photophysical and bioactivity studies |
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