Chelate ring size effect as a factor of selective fluorescent recognition of ions by pyrrolo[2,3-b]quinoxaline with a substituted 2-oyridyl group receptor

2015
journal article
article
17
dc.abstract.enAnalysis of the spectral properties and structural di ff erences of two turn-on ratiometric fl uorescent receptors for Zn 2+ and Cd 2+ ions, derivatives of pyrrolo[2,3- b ]quinoxaline ( 2 ), and earlier published 3 (Ostrowska et al. CrystEngComm 2015 , 17 , 498 − 502) was performed. Both ligands are E / Z push − pull ole fi ns interconverting at room temperature, with barriers to rotation about enamine double bonds, from E to Z isomers of 19.3 ± 0.1 and 16.9 ± 0.3 kcal/mol and from Z to E of 16.9 ± 0.3 and 15.7 ± 0.2 kcal/mol, respectively. Diastereoisomers ( E )- 2 and ( Z )- 2 were isolated and charac- terized by X-ray structural analysis. The formation of complexes by ( E / Z )- 2 with acetates and acetylacetonates of Zn 2+ and Cd 2+ was monitored by UV − vis, fl uorescence, and 1 H NMR titrations in acetonitrile, respectively. X-ray structural analysis for isolated [( E )- 2 ] 2 Zn in relation to earlier published ( E )- 3 -ZnOAc revealed the formation of a six-coordinated zinc ion with six- and four-membered bis-chelate rings by ( E )- 2 . The chelate e ff ect increases the ligand a ffi nity for Zn 2+ (log β 12 = 12.45) and causes the elongation of nitrogen − metal bonds. Extension of the coordination cavity size allows coordination of a cadmium ion. The introduction of a fl exible ethylene linker between the fl uorophore and ionophore pyridyl groups in 3 signi fi cantly a ff ects the selectivity of zinc-ion recognition. The distorted tetrahedral geometry of ( E )- 3 -ZnOAc with a four-coordinated zinc ion appears to be the most preferred because of the short donor − zinc distance with a 1:1 binding mode. The formation of the small coordination cavity size with six-membered bis-chelate rings provides an e ff ective overlap of zinc and donor orbitals, precluding the coordination of a cadmium ion in the same manner as zinc.pl
dc.affiliationWydział Chemii : Zakład Krystalochemii i Krystalofizykipl
dc.affiliationWydział Chemii : Pracownia Spektroskopii NMRpl
dc.affiliationWydział Chemii : Zakład Chemii Organicznejpl
dc.contributor.authorOstrowska, Katarzyna - 131207 pl
dc.contributor.authorMusielak, Bogdan - 126144 pl
dc.contributor.authorSzneler, Edward - 132246 pl
dc.contributor.authorGryl, Marlena - 141879 pl
dc.contributor.authorStadnicka, Katarzyna - 132048 pl
dc.contributor.authorDudek, Łukasz - 173718 pl
dc.date.accessioned2015-12-04T13:51:05Z
dc.date.available2015-12-04T13:51:05Z
dc.date.issued2015pl
dc.description.admin[AB] Dudek, Łukasz [SAP11019915] 50000141pl
dc.description.admin[AB] Stadnicka, Katarzyna [SAP11004149] 50000141pl
dc.description.number17pl
dc.description.physical8423-8435pl
dc.description.volume54pl
dc.identifier.doi10.1021/acs.inorgchem.5b01533pl
dc.identifier.eissn1520-510Xpl
dc.identifier.issn0020-1669pl
dc.identifier.urihttp://ruj.uj.edu.pl/xmlui/handle/item/17673
dc.languageengpl
dc.language.containerengpl
dc.rights.licencebez licencji
dc.subtypeArticlepl
dc.titleChelate ring size effect as a factor of selective fluorescent recognition of $Zn^{2+}$ ions by pyrrolo[2,3-b]quinoxaline with a substituted 2-oyridyl group receptorpl
dc.title.journalInorganic Chemistrypl
dc.typeJournalArticlepl
dspace.entity.typePublication
dc.abstract.enpl
Analysis of the spectral properties and structural di ff erences of two turn-on ratiometric fl uorescent receptors for Zn 2+ and Cd 2+ ions, derivatives of pyrrolo[2,3- b ]quinoxaline ( 2 ), and earlier published 3 (Ostrowska et al. CrystEngComm 2015 , 17 , 498 − 502) was performed. Both ligands are E / Z push − pull ole fi ns interconverting at room temperature, with barriers to rotation about enamine double bonds, from E to Z isomers of 19.3 ± 0.1 and 16.9 ± 0.3 kcal/mol and from Z to E of 16.9 ± 0.3 and 15.7 ± 0.2 kcal/mol, respectively. Diastereoisomers ( E )- 2 and ( Z )- 2 were isolated and charac- terized by X-ray structural analysis. The formation of complexes by ( E / Z )- 2 with acetates and acetylacetonates of Zn 2+ and Cd 2+ was monitored by UV − vis, fl uorescence, and 1 H NMR titrations in acetonitrile, respectively. X-ray structural analysis for isolated [( E )- 2 ] 2 Zn in relation to earlier published ( E )- 3 -ZnOAc revealed the formation of a six-coordinated zinc ion with six- and four-membered bis-chelate rings by ( E )- 2 . The chelate e ff ect increases the ligand a ffi nity for Zn 2+ (log β 12 = 12.45) and causes the elongation of nitrogen − metal bonds. Extension of the coordination cavity size allows coordination of a cadmium ion. The introduction of a fl exible ethylene linker between the fl uorophore and ionophore pyridyl groups in 3 signi fi cantly a ff ects the selectivity of zinc-ion recognition. The distorted tetrahedral geometry of ( E )- 3 -ZnOAc with a four-coordinated zinc ion appears to be the most preferred because of the short donor − zinc distance with a 1:1 binding mode. The formation of the small coordination cavity size with six-membered bis-chelate rings provides an e ff ective overlap of zinc and donor orbitals, precluding the coordination of a cadmium ion in the same manner as zinc.
dc.affiliationpl
Wydział Chemii : Zakład Krystalochemii i Krystalofizyki
dc.affiliationpl
Wydział Chemii : Pracownia Spektroskopii NMR
dc.affiliationpl
Wydział Chemii : Zakład Chemii Organicznej
dc.contributor.authorpl
Ostrowska, Katarzyna - 131207
dc.contributor.authorpl
Musielak, Bogdan - 126144
dc.contributor.authorpl
Szneler, Edward - 132246
dc.contributor.authorpl
Gryl, Marlena - 141879
dc.contributor.authorpl
Stadnicka, Katarzyna - 132048
dc.contributor.authorpl
Dudek, Łukasz - 173718
dc.date.accessioned
2015-12-04T13:51:05Z
dc.date.available
2015-12-04T13:51:05Z
dc.date.issuedpl
2015
dc.description.adminpl
[AB] Dudek, Łukasz [SAP11019915] 50000141
dc.description.adminpl
[AB] Stadnicka, Katarzyna [SAP11004149] 50000141
dc.description.numberpl
17
dc.description.physicalpl
8423-8435
dc.description.volumepl
54
dc.identifier.doipl
10.1021/acs.inorgchem.5b01533
dc.identifier.eissnpl
1520-510X
dc.identifier.issnpl
0020-1669
dc.identifier.uri
http://ruj.uj.edu.pl/xmlui/handle/item/17673
dc.languagepl
eng
dc.language.containerpl
eng
dc.rights.licence
bez licencji
dc.subtypepl
Article
dc.titlepl
Chelate ring size effect as a factor of selective fluorescent recognition of $Zn^{2+}$ ions by pyrrolo[2,3-b]quinoxaline with a substituted 2-oyridyl group receptor
dc.title.journalpl
Inorganic Chemistry
dc.typepl
JournalArticle
dspace.entity.type
Publication

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