DC Field | Value | Language |
---|---|---|
dc.contributor.author | Choi, Shin-Hei | ko |
dc.contributor.author | Pang, Keliang | ko |
dc.contributor.author | Kim, Ki-Bong | ko |
dc.contributor.author | Churchill, David G | ko |
dc.date.accessioned | 2009-09-09T08:21:24Z | - |
dc.date.available | 2009-09-09T08:21:24Z | - |
dc.date.created | 2012-02-06 | - |
dc.date.created | 2012-02-06 | - |
dc.date.issued | 2007-12 | - |
dc.identifier.citation | INORGANIC CHEMISTRY, v.46, no.25, pp.10564 - 10577 | - |
dc.identifier.issn | 0020-1669 | - |
dc.identifier.uri | http://hdl.handle.net/10203/11117 | - |
dc.description.abstract | Four novel tetrathienyl-substituted boron-dipyrrin-type (BODIPY-type) complexes, 3-(R')-4+di(R')-8-R-4-bora3a,4a-diaza-s-indacene (4a, R = 2-T, R' = 2-T; 4b, R = 3-T, R' = 2-T; 5a, R = 2-T, R' = 3-T; 5b, R = 3-T, R' = 3-T; T = thienyl) have been prepared and fully characterized to explore patterns of stoichiometric Mn+ recognition in solution. Treatment of the respective parent BF2 dipyrrin with 2- or 3-thienyllithium gave the unexpected asymmetric tetrathienyl-substituted products in 8.5-35% yield. Compounds 4a and 4b bear a neutral "scorpionate"like [SSS] tridentate binding pocket. Extensive NMR and UV-vis spectroscopic studies were performed on 4a-5b; 5a, 4b, and 5b were structurally characterized. The Phi(F) values for 4a-5b all decrease compared to the BF2-containing parent molecules (0.00058, 0.012, 0.00090, and 0.0051, respectively), with lambda(abs,max) values (is an element of, M-1 cm(-1)) of 563 (44 000), 553 (29 000), 539 (33 000), and 531 (44 000) nm, respectively, and Stokes' shifts of 25-36 nm. Upon treatment with metal ion (Ca2+, CS+, Mn2+, CO2+, Cu2+, Ag+, Zn2+, Cd2+, Hg2+, Pb2+) perchlorate salts, the solution of 4b undergoes rapid pink-to-clear switch-off behavior upon Cu2+ addition (10 mu M scale) with smaller effects seen for 4a. Further, there were 2- to 19-fold Cu2+ fluorescence enhancements for these ligands. Cu2+ and Hg2+-L (L = 4a-5b) binding was modeled, and response patterns for Mn+-L 1:1 molar solutions upon Cu2+ addition were measured. Upon treatment with Hg2+, all ligand solutions show a significant fluorescence decrease accompanied by minor absorption increases. The UV-vis spectroscopic detection limit for Cu2+ and Hg2+ is similar to 270 ppb and similar to 1.7 ppm, respectively; the naked eye detection limit for Cu2+ with 4b (1.0 x 10(-5) M) is similar to 23 mu M. DFT calculations gave HOMO-LUMO gaps of 478 (4a), 462 (4b), 448 (5a), and 442 nm (5b). Molecular orbital diagrams for 4a-5b revealed that the HOMO and LUMO electron density is distributed onto the 3-position-thienyl group and to a lesser degree the B(thienyl)(2) moiety. | - |
dc.description.sponsorship | financial support from KAIST, KRF, the BK 21 Project, and the Korea Science Academy (Busan, South Korea) | en |
dc.language | English | - |
dc.language.iso | en_US | en |
dc.publisher | AMER CHEMICAL SOC | - |
dc.subject | SELECTIVE RECOGNITION | - |
dc.subject | DERIVATIVES | - |
dc.subject | ION | - |
dc.subject | CHEMOSENSOR | - |
dc.subject | SENSOR | - |
dc.subject | FLUOROIONOPHORE | - |
dc.subject | CHEMODOSIMETER | - |
dc.subject | COPPER(II) | - |
dc.subject | COMPLEXES | - |
dc.subject | CU(II) | - |
dc.title | Cu2+ colorimetric sensing and fluorescence enhancement and Hg2+ fluorescence diminution in "Scorpionate"-like tetrathienyl-substituted boron-dipyrrins | - |
dc.type | Article | - |
dc.identifier.wosid | 000251393900020 | - |
dc.identifier.scopusid | 2-s2.0-37449019312 | - |
dc.type.rims | ART | - |
dc.citation.volume | 46 | - |
dc.citation.issue | 25 | - |
dc.citation.beginningpage | 10564 | - |
dc.citation.endingpage | 10577 | - |
dc.citation.publicationname | INORGANIC CHEMISTRY | - |
dc.embargo.liftdate | 9999-12-31 | - |
dc.embargo.terms | 9999-12-31 | - |
dc.contributor.localauthor | Churchill, David G | - |
dc.contributor.nonIdAuthor | Choi, Shin-Hei | - |
dc.contributor.nonIdAuthor | Pang, Keliang | - |
dc.type.journalArticle | Article | - |
dc.subject.keywordPlus | SELECTIVE RECOGNITION | - |
dc.subject.keywordPlus | DERIVATIVES | - |
dc.subject.keywordPlus | ION | - |
dc.subject.keywordPlus | CHEMOSENSOR | - |
dc.subject.keywordPlus | SENSOR | - |
dc.subject.keywordPlus | FLUOROIONOPHORE | - |
dc.subject.keywordPlus | CHEMODOSIMETER | - |
dc.subject.keywordPlus | COPPER(II) | - |
dc.subject.keywordPlus | COMPLEXES | - |
dc.subject.keywordPlus | CU(II) | - |
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