caa a22 4500 46318498X CHVBK 20180406164850.0 cr unu---uuuuu 170326e20070501xx s 000 0 eng 10.1007/s10870-006-9126-0 doi (NATIONALLICENCE)springer-10.1007/s10870-006-9126-0 X-ray diffraction, DFT, and spectroscopic study of N , N ′-difluoroboryl-5-(2-thienyl)dipyrrin and fluorescence studies of related dipyrromethanes, dipyrrins and BF2-dipyrrins and DFT conformational study of 5-(2-thienyl)dipyrrin [Elektronische Daten] [Shin Choi, Kibong Kim, Junseong Lee, Youngkyu Do, David Churchill] To explore the characteristics of potential fluorescent probes that could be used to screen prospective HDS catalysts, new 5-thienyl dipyrromethene derivatives have been prepared. 5-(2-thienyl)- (1a), 5-(3-thienyl)- (1b), and 5-(3-(2,5-dibromothienyl))-dipyrromethane (1c), were oxidized with DDQ (2,3-dichloro-5,6-dicyano-1,4-benzoquinone) separately to give the corresponding dipyrrins 2a-2c. These were subsequently treated with F3B·OEt2 to afford the respective N,N′-difluoroboryl-5-(thienyl)dipyrrin compounds, 3a-3c; the latter two may serve as polymer precursors. Significant fluorescence signal enhancement is achieved with 3a-3c over 2a-2c. Orange fluorescence is observed for 3a whereas its isomer 3b gives green fluorescence (365nm). An X-ray diffraction study of 3a was performed (orthorhombic, P212121, a=10.684(10)Å, b=15.208(13)Å, c=7.256(6)Å, V=1179.0(17)Å3, Z=4, R 1=0.0428, wR 2=0.0686) and its geometry was studied by way of DFT (Gaussian 03; B3LYP/6-31G*) to give a HOMO/LUMO energy level difference of 414nm, and a 2-thienyl group rotational barrier of ∼6kcal/mol, compared to that of ∼12kcal/mol for the phenyl derivative. Theoretical modeling of 2a demonstrated that the [N-H⋯N] interaction is favored by ca. 10kcal/mol, whereas [N-H⋯S] bonding is sterically unattainable. Springer Science+Business Media, Inc., 2007 thienyl nationallicence difluoroboryl-dipyrrin nationallicence crystal structure nationallicence DFT calculation nationallicence fluorescence nationallicence Choi Shin Department of Chemistry and School of Molecular Science - BK 21, Korea Advanced Institute of Science and Technology, 373-1 Guseong-dong, Yuseong-gu, 305-701, Daejeon, Republic of Korea aut Kim Kibong Department of Chemistry and School of Molecular Science - BK 21, Korea Advanced Institute of Science and Technology, 373-1 Guseong-dong, Yuseong-gu, 305-701, Daejeon, Republic of Korea aut Lee Junseong Department of Chemistry and School of Molecular Science - BK 21, Korea Advanced Institute of Science and Technology, 373-1 Guseong-dong, Yuseong-gu, 305-701, Daejeon, Republic of Korea aut Do Youngkyu Department of Chemistry and School of Molecular Science - BK 21, Korea Advanced Institute of Science and Technology, 373-1 Guseong-dong, Yuseong-gu, 305-701, Daejeon, Republic of Korea aut Churchill David Department of Chemistry and School of Molecular Science - BK 21, Korea Advanced Institute of Science and Technology, 373-1 Guseong-dong, Yuseong-gu, 305-701, Daejeon, Republic of Korea aut Journal of Chemical Crystallography Kluwer Academic Publishers-Plenum Publishers; http://www.springer-ny.com 37/5(2007-05-01), 315-331 1074-1542 37:5<315 2007 37 10870 https://doi.org/10.1007/s10870-006-9126-0 text/html Onlinezugriff via DOI 1 research-article jats NATIONALLICENCE 856 40 https://doi.org/10.1007/s10870-006-9126-0 text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Choi Shin Department of Chemistry and School of Molecular Science - BK 21, Korea Advanced Institute of Science and Technology, 373-1 Guseong-dong, Yuseong-gu, 305-701, Daejeon, Republic of Korea aut NATIONALLICENCE 700 1- Kim Kibong Department of Chemistry and School of Molecular Science - BK 21, Korea Advanced Institute of Science and Technology, 373-1 Guseong-dong, Yuseong-gu, 305-701, Daejeon, Republic of Korea aut NATIONALLICENCE 700 1- Lee Junseong Department of Chemistry and School of Molecular Science - BK 21, Korea Advanced Institute of Science and Technology, 373-1 Guseong-dong, Yuseong-gu, 305-701, Daejeon, Republic of Korea aut NATIONALLICENCE 700 1- Do Youngkyu Department of Chemistry and School of Molecular Science - BK 21, Korea Advanced Institute of Science and Technology, 373-1 Guseong-dong, Yuseong-gu, 305-701, Daejeon, Republic of Korea aut NATIONALLICENCE 700 1- Churchill David Department of Chemistry and School of Molecular Science - BK 21, Korea Advanced Institute of Science and Technology, 373-1 Guseong-dong, Yuseong-gu, 305-701, Daejeon, Republic of Korea aut NATIONALLICENCE 773 0- Journal of Chemical Crystallography Kluwer Academic Publishers-Plenum Publishers; http://www.springer-ny.com 37/5(2007-05-01), 315-331 1074-1542 37:5<315 2007 37 10870 Metadata rights reserved Springer special CC-BY-NC licence nationallicence BK010053 XK010053 XK010000 NATIONALLICENCE NATIONALLICENCE NL-springer