title: Synthetic, cyclic voltammetric, structural, EPR, and UV-Vis spectroscopic studies of thienyl-containing meso-A(2)B-cor(Cr(V)=O) systems: consideration of three interrelated molecular detection modalities.
abstract: We report eight new A(2)B-type (M(n+)) corrolate compounds (two structural studies) that include the oxo[5,15-bis(pentafluorophenyl)-10-R-corrolatochromium(V)] [R = 2-/3-thienyl (1a/2a), 3-thianaphthyl (3a)] species. The first examples of meso-A(2) (thienyl)- and Cr-A(2)B-corrole types are represented herein. Characterization includes cyclic voltammetry, electron paramagnetic resonance, 2D ((1)H and (13)C) NMR, and UV-vis spectroscopy, mass spectrometry, and elemental analysis. Compounds 1a-3a have enabled analyte binding capacity studies. [Cu(2+)...O=Cr(cor)] binding represents a new selective mode of corrole-based detection, whereas free-base A(2)B-corroles exhibited limited M(n+) selectivity. The 10-position substitution affects optical profiles in analyte titrations. A limited amount of PPh(3) O-atom uptake from [O=Cr(cor)] was also demonstrated.
authors.affiliation: Molecular Logic Gate Laboratory, KoreaAdvanced Institute of Science and Technology (KAIST), 373-1 Guseong-dong, Yuseong-gu,Daejeon 305-701, Republic of Korea.
authors.forename: Olga A
authors.initials: OA
authors.lastname: Egorova
authors.forename: Olga G
authors.initials: OG
authors.lastname: Tsay
authors.forename: Snehadrinarayan
authors.initials: S
authors.lastname: Khatua
authors.forename: Bhupal
authors.initials: B
authors.lastname: Meka
authors.forename: Nilkamal
authors.initials: N
authors.lastname: Maiti
authors.forename: Min-Kyu
authors.initials: MK
authors.lastname: Kim
authors.forename: Seong Jung
authors.initials: SJ
authors.lastname: Kwon
authors.forename: Jung Oh
authors.initials: JO
authors.lastname: Huh
authors.forename: Daniela
authors.initials: D
authors.lastname: Bucella
authors.forename: Sa-Ouk
authors.initials: SO
authors.lastname: Kang
authors.forename: Juhyoun
authors.initials: J
authors.lastname: Kwak
authors.forename: David G
authors.initials: DG
authors.lastname: Churchill
mesh_terms: D002384:Catalysis; D017608:Chromium Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D018360:Crystallography, X-Ray; D004563:Electrochemistry; D004578:Electron Spin Resonance Spectroscopy; D008670:Metals / Q000737:chemistry; D008958:Models, Molecular; D015394:Molecular Structure; D011166:Porphyrins / Q000138:chemical synthesis / Q000737:chemistry*; D013056:Spectrophotometry, Ultraviolet
chemical_list: D017608:Chromium Compounds; D008670:Metals; D011166:Porphyrins; C431863:corrole