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The characters of σ- and π-holes of bromopentafluorobenzene (C6F5Br) enable it to interact with an electron-rich atom or group like pyridine which possesses an electron lone-pair N atom and a π ring. Theoretical studies of intermolecular interactions between C6F5Br and C5H5N have been carried out at the M06-2X/aug-cc-pVDZ level without and with the counterpoise method, together with single point calculations at M06-2X/TZVP, wB97-XD/aug-cc-pVDZ and CCSD(T)/aug-cc-pVDZ levels. The σ- and π-holes of C6F5Br exhibiting positive electrostatic potentials make these sites favorably interact with the N atom and the π ring of C5H5N with negative electrostatic potentials, leading to five different dimers connected by a σ-hole…n bond, a σ-hole…π bond or a π-hole…π bond. Their geometrical structures, characteristics, nature and spectroscopy behaviors were systematically investigated. EDA analyses reveal that the driving forces in these dimers are different. NCI, QTAIM and NBO analyses confirm the existence of intermolecular interactions formed viaσ- and π-holes of C6F5Br and the N atom and the π ring of C5H5N. The experimental IR and Raman spectra gave us important information about the formation of molecular complexes between C6F5Br and C5H5N. We expect that the results could provide valuable insights into the investigation of intermolecular interactions involving σ- and π-holes. [ABSTRACT FROM AUTHOR]

Prototype lanthanide metal–organic frameworks (LnMOFs), Ln(BTC) (Ln = Eu and Tb; BTC = benzene-1,3,5-tricarboxylate), have been considered as luminescent sensors for detecting toxic anions, while their neutral pore structures have limited the entrance and encapsulation of anions to produce highly anion-responsive photoluminescence (PL). To facilitate anions to enter the pore space of Ln(BTC), a one-pot synthesis method was proposed in which BTC was partially replaced with its structural analogue L·BF4 (H3L·BF4 = 2,4,6-tricarboxy-1-methylpyridinium tetrafluoroborate) which consists of an anion affinity site of cationic methylpyridinium. Compared to the original Ln(BTC), the co-doped cationic framework Eu0.05Tb0.95-BTC0.9L0.1 is highly sensitive for detecting different toxic anions by tuning the energy absorption of organic chromophores, the energy transfer efficiency to Ln3+ ions and the energy allocation between different Ln3+ ions in the PL spectra. We demonstrated that the Eu0.05Tb0.95-BTC0.9L0.1 PL sensor has the capability of decoding various toxic anions with a clearly differentiable and unique emission intensity ratio of 5D4→7F5 (Tb3+, 545 nm) to 5D0→7F2 (Eu3+, 618 nm) transitions (ITb/IEu). Compared to Ln(BTC), the co-doped Eu0.05Tb0.95-BTC0.9L0.1 presents self-calibrating, high distinguishable and stable PL signals for detecting toxic anions. [ABSTRACT FROM AUTHOR]

Theoretical investigations of the interactions between carbon monoxide (CO) and bromopentafluorobenzene (C6F5Br) have been carried out at both M06-2X/6-311++G(2d,2p) and M06-2X/aug-cc-pVTZ levels of theory. Because both C and O atom-ends of CO show negative electrostatic potential, they can favorably interact with the positive electrostatic potential generated by the σ-hole of Br and the π-hole of the aromatic ring of C6F5Br, yielding four different dimers and trimers. Their structures, spectroscopy and nature were systematically studied. The competition between the interactions involving the σ-hole of the Br atom and the π-hole of C6F5Br with the C and O atom-ends of CO was illustrated for the dimers and trimers, and meanwhile, the cooperativity between the two components of the trimers was elaborated. In addition, the experimental FT-IR and fluorescence spectra were measured for C6F5Br and the mixed C6F5Br and CO system without and with the solvent of hexane to gain information on the formation of molecular complexes between C6F5Br and CO. The results presented in this work are beneficial for the understanding of the competition and cooperativity of σ- and π-hole intermolecular interactions. [ABSTRACT FROM AUTHOR]

A novel fluorescent Fe3+ probe (L)based on 2-(2-hydroxyphenyl)benzothiazole has been synthesized and characterized. Both UV-vis and fluorescence spectroscopic studies demonstrated that L was highly sensitive and selective towards Fe3+ over other metal ions in acetonitrile. Upon binding with Fe3+, the emission band of L red-shifted from 370 nm to 420 nm and the fluorescence intensity was enhanced ∼103-fold. The lowest detection limit for L is 6.04 × 10−8 M and the dissociation constants Kd is 1.13 × 10−11 M, which were calculated from the fluorescence titration curves. The detailed UV-vis and fluorescent titrations studies suggested that the binding stoichiometry of the L–Fe3+ complex was 2 : 1, and the structure between L and the Fe3+ complex was confirmed by the 1H NMR titration. Then IR spectra provided further proof of the binding mode of the L–Fe3+ complex. [ABSTRACT FROM AUTHOR]

Prototype lanthanide metal-organic frameworks (LnMOFs), Ln(BTC) (Ln = Eu and Tb; BTC = benzene-1,3,5-tricarboxylate), have been considered as luminescent sensors for detecting toxic anions, while their neutral pore structures have limited the entrance and encapsulation of anions to produce highly anion-responsive photoluminescence (PL). To facilitate anions to enter the pore space of Ln(BTC), a one-pot synthesis method was proposed in which BTC was partially replaced with its structural analogue L·BF 4 (H 3 L·BF 4 = 2,4,6-tricarboxy-1-methylpyridinium tetrafluoroborate) which consists of an anion affinity site of cationic methylpyridinium. Compared to the original Ln(BTC), the co-doped cationic framework Eu 0.05 Tb 0.95 -BTC 0.9 L 0.1 is highly sensitive for detecting different toxic anions by tuning the energy absorption of organic chromophores, the energy transfer efficiency to Ln 3+ ions and the energy allocation between different Ln 3+ ions in the PL spectra. We demonstrated that the Eu 0.05 Tb 0.95 -BTC 0.9 L 0.1 PL sensor has the capability of decoding various toxic anions with a clearly differentiable and unique emission intensity ratio of 5 D 4 → 7 F 5 (Tb 3+ , 545 nm) to 5 D 0 → 7 F 2 (Eu 3+ , 618 nm) transitions (I Tb /I Eu ). Compared to Ln(BTC), the co-doped Eu 0.05 Tb 0.95 -BTC 0.9 L 0.1 presents self-calibrating, high distinguishable and stable PL signals for detecting toxic anions.