Dual-Functional Manganese-Doped ZnO-MOF Hybrid Material with Enhanced Hydrolytic Stability: A Fluorescent Photoinduced Electron Transfer Sensor for the Ultraselective Detection of Acetic Acid and Chromium (VI).

In recent years, the synthesis of metal-organic framework (MOF)─nanocomposites has received wide attention from the scientific fraternity due to the presence of a tunable hierarchical architecture and invasive versatility in applications. The present work focuses on the solvothermal synthesis of a novel hybrid MOF-nanocomposite through the impregnation of Mn-doped ZnO nanoparticles onto the matrix of a pioneer metal-organic framework that is composed of zinc metal connected with terephthalic acid linkers (MOF-5). The hierarchical arrangements of the prepared material were further assessed by Fourier-transform infrared spectroscopy (FTIR), powder X-ray diffraction (PXRD), high-resolution transmission electron microscopy (HR-TEM), UV-visible, photoluminescence (PL), and dynamic light scattering (DLS) measurements. The porosity analysis via nitrogen sorption measurements at 77 K showed that the material is porous with hierarchical micro-, wide micro-, and mesopores. The SAED pattern confirms the polycrystallinity of the material, which is in good agreement with the data obtained from PXRD analysis. Effective integration of Mn-doped ZnO onto the MOF structure was confirmed by XPS analysis, and the study further identified the oxidation state of the elements present. The synthesized analyte is an efficient fluorescent chemosensor for the detection of acetic acid, which can find further potential applications in intracellular imaging. Interestingly, the same compound also selectively detects the presence of Cr(VI) ions, thereby acting as a dual sensor, which finds applications in the sensing and removal of environmental contaminants. The material showed a sharp and intense emission at 569 nm at an excitation wavelength of 320 nm, and it exhibits high quenching efficiencies of 99.87 and 71.43% toward the sensing of µM level concentration of acetic acid and Cr2O72-, respectively. The highly efficient fluorescent sensing of pollutants, even at a shorter linear range, discarded the possibility of sensing the pollutants at higher concentration ranges. The Ksv value for the detection of acetic acid and Cr(VI) is found to be 3.7017 × 106 and 11.0324 × 106 M-1, respectively, which further confirms the higher sensing ability of the synthesized fluorophore. The mechanistic studies and density functional theory calculations of Mn-doped ZnO@MOF-5 reveal that photoinduced electron transfer plays a significant role in the turn-off response toward acetic acid and Cr2O72- ions. In the case of acetic acid, in addition to photoinduced electron transfer, hydrogen bonding interactions may also lead to fluorescence quenching. To the best of our knowledge, no precedent work has been reported for the sensing of acetic acid in the solution state. All other fluorescent sensing reports put forward the sensing and adsorption of acetic acid in the gaseous state, which makes this material a pioneer among others for the detection of acetic acid in the solution phase.

Axial vs equatorial: Capturing the intramolecular charge transfer state geometry in conformational polymorphic crystals of a donor-bridge-acceptor dyad in nanosecond-time-scale.

Two conformational polymorphs of a donor-bridge-acceptor (D-B-A) dyad, p-(CH3)2N-C6H4-(CH2)2-(1-pyrenyl)/PyCHDMA, were studied, where the electron donor (D) moiety p-(CH3)2N-C6H4/DMA is connected through a bridging group (B), -CH2-CH2-, to the electron acceptor (A) moiety pyrene. Though molecular dyads like PyCHDMA have the potential to change solar energy into electrical current through the process of photoinduced intramolecular charge transfer (ICT), the major challenge is the real-time investigation of the photoinduced ICT process in crystals, necessary to design solid-state optoelectronic materials. The time-correlated single photon counting (TCSPC) measurements with the single crystals showed that the ICT state lifetime of the thermodynamic form, PyCHDMA1 (pyrene and DMA: axial), is ∼3 ns, whereas, for the kinetic form, PyCHDMA20 (pyrene and DMA: equatorial), it is ∼7 ns, while photoexcited with 375 nm radiation. The polymorphic crystals were photo-excited and subsequently probed with a pink Laue x-ray beam in time-resolved x-ray diffraction (TRXRD) measurements. The TRXRD results suggest that in the ICT state, due to electron transfer from the tertiary N-atom in DMA moiety to the bridging group and pyrene moiety, a decreased repulsion between the lone-pair and the bond-pair at N-atom induces planarity in the C-N-(CH3)2 moiety, in both polymorphs. The Natural Bond Orbital calculations and partial atomic charge analysis by Hirshfeld partitioning also corroborated the same. Although the interfragment charge transfer (IFCT) analysis using the TDDFT results showed that for the charge transfer excitation in both conformers, the electrons were transferred from the DMA moiety to mostly the pyrene moiety, the bridging group has little role to play in that.

Cationic and Anionic Impact on the Electronic Structure of Liquid Water.

Hydration shells around ions are crucial for many fundamental biological and chemical processes. Their local physicochemical properties are quite different from those of bulk water and hard to probe experimentally. We address this problem by combining soft X-ray spectroscopy using a liquid jet and molecular dynamics (MD) simulations together with ab initio electronic structure calculations to elucidate the water-ion interaction in a MgCl2 solution at the molecular level. Our results reveal that salt ions mainly affect the electronic properties of water molecules in close vicinity and that the oxygen K-edge X-ray emission spectrum of water molecules in the first solvation shell differs significantly from that of bulk water. Ion-specific effects are identified by fingerprint features in the water X-ray emission spectra. While Mg2+ ions cause a bathochromic shift of the water lone pair orbital, the 3p orbital of the Cl- ions causes an additional peak in the water emission spectrum at around 528 eV.

Crystal structure of trans-1-{2-[4-(di-methyl-amino)-phen-yl]eth-yl}-4-[2-(pyren-1-yl)eth-yl]cyclo-hexa-ne.

The title compound, C34H37N, is a pyrene derivative in which the pyrene ring system is linked to an ethyl-cyclo-hexane unit which, in turn, carries a [4-(di-methyl-amino)-phen-yl]ethyl substituent in the para position. The central cyclo-hexane ring has a chair conformation, with the exocyclic C-C bonds in equatorial orientations. The benzene ring is inclined to the mean plane of the pyrene ring system [maximum deviation = 0.038 (4) Å] by 14.84 (15)°. In the crystal, mol-ecules are linked by C-H⋯π inter-actions, forming chains propagating along [010]. The crystal was refined as a non-merohedral twin [domain ratio = 0.9989 (4):0.0011 (4)].

Ultrafast dynamical study of pyrene-N,N-dimethylaniline (PyDMA) as an organic molecular diode in solid state.

Femtosecond optical pump-probe spectroscopy has been employed for studying the directly linked electron donor-acceptor system pyrene-N,N-dimethylaniline (PyDMA) in solid state. This DMA-pyrene derivative discussed is being applied as a molecular diode system switching on an ultrafast time scale. Our ultrafast solid-state studies reveal a complex photochemistry of this molecular crystal system. Strong couplings of the optically induced charge-transfer state with the radical ion pair state allow a femtosecond transition of the latter. One could see on the highest occupied molecular orbital-lowest unoccupied molecular orbital (HOMO-LUMO) description that a pure optical transition switches the system from a conducting to a blocked system because the molecular orbitals (MOs) of DMA moiety lie in a node plane of the LUMO. Within 800 fs the system relaxes back to the ground state and/or forms a radical ion pair, which is the surprising result of our study; when the system was probed further, the system underwent vibrational cooling and enhanced population inversion of the radical ion pair.

N,N-Dimethyl-4-(pyren-1-yl)aniline.

In the title compound, C24H19N, the di-methyl-amino group is inclined to the benzene ring by 2.81 (9)°. Their mean plane makes a dihedral angle of 64.12 (2)° with the mean plane of the pyrene ring system [r.m.s. deviation = 0.031 (1) Å]. In the crystal, mol-ecules are linked via C-H⋯π inter-actions, which connect neighbouring mol-ecules into columns along the c axis.