Utilization of a trinuclear Cu-pyrazolate inorganic motif to build multifunctional MOFs.

The current work aims to generate multifunctional MOFs by incorporating a well-known inorganic motif, a trinuclear Cu-pyrazolate [Cu3(µ3-OH)(µ-Pyz)3] (T-CuP) unit, as a node of the network. Accordingly, we report herein the synthesis and properties of five new compounds using five V-shaped dicarboxylic acids as auxiliary ligands. The structural features are consistent with the theme of grafting T-CuP units as nodal points of architectures whose chassis are primarily made of bent acids. V-shaped acids also induce a helical nature inside resulting frameworks. Beside their structural and physical features, T-CuP unit-based MOFs also vindicate our thematic approach of the trinuclear Cu-pyrazolate unit imparting specific physicochemical properties, such as magnetic, electrical, and catalytic properties, to resultant MOFs. The MOFs show excellent catalytic properties in reducing 4-nitrophenol, which could be attributed to the porous nature of the network along with the presence of metal centres with unsaturated coordination within the T-CuP unit. Furthermore, efficient photocatalytic degradation of harmful organic dyes confirms their importance for environmental remediation. The presence of a T-CuP unit and various functional groups also make some of the MOFs suitable candidates for electrical applications, which is indeed manifested in encouraging proton conductivity. Finally, the potential of current MOFs, fitted with a magnetically important trinuclear Cu-pyrazolate motif, as magnetic materials has also been thoroughly investigated.

A Nd6 molecular butterfly: a unique all-in-one material for SMM, MCE and maiden photosensitized opto-electronic device fabrication.

Besides iron, ironically neodymium (Nd) is the most ubiquitously used metal for magnetic purposes, even among the lanthanides, when it comes to the field of molecular magnetism, yet it ranks among the least studied metals. However, strong apathy towards this magnetic lanthanide means that vital information will be missed, which is required for the advancement of the subject. Herein, we have successfully demonstrated the usefulness of a hexanuclear neodymium complex as a magnetic material, and also in electronic device fabrication. A {NdIII6} cage with an aesthetically pleasing butterfly topology was synthesized using a rather non-conventional N-rich pyridyl-pyrazolyl based ligand. The cage shows single molecule magnet (SMM) properties, with an effective energy barrier, Ueff, value of 3.4 K and relaxation time, τ0, of 3.1 × 10-4 s, originating from an unusual occurrence of metal centres with different coordination environments. Furthermore, magnetic studies reveal significant cyrogenic magnetic cooling, with a magnetic entropy change of 8.28 J kg-1 K-1 at 5 T and 3 K. To the best of our knowledge, the titular compound is the only example of a Nd-complex that exhibits concomitant magnetocaloric effect (MCE) and SMM properties. Complete active space self-consistent field (CASSCF) calculations were carried out to shed light on the origin of the magnetic anisotropy and magnetic relaxation of the compound. The same uniqueness is also true for the first electronic investigation carried out on the Nd complex. The maiden electronic device fabricated using the Nd complex shows an interesting intertwining of electronic and optical features, which contribute towards its improved photosensitized optoelectronic data.

Fascinating interlocked triacontanuclear giant nanocages.

We report herein three air, thermal and solvent stable interlocked triacontanuclear giant nanocages, generated using a node and spacer concept. Interestingly, the crystal structures of the cages are not only nano-dimensional but also exist in the nano-dimension range, which was corroborated with microscopic images. The combination of microscopic and crystallographic data, in effect, led us to a unique advantageous situation of generating nanomaterials with hard-to-come-by structural information at the molecular level.

Lanthanide clusters of phenanthroline containing a pyridine-pyrazole based ligand: magnetism and cell imaging.

In this contribution, we report the synthesis, characterization and luminescence-magnetic properties of Ln-clusters (Ln = Gd3+, Eu3+ and Tb3+) using a new pyridine-pyrazole functionalized ligand fitted with a chromophoric phenanthroline backbone. The unorthodox N-rich ligand forms isostructural trinuclear lanthanide complexes with a topology that closely resembles two interdigitating hairpins. The clusters crystallize in chiral space groups and also exhibit chirality for bulk samples, which were further confirmed using solid state CD spectra. Magnetic studies on the complexes reveal their interesting features while the Gd cluster shows a significant cryogenic magnetic cooling behaviour with a moderately high magnetic entropy change of -23.42 J kg-1 K-1 at 7 T and 2 K. On the other hand, Eu and Tb complexes exhibit interesting fluorescence properties. The compounds were subsequently used as fluorescent probes for the imaging of human breast adenocarcinoma (MCF7) cells. Live cell confocal microscopy images show that the complexes penetrate beyond the usual cytoplasm region and can be useful in imaging the nucleus region of MCF7 cells.

Pyridine-pyrazole based Al(iii) 'turn on' sensor for MCF7 cancer cell imaging and detection of picric acid.

We report herein the development of a new pyridine-pyrazole based bis-bidentate asymmetric chemosensor that shows excellent turn-on chelation-enhanced Al3+-responsive fluorescence. The presence of two 'hard' phenolic hydroxyl groups plays a pivotal role in switching-on the sensing through coordination to the 'hard' Al3+ ion, while the mechanism can be interpreted by the chelation-enhanced fluorescence (CHEF) process. The X-ray single structure show a planar conjugated structure of the ligand, which was further stabilized by extensive H-bonding and π-π stacking. The photophysical studies related to the sensing behavior of the titular ligand toward aluminum was investigated in detail using various spectroscopic techniques like UV-Vis, photoluminescence, fluorescence and time-correlated single-photon count (TCSPC) and time-resolved NMR. The spectroscopic methods also confirm the selective detection of Al3+ ion in the presence of other metal ions. The theoretical calculations using Density Functional Theory (DFT) and the Time Dependent Density Functional Theory (TD-DFT) provide further insight on the mechanistic aspects of the turn-on sensing behavior including the electronic spectra of both the ligand and the complex. Interestingly, the as-synthesized H2DPC-Al complex can also be utilized as a fluorescence-based sensor for various nitroaromatics including picric acid, for which an INHIBIT logic gate can also be constructed. The as synthesized complex was subsequently used as a fluorescent probe for imaging of human breast adenocarcinoma (MCF7) cells using live cell confocal microscopic techniques.

Utilization of counter anions for charge transportation in the electrical device fabrication of Zn(II) metal-organic frameworks.

The present work reports the fabrication of anion-induced electrical devices with Zn(ii) metal-organic frameworks. The essence of our electronic device fabrication is to utilize the anionic species entrapped inside of the three-dimensional network of the MOFs for charge transportation. The idea is to generate MOFs as a host-guest system with encapsulated anions or anion-solvent clusters as guests and a cationic yet insulating three-dimensional framework as the host. Accordingly, we have synthesized two Zn(ii) MOFs using a neutral bispyrazole-based ligand, which results in a cationic chassis with substantial void space and porous channels inside the network. For both MOFs, the porous channels are occupied by infinitely hydrogen bonded networks of anions and anion-solvent clusters. This provides an excellent platform for anionic species-induced charge transportation and improved electrical conductivity. Indeed, the impedance spectroscopy data and current density-voltage (J-V) characteristics of the fabricated electrical devices further vindicate our idea. The current-voltage measurements clearly indicate the usefulness of modified host-guest-type MOFs for electronic device fabrication with corroborating conductivity values of 8.71 × 10-5 S m-1 and 5.79 × 10-4 S m-1 for compound 1 and compound 2, respectively.

Correction to "Temperature-Induced Single-Crystal-to-Single-Crystal Transformations with Consequential Changes in the Magnetic Properties of Fe(III) Complexes".

[This corrects the article DOI: 10.1021/acsomega.8b03400.].

Temperature-Induced Single-Crystal-to-Single-Crystal Transformations with Consequential Changes in the Magnetic Properties of Fe(III) Complexes.

The present article deals with an one-to-one structure-property correspondence of a dinuclear iron complex, [Dipic(H2O)FeOH]2·H2O (1) (Dipic = pyridine-2,6-dicarboxylic acid). Variable-temperature X-ray single-crystal structural analysis confirms a phase transition of complex 1 to complex 2 ([Dipic(H2O)FeOH]2) at 120 °C. Further, single-crystal-to-single-crystal (SCSC) transformation was monitored by temperature-dependent single crystal X-ray diffraction, powder X-ray diffraction, time-dependent Fourier-transform infrared spectroscopy, and differential scanning calorimetry. SCSC transformation brings the change in space group of single crystal. Complex 1 crystallizes in the C2/c space group, whereas complex 2 crystallizes in the Pi̅ space group. SCSC transformation brings the change in packing diagram as well. Complex 1 shows two-dimensional network through H-bonding, whereas the packing diagram of complex 2 shows a zigzag-like arrangement. Phase transformation not only fetches structural changes but also in the magnetic properties. Difference in Fe-O-Fe bond angles of two complexes creates notable variation in their antiferromagnetic interactions with adjacent metal centers.