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 [Cu(μ-OH)(μ-Pyz)] (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.

A Silver-Based Integrated System Showing Mutually Inclusive Super Protonic Conductivity and Photoswitching Behavior.

Photoinduced electricity and proton conductivity led fuel cells have emerged, , as highly promising systems for unconventional energy harvesting. Notwithstanding their individual presence with widely acclaimed results, an integrating system with mutually inclusive manifestation of both features has hitherto not been reported in the literature. To achieve this objective, our approach was to design a ligand system incorporating prerequisite features of both systems, like extended conjugation instigating photophysical activity and functional groups facilitating ionic conduction.

Synergistic Experimental and Theoretical Studies of Luminescent-Magnetic LnZn Clusters.

The present work is part of our ongoing quest for developing functional inorganic complexes using unorthodox pyridyl-pyrazolyl-based ligands. Accordingly, we report herein the synthesis, characterization, and luminescence and magnetic properties of four 3d-4f mixed-metal complexes with a general core of LnZn (Ln = Dy, Gd, Tb, and Eu). In stark contrast to the popular wisdom of using a compartmental ligand with separate islands of and coordinating sites for selective coordination, we have vindicated our approach of using a ligand with overcrowded N-coordinating sites that show equal efficiency with both 4f and 3d metals toward multinuclear cage-cluster formation.

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.

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.

Hysteretic four-step spin-crossover in a 3D Hofmann-type metal-organic framework with aromatic guest.

A new Hofmann-type metal-organic framework with bent pillar ligand, [Fe(dpoda){Ag(CN)}] (dpoda = 2,5-di-(pyridyl)-1,3,4-oxadiazole), was synthesized. Four-, two- and one-step spin-crossover (SCO) properties were obtained by using different sizes of aromatic guests. Most importantly, hysteretic four-step SCO behaviour with the sequence of LS ↔ HSLS↔ HSLS↔ HSLS↔ HS is observed for the first time.

A square antiprism dysprosium single-ion magnet with an energy barrier over 900 K.

Herein we report a stable and high-performance Dy(iii) single-ion magnet (SIM) showing an energy barrier of 944 K under zero dc field, with an open hysteresis loop up to 6 K. To the best of our knowledge, this is the highest energy barrier for a square antiprism as well as phosphine oxide based Dy-SIMs, reported so far.

Construction of Polynuclear Lanthanide (Ln = Dy(III), Tb(III), and Nd(III)) Cage Complexes Using Pyridine-Pyrazole-Based Ligands: Versatile Molecular Topologies and SMM Behavior.

Employment of two different pyridyl-pyrazolyl-based ligands afforded three octanuclear lanthanide(III) (Ln = Dy, Tb) cage compounds and one hexanuclear neodymium(III) coordination cage, exhibiting versatile molecular architectures including a butterfly core. Relatively less common semirigid pyridyl-pyrazolyl-based asymmetric ligand systems show an interesting trend of forming polynuclear lanthanide cage complexes with different coordination environments around the metal centers. It is noteworthy here that construction of lanthanide complex itself is a challenging task in a ligand system as soft N-donor rich as pyridyl-pyrazol.

Synthesis, crystal structure and optical properties of a naphthylbisimide-Ni complex: a framework on TiO2 for visible light H2 production.

A novel ligand N,N'-di-(3-(pyridin-2-yl)-1H-pyrazole-5-carbohydrazide) naphthalene 1,4,5,8-tetracarboxylic acid bisimide (PPNB) and its nickel (ii) complex (Ni-PPNB) were synthesized and systematically characterized. Both the molecules show higher sensitization activity on the TiO2 semiconducting system. These composites have interesting photophysical properties as they enable photocatalytic hydrogen production from water with a sacrificial electron donor (SED) using visible light, while neither component alone is able to do so.

Azide-functionalized lanthanide-based metal-organic frameworks showing selective CO2 gas adsorption and postsynthetic cavity expansion.

We report herein selective CO2 gas adsorption by two azide-functionalized lanthanide-based metal-organic frameworks (MOFs). This work also demonstrates that azide-functionalized MOFs can be used for postsynthetic cavity expansion, further corroborated by enhanced gas-sorption data.

Tetra-kis-(μ-3-meth-oxy-benzoato-κO:O)bis[acetonitrilecopper(II)].

The centrosymmetric binuclear Cu(II) title complex, [Cu(2)(C(8)H(7)O(3))(4)(CH(3)CN)(2)], has a paddle-wheel-type structure [Cu-Cu distance = 2.6433 (3) Å]. Each Cu(II) ion is coordin-ated by four O atoms from two 3-meth-oxy-benzoate ligands and one acetonitrile N atom in a square-pyramidal geometry.