Crystal engineering, the ability to predict and control packing of molecular building units in solid state, has attracted much attention over past three decades owing its potential exploitation for synthesis technologically important materials. We present here development crystal-engineering strategies toward noncentrosymmetric infinite coordination networks use as second-order nonlinear optical (NLO) Work performed mainly our laboratory demonstrated that solids based on can be rationally...

A homochiral porous noninterpenetrating metal-organic framework (MOF), 1, was constructed by linking infinite 1D [Cd(mu-Cl)2]n zigzag chains with axially chiral bipyridine bridging ligands containing orthogonal secondary functional groups. The dihydroxy groups accessible via the large open channels in 1 were utilized to generate a heterogeneous asymmetric catalyst for addition of diethyzinc aromatic aldehydes afford alcohols at up 93% enantiomeric excess (ee). Control experiments dendritic...

Fe(III)-carboxylate nanoscale metal−organic frameworks (NMOFs) with the MIL-101 structure were synthesized using a solvothermal technique microwave heating. The ∼200 nm particles characterized variety of methods, including SEM, PXRD, nitrogen adsorption measurements, TGA, and EDX. By replacing percentage bridging ligand (terephthalic acid) 2-amino terephthalic acid, amine groups incorporated into framework to provide sites for covalent attachment biologically relevant cargoes while still...

Catalytically competent Ir, Re, and Ru complexes H(2)L(1)-H(2)L(6) with dicarboxylic acid functionalities were incorporated into a highly stable porous Zr(6)O(4)(OH)(4)(bpdc)(6) (UiO-67, bpdc = para-biphenyldicarboxylic acid) framework using mix-and-match synthetic strategy. The matching ligand lengths between L(1)-L(6) ligands allowed the construction of crystalline UiO-67 frameworks (metal-organic (MOFs) 1-6) that doped ligands. MOFs 1-6 isostructural to parent as shown by powder X-ray...

Metal-organic frameworks (MOFs), also known as coordination polymers, represent an interesting class of crystalline molecular materials that are synthesized by combining metal-connecting points and bridging ligands. The modular nature mild conditions for MOF synthesis have permitted the rational structural design numerous MOFs incorporation various functionalities via constituent building blocks. resulting designer shown promise applications in a number areas, including gas...

Nanoscale metal−organic frameworks (NMOFs) based on Gd3+ centers and benzenedicarboxylate benzenetricarboxylate bridging ligands were synthesized using reverse microemulsions characterized SEM, PXRD, TGA. These NMOFs exhibit extraordinarily large R1 R2 relaxivities because of the presence up to tens millions in each nanoparticle are thus efficient T1 T2 contrast agents for MRI. The can also be made highly luminescent by doping with Eu3+ or Tb3+ centers. results from this work suggest that...

Ovarian cancer is the leading cause of death among women with gynecological malignancies. Acquired resistance to chemotherapy a major limitation for ovarian treatment. We report here first use nanoscale metal–organic frameworks (NMOFs) co-delivery cisplatin and pooled small interfering RNAs (siRNAs) enhance therapeutic efficacy by silencing multiple drug (MDR) genes resensitizing resistant cells UiO NMOFs hexagonal-plate morphologies were loaded prodrug MDR gene-silencing siRNAs (Bcl-2,...

Pt-containing nanoscale coordination polymer (NCP) particles with the formula of Tb2(DSCP)3(H2O)12 (where DSCP represents disuccinatocisplatin), NCP-1, were precipitated from an aqueous solution Tb3+ ions and bridging ligands via addition a poor solvent. SEM TEM images showed that as-synthesized NCP-1 exhibited spherical morphology DLS diameter 58.3 ± 11.3 nm. stabilized against rapid dissolution in water by encapsulation shells amorphous silica. The resulting silica-coated NCP-1′...

Metal–organic frameworks (MOFs), a new class of crystalline molecular solids built from linking organic ligands with metal or metal-cluster connecting points, have recently emerged as versatile platform for developing single-site solid catalysts. MOFs been used to drive range reactions, including Lewis acid/base catalyzed redox asymmetric and photocatalysis. MOF catalysts are easily separated the reaction mixtures reuse, yet their nature introduces unprecedented chemical diversity tunability...

Abstract Advanced colorectal cancer is one of the deadliest cancers, with a 5-year survival rate only 12% for patients metastatic disease. Checkpoint inhibitors, such as antibodies inhibiting PD-1/PD-L1 axis, are among most promising immunotherapies advanced colon cancer, but their durable response remains low. We herein report use immunogenic nanoparticles to augment antitumour efficacy PD-L1 antibody-mediated immunotherapy. Nanoscale coordination polymer (NCP) core-shell carry oxaliplatin...

Pt nanoparticles of 2-3 nm and 5-6 in diameter were loaded into stable, porous, phosphorescent metal-organic frameworks (MOFs 1 2) built from [Ir(ppy)(2)(bpy)](+)-derived dicarboxylate ligands (L(1) L(2)) Zr(6)(μ(3)-O)(4)(μ(3)-OH)(4)(carboxylate)(12) secondary building units, via MOF-mediated photoreduction K(2)PtCl(4). The resulting Pt@MOF assemblies serve as effective photocatalysts for hydrogen evolution by synergistic photoexcitation the MOF electron injection nanoparticles. Pt@2 gave a...

Photodynamic therapy (PDT) is an effective anticancer procedure that relies on tumor localization of a photosensitizer followed by light activation to generate cytotoxic reactive oxygen species (e.g., 1O2). Here we report the rational design Hf–porphyrin nanoscale metal–organic framework, DBP–UiO, as exceptionally for PDT resistant head and neck cancer. DBP–UiO efficiently generates 1O2 owing site isolation porphyrin ligands, enhanced intersystem crossing heavy Hf centers, facile diffusion...

A family of isoreticular chiral metal-organic frameworks (CMOFs) the primitive cubic network topology was constructed from [Zn(4)(μ(4)-O)(O(2)CR)(6)] secondary building units and systematically elongated dicarboxylate struts that are derived Mn-Salen catalytic subunits. CMOFs 1-5 were synthesized by directly incorporating three different into under solvothermal conditions, they characterized a variety methods, including single-crystal X-ray diffraction, PXRD, TGA, (1)H NMR. Although 1 vs 2 3...

Packing them in: Based on zinc and aromatic-rich dicarboxylic acids these new coordination networks (see structure; green Cl, red O, yellow Zn, blue N, gray C) have hydrogen uptakes comparable to those of the best carbon nanotubes metal–organic frameworks. The highly interpenetrating nature points a design strategy for hydrogen-storage materials that employ an entrapment mechanism. Supporting information this article is available WWW under...

Manganese-containing nanoscale metal−organic frameworks (NMOFs) with controllable morphologies were synthesized using reverse-phase microemulsion techniques at room temperature and a surfactant-assisted procedure 120 °C microwave heating. The nanoparticles characterized variety of methods including SEM, TEM, TGA, PXRD, ICP−MS. Although the gave modest longitudinal relaxivity (r1) on per Mn basis, they provided an efficient vehicle for delivery large doses Mn2+ ions which exhibited very high...

Immunotherapy has become a promising cancer therapy, but only works for subset of patients. Immunogenic photodynamic therapy (PDT) can prime immunotherapy to increase the response rates, its efficacy is severely limited by tumor hypoxia. Here we report nanoscale metal-organic framework, Fe-TBP, as novel nanophotosensitizer overcome hypoxia and sensitize effective PDT, priming non-inflamed tumors immunotherapy. Fe-TBP was built from iron-oxo clusters porphyrin ligands sensitized PDT under...