Nanoscale Two-Dimensional FeII- and CoII-Based Metal-Organic Frameworks of Porphyrin Ligand for the Photodynamic Therapy of Breast Cancer.

The delivery of biocompatible reagents into cancer cells can elicit an anticancer effect by taking advantage of the unique characteristics of the tumor microenvironment (TME). In this work, we report that nanoscale two-dimensional FeII- and CoII-based metal-organic frameworks (NMOFs) of porphyrin ligand meso-tetrakis (6-(hydroxymethyl) pyridin-3-yl) porphyrin (THPP) can catalyze the generation of hydroxyl radicals (•OH) and O2 in the presence of H2O2 that is overexpressed in the TME. Photodynamic therapy consumes the generated O2 to produce a singlet oxygen (1O2). Both •OH and 1O2 are reactive oxygen species (ROS) that inhibit cancer cell proliferation. The FeII- and CoII-based NMOFs were non-toxic in the dark but cytotoxic when irradiated with 660 nm light. This preliminary work points to the potential of porphyrin-based ligands of transition metals as anticancer drugs by synergizing different therapeutic modalities.

Similarities and differences between Mn(II) and Zn(II) coordination polymers supported by porphyrin-based ligands: synthesis, structures and nonlinear optical properties.

Four coordination polymers (CPs) Mn-TMPP (1), Zn-TMPP (2), Mn-THPP (3), and Zn-THPP (4) have been synthesized and characterized (H2TMPP = meso-tetrakis (6-methylpyridin-3-yl) porphyrin; H2THPP = meso-tetrakis (6-(hydroxymethyl) pyridin-3-yl) porphyrin). The one-dimensional (1D) chain compound 1 is formed via a head-to-tail connection of the Mn-TMPP unit, wherein the central Mn2+ features a square pyramidal geometry coordinated by four N atoms from the porphyrin skeleton and one additional N atom from an adjacent Mn-TMPP unit. Compound 2 features an octahedral Zn2+ center associated with four N atoms from the porphyrin skeleton to define the equatorial plane and two additional N donors at the axial positions to give a two-dimensional (2D) CP. The 1D chain of 1 and the 2D layer of 2 possess distinctive molecular structures but nearly identical molecular arrangements in their unit cells viewed along all three crystallographic axes. By contrast, Mn- and Zn-based CPs 3 and 4 supported by the THPP ligand share both identical molecular connectivities and crystal packing. In 3/4, each Mn/Zn center is chelated by four N donors of the porphyrin interior to define the equatorial plane of an octahedron, whose axial sites are occupied by two alcoholic OH groups from a pair of trans-located pyridinemethanol moieties. The third-order nonlinear optical properties of 1-4 investigated using the Z-scan technique at 532 nm revealed reverse saturable absorption and self-focusing effects for all four CPs, with hyperpolarizability values (γ) in the range 1.42 × 10-28 esu to 7.64 × 10-28 esu. These high γ values are comparable to the best porphyrin-based molecular assemblies, demonstrating potential for these materials in optical limiting applications.

An N,N'-diethylformamide solvent-induced conversion cascade within a metal-organic framework single crystal.

Crystals of a two-dimensional (2D) metal-organic framework (MOF) [Cd3(BTB)2(DEF)4]·2(DEF)0.5 (1; BTB = benzene-1,3,5-tribenzolate; DEF = N,N'-diethylformamide) immersed in a solution of trans-1,2-bis(4-pyridyl)ethylene (BPEE) yields an interpenetrated three-dimensional (3D) MOF of [Cd3(BTB)2(BPEE)(H2O)2]·(BPEE)·xSol (2). Crystals of MOF 2, in turn, undergo a cascade conversion when immersed in DEF, yielding [Cd3(BTB)2(BPEE)1.8(DEF)0.9(H2O)0.8]·xSol (3a) over 100 seconds and [Cd3(BTB)2(BPEE)2(DEF)2]·xSol (4) after one hour, before finally shuttling back to MOF 1 after six hours.

A Heterometallic Three-Dimensional Metal-Organic Framework Bearing an Unprecedented One-Dimensional Branched-Chain Secondary Building Unit.

A heterometallic metal-organic framework (MOF) of [Cd6Ca4(BTB)6(HCOO)2(DEF)2(H2O)12]∙DEF∙xSol (1, H3BTB = benzene-1,3,5-tribenzoic acid; DEF = N,N'-diethylformamide; xSol. = undefined solvates within the pore) was prepared by solvothermal reaction of Cd(NO3)2·4H2O, CaO and H3BTB in a mixed solvent of DEF/H2O/HNO3. The compatibility of these two divalent cations from different blocks of the periodic table results in a solid-state structure consisting of an unusual combination of a discrete V-shaped heptanuclear cluster of [Cd2Ca]2Ca' and an infinite one-dimensional (1D) chain of [Cd2CaCa']n that are orthogonally linked via a corner-shared Ca2+ ion (denoted as Ca'), giving rise to an unprecedented branched-chain secondary building unit (SBU). These SBUs propagate via tridentate BTB to yield a three-dimensional (3D) structure featuring a corner-truncated P41 helix in MOF 1. This outcome highlights the unique topologies possible via the combination of carefully chosen s- and d-block metal ions with polydentate ligands.