Nanoscale Two-Dimensional Fe- and Co-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 Fe- and Co-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 O in the presence of HO that is overexpressed in the TME. Photodynamic therapy consumes the generated O to produce a singlet oxygen (O).

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.

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

A heterometallic metal-organic framework (MOF) of [CdCa(BTB)(HCOO)(DEF)(HO)]∙DEF∙Sol (, HBTB = benzene-1,3,5-tribenzoic acid; DEF = ,'-diethylformamide; Sol. = undefined solvates within the pore) was prepared by solvothermal reaction of Cd(NO)·4HO, CaO and HBTB in a mixed solvent of DEF/HO/HNO. 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 [CdCa]Ca' and an infinite one-dimensional (1D) chain of [CdCaCa'] that are orthogonally linked via a corner-shared Ca ion (denoted as Ca'), giving rise to an unprecedented branched-chain secondary building unit (SBU).

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.