Tris(2-pyridylborate) (Tpyb) metal complexes: synthesis, characterization, and formation of extrinsically porous materials with large cylindrical channels.

Sandwich-like metal complexes (Tpyb)2M (M = Mg, Fe, Mn) that are based on the novel t-butylphenyltris(2-pyridyl)borate ligand were prepared and fully characterized by multinuclear NMR spectroscopy, high-resolution matrix-assisted laser desorption/ionization (MALDI) mass spectrometry, and single crystal X-ray crystallography. The unique steric and electronic nature of the Tpyb ligand led to structural parameters and properties that are quite different to those of previously reported tris(pyrazolyl)borate and tris(2-pyridyl)aluminate complexes. Most importantly, depending on the crystallization procedure, supramolecular structures could be generated with relatively smaller (ca. 4-5 Å) or larger (ca. 8 Å) diameter pores propagating throughout the crystal lattice. Although the supramolecular structures are held together only by weak intermolecular C-H···π interactions, the solvent in the larger channels could be completely removed without any loss of crystallinity or degradation of the framework. Surface area and gas uptake measurements on the Mg complex further confirmed the permanent porosity, while the calculated non-localized density functional theory (NLDFT) pore diameter of 8.6 Å proved to be in excellent agreement with that obtained from single crystal X-ray crystallography. Our new materials are remarkably thermally stable as degradation did not occur up to about 400 °C based on thermogravimetric analysis (TGA), and a sample of the Mg complex showed no loss of crystallinity even after heating to 140 °C under high vacuum for 72 h according to single crystal X-ray diffraction data.

Poly(ε-caprolactone)-based copolymers bearing pendant cyclic ketals and reactive acrylates for the fabrication of photocrosslinked elastomers.

Block copolymers of poly(ethylene glycol) and poly(ε-caprolactone) (PCL) with chemically addressable functional groups were synthesized and characterized. Ring-opening polymerization of ε-caprolactone (CL) and 1,4,8-trioxaspiro-[4,6]-9-undecanone (TSU) using α-methoxy, ω-hydroxyl poly(ethylene glycol) as the initiator afforded a copolymer with cyclic ketals being randomly distributed in the hydrophobic PCL block. At an initiator/catalyst molar ratio of 10/1 and a TSU/CL weight ratio of 1/4, a ketal-carrying copolymer (ECT2-CK) with Mn of 52 kDa and a ketal content of 15 mol.% was obtained. Quantitative side-chain deacetalization revealed the reactive ketones without noticeable polymer degradation. In our study, 10 mol.% of cyclic ketals were deprotected and the ketone-containing copolymer was designated as ECT2-CO. Reaction of ECT2-CO with 2-(2-(aminooxy)acetoxy)-ethyl acrylate gave rise to an acrylated product (ECT2-AC) containing an estimated 3-5 acrylate groups per chain. UV-initiated radical polymerization of ECT2-AC in dichloromethane resulted in a crosslinked network (xECT2-AC). Thermal and morphological analyses employing differential scanning calorimetry and atomic force microscopy operated in PeakForce Tapping mode revealed the semicrystalline nature of the network, which contained stiff crystalline lamellae dispersed in a softer amorphous interstitial. Macroscopic and nanoscale mechanical characterizations showed that ECT2-CK exhibited a significantly lower modulus than PCL of a similar molecular weight. Whereas ECT2-CK undergoes a plastic deformation with a distinct yield point and a cold-drawing region, xECT2-AC exhibits a compliant, elastomeric deformation with a Young's modulus of 0.5±0.1 MPa at 37°C. When properly processed, the crosslinked network exhibited shape-memory behaviors, with shape fixity and shape recovery values close to 1 and a shape recovery time of less than 4s at 37°C. In vitro studies showed that xECT2-AC films did not induce any cytotoxic effects on the cultured mesenchymal stem cells. The crosslinkable polyester copolymers can be potentially used as tissue engineering scaffolds and minimally invasive medical devices.

Nitroxide-Mediated Controlled Free Radical Polymerization of the Chelate Monomer 4-Styryl-tris(2-pyridyl)borate (StTpyb) and Supramolecular Assembly via Metal Complexation.

The reaction of 4-(dibromoboryl)styrene with 2-pyridylmagnesium chloride resulted in the formation of 4-styryl-tris(2-pyridyl)borate free acid (StTypb), a new polymerizable nonpyrazolyl "scorpionate" ligand. StTypb did not undergo self-initiated polymerization under ambient conditions and proved to slowly polymerize through standard radical polymerization at 90 °C. Nitroxide-mediated polymerization (NMP) of StTypb at 135 °C proceeded with good control, resulting in a polymer of Mn = 27400 and PDI = 1.21. The TEMPO-terminated homopolymer successfully initiated the polymerization of styrene, generating an amphiphilic block copolymer with DPn of 1200 and 78 for the PS and the StTypb block, respectively. A similar block copolymer with DPn of 29 and 20 for the PS and the StTypb block respectively was obtained in a reverse polymerization procedure from a PS macroinitiator. The self-assembly of these block copolymers was examined in selective solvents and preliminary metal complexation studies were performed.

The elusive tripodal tris(2-pyridyl)borate ligand: a strongly coordinating tetraarylborate.

Tris(2-pyridyl)borates are introduced as a new robust and tunable "scorpionate"-type ligand family. A facile synthesis of this hitherto unknown ligand and its complexation to Fe(II) are described; the optical and electrochemical properties of the resulting iron complex are compared to complexes derived from tris(pyrazolyl)borate, tris(2-pyridyl)aluminate, and corresponding charge-neutral ligands.

Weakly coordinating amphiphilic organoborate block copolymers.

Selective functionalization of polystyrene with weakly coordinating organoborate functionalities BAr(4)(-) (Ar = Ph, C(6)F(5)) has been accomplished by a polymer modification strategy. The first examples of perfluoroarylborate block copolymers have been prepared; light scattering and TEM studies confirm the formation of reverse micelles, in which the weakly coordinating anion sites are covered by a shell of "inert" polystyrene. The core of the micelles was successfully loaded with a cationic rhodium complex.

Organoboronium-functionalized polystyrenes as a new class of polycations.

The facile preparation of organoboronium polymers via spontaneous reaction of bromoborylated polystyrene with 2,2'-bipyridine is reported; these novel polycations represent an interesting alternative to commonly used ammonium-based polycations.