Barry A. Blight

Luminescent triarylboron-functionalized zinc carboxylate metal-organic framework.

A luminescent triarylboron ligand functionalized with three carboxylic groups has been synthesized and fully characterized. Its use in boron-containing metal-organic frameworks (B-MOFs) has been demonstrated by the synthesis and isolation of a Zn(II)B-MOF compound (B-MOF-1). The crystals of B-MOF-1 belong to the cubic space group F432 with 8-fold interpenetrated networks and ∼21% void space. B-MOF-1 exhibits blue fluorescence and is capable of modest gas sorption of N(2), argon, and CO(2).

Selective activation of lanthanide luminescence with triarylboron-functionalized ligands and visual fluoride indicators

Two triarylboron-functionalized carboxylate ligands have been found to be highly effective in selective activation of Tb(III) and Eu(III) emission and enable the use of the Tb(III) and Eu(III) complexes as highly effective luminescent indicators for F(-) and CN(-) in solution and on a solid substrate.

Triarylboryl-functionalized dibenzoylmethane and its phosphorescent platinum(II) complexes

An acetylacetonato derivative ligand, dibenzoylmethane (dbm), has been functionalized with a dimesitylboryl group. Phosphorescent N^C-chelate Pt(II) compounds with the new molecule as an ancillary ligand have been achieved and used as effective turn-on phosphorescent sensors for fluoride ions under air.

Triarylboron-Functionalized Cu(II) Carboxylate Paddlewheel Complexes

The assembly of two copper(II)-carboxylate dimer complexes appended with four peripheral triarylborane functionalities has been achieved. Complex stabilities in the presence of fluoride are examined.

Sensitizing Tb(III) and Eu(III) emission with triarylboron functionalized 1,3-diketonato ligands.

Four BMes2Ar (Mes = mesityl, Ar = phenyl or duryl) functionalized 1,3-diketonato ligands have been investigated for use in selective sensitization of Tb(III) and Eu(III) emission. These ligands have the general formula of [R1C(O)CR2C(O)R3](-) (R1 = Ph, R2 = H, R3 = p-Ph-BMes2, L1; R1 = R3 = p-Ph-BMes2, R2 = H, L2; R1 = R3 = Me, R2 = p-Ph-BMes2, L3; R1 = R3 = Me, R2 = p-duryl-BMes2, L4) and belong to class I (L1 and L2) and class II (L3 and L4), respectively. In class I, the boron unit is conjugated with the phenyl linker and the diketone backbone, while in class II, the boron unit, the linker unit, and the diketone unit are nonconjugated with a mutually orthogonal arrangement. To understand the impact of the location of the BMes2Ar unit on the electronic properties of the 1,3-diketone molecules and their ability in activating lanthanide emission, the difluoroboron chelate compounds (1-BF2 to 4-BF2) of ligands L1-L4 were synthesized and examined. The class I ligands were effective in activating Eu(III) emission, while the class II ligands were effective in activating Tb(III) emission. Four Ln(III) complexes, 1Eu, 2Eu, 3Tb, and 4Tb, based on the L1-L4 ligands, respectively, were prepared and examined. The emission quantum efficiency of 1Eu and 2Eu is low (Φ(Eu) ≤ 0.01 in THF, 0.07-0.13 in the solid state), but can be greatly enhanced by the addition of fluoride ions. In contrast, the complex 4Tb has a moderate emission efficiency (Φ(Tb) = 0.14 in THF, 0.47 in the solid state) and experiences a distinct emission quenching upon the addition of fluoride. The selective sensitization of Eu(III) and Tb(III) by L1-L4 and the distinct luminescent response of their Ln(III) complexes toward fluoride ions are caused by the distinct intraligand charge transfer transitions of the two different classes of ligands involving the BMes2 unit.

Stability of [2]pseudorotaxanes templated through second-sphere coordination.

A series of nine trans-dichlorobis(pyridine)palladium(II) complexes were prepared (2a-i), containing different 4-substituted pyridine co-ligands. The association constants between these Pd-complexes and 1 were measured, and their values plotted against corresponding sigma(p) degrees values. Measurement of the hydrogen bond acceptor capability of the chloride co-ligands revealed the presence of a linear free energy relationship between the electronic induction of a given 4-substituted pyridine co-ligand and the subsequent complexation strength in [2]pseudorotaxane formation. These trends also extended to trans-dibromobis(pyridine)palladium(II) (3a-e) and trans- dichlorobis(pyridine)platinum(II) complexes (5a-e) when plotted against sigma(p) degrees values. In addition, solid-state structures of three [2]pseudorotaxanes (1.2h, 1.2i, and 1.5e) were determined by single crystal X-ray diffraction further confirming the viability of this template in forming interpenetrated molecular architectures.