Search

Halogen bonds constitute an important and topical class of non-covalent interaction. We report a combined X-ray diffraction, multinuclear (77Se, 31P, 13C) solid-state magnetic resonance, and computational study of a series of crystalline triphenylphosphine selenide-iodoperfluorobenzene complexes which feature P=Se⋯I-C halogen bonds. Selenium-77 chemical shifts increase due to halogen bonding with iodine and correlate with the P=Se distance, which in turn correlates with the strength of the halogen bond. (77Se, 31P) coupling constants increase in magnitude as the halogen bond weakens. This observation is understood a natural localized molecular orbital (NLMO) DFT approach which shows that contributions from the selenium lone pair orbital tend to dominate both the magnitude and trends in (77Se, 31P), with the selenium-phosphorus bonding orbital being the second largest contributor. This work suggests that couplings measured NMR spectroscopy may play an important role in the characterization of halogen bonds, in clear analogy with their role in the characterization of hydrogen bonds. [ABSTRACT FROM AUTHOR]

Reaction of 2,4,6-tris(2-pyrimidyl)-1,3,5-triazine (TPymT) with Pb(NO3)2 in aqueous medium leads to the formation of a mixture of two pseudopolymorphs, {[Pb2(TPymT)(H2O)(NO3)4]·H2O}n, 1 and [Pb2(TPymT)(NO3)4]n, 2, where TPymT molecules are coordinated with two PbII ions in a bridging bis-terpyridine fashion. We demonstrate that fast evaporation of the solvent leads exclusively to the formation of 1, while 2 was formed upon slow evaporation. The two pseudopolymorphs can be interconverted by dissolving in water upon heating and controlling the evaporation rate. [ABSTRACT FROM AUTHOR]

Reaction of 2,4,6-tris(2-pyrimidyl)-1,3,5-triazine (TPymT) with Pb(NO3)2 in aqueous medium leads to the formation of a mixture of two pseudopolymorphs, {[Pb2(TPymT)(H2O)(NO3)4]·H2O}n, 1 and [Pb2(TPymT)(NO3)4]n, 2, where TPymT molecules are coordinated with two PbII ions in a bridging bis-terpyridine fashion. We demonstrate that fast evaporation of the solvent leads exclusively to the formation of 1, while 2 was formed upon slow evaporation. The two pseudopolymorphs can be interconverted by dissolving in water upon heating and controlling the evaporation rate. [ABSTRACT FROM AUTHOR]