Open Access. Powered by Scholars. Published by Universities.®

Physical Sciences and Mathematics Commons

Open Access. Powered by Scholars. Published by Universities.®

Chemistry

PDF

William & Mary

Arts & Sciences Articles

2017

Articles 1 - 4 of 4

Full-Text Articles in Physical Sciences and Mathematics

Tetragonal Diiodotetrapyridinedicopper(I): Structure, Luminescence, And Computational Modeling, Andrew W. Kelly, Joseph V. Handy, Aaron D. Nicholas, Et Al., Robert D. Pike Nov 2017

Tetragonal Diiodotetrapyridinedicopper(I): Structure, Luminescence, And Computational Modeling, Andrew W. Kelly, Joseph V. Handy, Aaron D. Nicholas, Et Al., Robert D. Pike

Arts & Sciences Articles

We report on a new crystal modification of (CuIPy2) n (Py = pyridine), a compound first reported by White et al. In contrast to White’s orthorhombic structure, which is comprised of rhomboid iodide-bridged dimers, Cu2I2Py4, our new tetragonal crystal structure in space group P41212 is disordered and can be interpreted as either iodide-bridged dimers or helical chains. To determine the structure type, variable temperature X-ray diffraction and luminescence measurements were carried out. The photoluminescence spectrum shows a distinct cluster-centered transition at high excitation energies which is consistent with the dimer structure. DFT and TD-DFT calculations were performed to explain …


Light-Induced Photochemical Changes In Copper(I) Thiocyanate Complexes Decorated With Halopyridines: Optical Memory Manifestation, Aaron D. Nicholas, Brooke M. Otten, Gerardo Ayala, Et Al., Robert D. Pike Oct 2017

Light-Induced Photochemical Changes In Copper(I) Thiocyanate Complexes Decorated With Halopyridines: Optical Memory Manifestation, Aaron D. Nicholas, Brooke M. Otten, Gerardo Ayala, Et Al., Robert D. Pike

Arts & Sciences Articles

We report on the photoluminescence of {CuSCN(3-XPy)2}n crystals (X = Br, Cl; Py = pyridine). Laser excitation at 266 nm for CuSCN(3-BrPy)2 at 78 K results in a decrease in the luminescence intensity with increasing irradiation time. Heating the sample to 298 K and recooling to 78 K results in recovery of the original luminescence intensity, hence manifesting an optical memory effect. Laser irradiation at longer or shorter wavelengths fails to produce a reduction in emission intensity. Interestingly, CuSCN(3-ClPy)2, despite being isomorphic, does not undergo emission intensity changes regardless of laser irradiation wavelength variation. Density functional theory (DFT) and …


Metal Substitution And Solvomorphism In Alkylthiolate-Bridged Zn3 And Hgzn2 Metal Clusters, Madeline R. Hallinger, Alison C. Gerhard, Mikhaila D. Ritz, Et Al., John C. Poutsma, Robert D. Pike Oct 2017

Metal Substitution And Solvomorphism In Alkylthiolate-Bridged Zn3 And Hgzn2 Metal Clusters, Madeline R. Hallinger, Alison C. Gerhard, Mikhaila D. Ritz, Et Al., John C. Poutsma, Robert D. Pike

Arts & Sciences Articles

The impact of substituting Hg(II) for Zn(II) in a thiolate-bridged trinuclear cluster with parallels to a metallothionein metal cluster was investigated. A new solvomorph of [Zn(ZnL)2](ClO4)2 (1) (L = N-(2-pyridylmethyl)-N-(2-(ethylthiolato)-amine) and five solvomorphs of a new compound [Hg(ZnL)2](ClO4)2 (2) were characterized by single-crystal X-ray crystallography. The interplay of hydrogen bonding and aromatic-packing interactions in producing lamellar, 2D lamellar, and columnar arrangements of complex cations in the crystalline state is discussed. Both variable temperature proton nuclear magnetic resonance and electrospray ion-mass spectrometry (ESI-MS) suggest that the complex ions of 1 and 2 are the predominant solution species at …


Iodobismuthate(Iii) And Iodobismuthate(Iii)/Iodocuprate(I) Complexes With Organic Ligands, Andrew W. Kelly, Amelia M. Wheaton, Aaron D. Nicholas, Francis H. Barnes, Howard H. Patterson, Robert D. Pike Oct 2017

Iodobismuthate(Iii) And Iodobismuthate(Iii)/Iodocuprate(I) Complexes With Organic Ligands, Andrew W. Kelly, Amelia M. Wheaton, Aaron D. Nicholas, Francis H. Barnes, Howard H. Patterson, Robert D. Pike

Arts & Sciences Articles

Iodobismuthate(III) and iodobismuthate(III)/cuprate(I) complexes with chelating and bridging organic ligands are structurally characterized, including the first iodobismuthate(III) metal–organic polymers. BiIII/CuI clusters show ligand binding at copper. Diffuse reflectance spectra show UV/Vis absorptions, and DFT calculations suggest MLCT and metal–halide centered transitions.