Spectroscopic and Photophysical Studies of Charge‐Transfer in a Cd₈ Thiolate Cluster Complex Containing a Coordinated N‐Methyl‐4,4′‐bipyridinium Ligand

Abstract

The hybrid cluster complex Cd 8 S(SPh) 15 (MeQ)·CH 3 CN (1) (MeQ + = N-methyl-4,4Ј-bipyridinium) was synthesized and characterized structurally by single-crystal X-ray diffraction analysis. The MeQ + ion is coordinated to one of the cadmium atoms of the cluster by the nitrogen atom of its pyridine

Ab Initio Analysis and Harmonic Force Fields of Gallium Nitride Nanoclusters

“…Except for the G3 method, which yields an excellent agreement with the experiment, the B3PW91 with basis sets 6-31G(d) and 6-311G(d) yields better results than all the expensive G1, G2, and CBS-4 M methods, and it yields results similar to those from the CBS-QB3. This high quality of the B3PW91 is also consistent with the recent comparisons with experiment showing excellent reproduction of experimental electronic spectra. , Similar or related procedures using B3PW91 have been widely tested in the past with energetic materials, − molecular devices, − metallic clusters, − and combined procedures of molecular dynamics and DFT , calculations. DFT improves over HF-based calculations, which in the past provided good qualitative results, , and properties can be calculated from the wave function obtained solving the Schrodinger equation.…”

“…This high quality of the B3PW91 is also consistent with the recent comparisons with experiment showing excellent reproduction of experimental electronic spectra. 54,55 Similar or related procedures using B3PW91 have been widely tested in the past with energetic materials, 56À62 molecular devices, 63À65 metallic clusters, 66À69 and combined procedures of molecular dynamics and DFT 58,70 calculations. DFT improves over HF-based calculations, which in the past provided good qualitative results, 71,72 and properties can be calculated from the wave function obtained solving the Schrodinger equation.…”

Synthesis and Structure Determination of Two Neutral Cadmium Thiophenolate Clusters

“…Compared with the corresponding absorptions of (NEt 4 )[Cd 8 S(SPh) 16 ] the spectrum of 1 is red‐shifted. Interestingly, an analogue effect was found in Cd 8 clusters where thiophenyl ligands were substituted with other molecules 6. Preliminary time‐dependent density functional molecular orbital calculations of 1 based on the structure solution from X‐ray diffraction, were performed.…”

Stepwise assembly of a semiconducting coordination polymer [Cd8S(SPh)14(DMF)(bpy)]n and its photodegradation of organic dyes

“…42,43 Their rich chemistry and well-defined atomic structures have allowed studies of size-dependent quantum confinement effects. 25,30,46 It provides a new way to control the optical and electronic properties of such clusters for applications like photocatalysis and photovoltaic cells. 25,30,46 It provides a new way to control the optical and electronic properties of such clusters for applications like photocatalysis and photovoltaic cells.…”

“…44,45 In addition, when semiconducting clusters are interlinked or counterparted with conjugated organic ligands, one would expect the band gap to narrow due to synergetic electronic coupling. 25,30,46 It provides a new way to control the optical and electronic properties of such clusters for applications like photocatalysis and photovoltaic cells. For example, ion-pair charge transfer between cluster ions of [Cd 8 S(SPh) 16 ] 2− and methyl viologen cations resulted the cluster salts with dramatically red-shift UV-visible absorptions.…”