Tetrahedral molecular geometry

About: Tetrahedral molecular geometry is a research topic. Over the lifetime, 1795 publications have been published within this topic receiving 30706 citations.

Importance of out-of-state spin-orbit coupling for slow magnetic relaxation in mononuclear Fe(II) complexes.

Abstract: Two mononuclear high-spin FeII complexes with trigonal planar ([FeII(N(TMS)2)2(PCy3)] (1) and distorted tetrahedral ([FeII(N(TMS)2)2(depe)] (2) geometries are reported (TMS = SiMe3, Cy = cyclohexyl, depe = 1,2-bis(diethylphosphino)ethane). The magnetic properties of 1 and 2 reveal the profound effect of out-of-state spin–orbit coupling (SOC) on slow magnetic relaxation. Complex 1 exhibits slow relaxation of the magnetization under an applied optimal dc field of 600 Oe due to the presence of low-lying electronic excited states that mix with the ground electronic state. This mixing re-introduces orbital angular momentum into the electronic ground state via SOC, and 1 thus behaves as a field-induced single-molecule magnet. In complex 2, the lowest-energy excited states have higher energy due to the ligand field of the distorted tetrahedral geometry. This higher energy gap minimizes out-of-state SOC mixing and zero-field splitting, thus precluding slow relaxation of the magnetization for 2.

Ultrafast structural rearrangements in the MLCT excited state for copper(I) bis-phenanthrolines in solution.

Abstract: Ultrafast excited-state structural dynamics of [Cu(I)(dmp)(2)](+) (dmp = 2,9-dimethyl-1,10-phenanthroline) have been studied to identify structural origins of transient spectroscopic changes during the photoinduced metal-to-ligand charge-transfer (MLCT) transition that induces an electronic configuration change from Cu(I) (3d(10)) to Cu(II) (3d(9)). This study has important connections with the flattening of the Franck-Condon state tetrahedral geometry and the ligation of Cu(II)* with the solvent observed in the thermally equilibrated MLCT state by our previous laser-initiated time-resolved X-ray absorption spectroscopy (LITR-XAS) results. To better understand the structural photodynamics of Cu(I) complexes, we have studied both [Cu(I)(dmp)(2)](+) and [Cu(I)(dpp)(2)](+) (dpp = 2,9-diphenyl-1,10-phenanthroline) in solvents with different dielectric constants, viscosities, and thermal diffusivities by transient absorption spectroscopy. The observed spectral dynamics suggest that a solvent-independent inner-sphere relaxation process is occurring despite the large amplitude motions due to the flattening of the tetrahedral coordinated geometry. The singlet fluorescence dynamics of photoexcited [Cu(I)(dmp)(2)](+) were measured in the coordinating solvent acetonitrile, using the fluorescence upconversion method at different emission wavelengths. At the bluest emission wavelengths, a prompt fluorescence lifetime of 77 fs is attributed to the excited-state deactivation processes due to the internal conversion and intersystem crossing at the Franck-Condon state geometry. The differentiation between the prompt fluorescence lifetime with the tetrahedral Franck-Condon geometry and that with the flattened tetrahedral geometry uncovers an unexpected ultrafast flattening process in the MLCT state of [Cu(I)(dmp)(2)](+). These results provide guidance for future X-ray structural studies on ultrafast time scale, as well as for synthesis toward its applications in solar energy conversion.

Polymorphism of Zn[Au(CN)2]2 and Its Luminescent Sensory Response to NH3 Vapor

Abstract: Four polymorphic forms of the complex Zn[Au(CN)2]2 have been synthesized and both structurally and spectroscopically characterized. In each of the four polymorphs, a zinc center in a tetrahedral geometry with a Au(CN)2− unit at each tetrahedral vertex is observed. All four structures contain three-dimensional networks based on corner-sharing tetrahedra. Because of the long Au(CN)2− bridging unit, the extra space not occupied by one network is filled by two to five additional interpenetrated networks. Short gold−gold bonds with lengths ranging from 3.11 to 3.33 A hold the interpenetrated networks together. Three of the four polymorphs are luminescent, having solid-state emissions with wavelengths ranging from 390 to 480 nm. A linear correlation between the emission energy and the gold−gold distance was observed. Upon exposure to ammonia vapor, the polymers altered their structures and emission energies, with the emission wavelength shifting to 500 nm for {Zn(NH3)2[Au(CN)2]2}, which adopts a two-dimensional...

A local mode model for tetrahedral molecules

Abstract: A three parameter coupled Morse oscillator model fitted to the known stretching vibrational energy levels is used to predict the energies of all stretching overtone bands with total quantum number ν ⩽ 5> for the molecules CH4, SiH4, GeH4 and their deuterium and 13C isotopic substituents. Close local mode degeneracies, with splittings of 3 cm-1 or less, are predicted at the highest energies for all molecules except CD4. Such degeneracies prevail at all excitation levels for SiH4 and GeH4, but those for ν ⩽ 3> are removed by deuterium substitution. The overtone splitting patterns of different molecules and the effects of isotopic substitution are rationalized by means of a correlation diagram, in which the ratio of bond anharmonicity to interbond coupling strength is used to rank the molecules on a scale running from local mode to harmonic normal mode limits. The ranking by local mode character is GeH4 > SiH4 > GeD4 > CH4 > SiD4 > CD4. A model intensity calculation for CH4 confirms the local mode picture wi...