Agus Aris Munandar, Ibukota Majapahit; Masa Jaya dan Pencapaian. Depok: Komunitas Bambu, 2008, X + 161 Pp. ISBN 979-37-31-39-7. Price: IDR 34,000 (Soft Cover).

Palladium-catalyzed cross-coupling reactions between chlorinated 1,3,5-triazines (TZ) and tetrathiafulvalene (TTF) trimethyltin derivatives afford mono- and <i>C</i>₃ symmetric tris­(TTF)-triazines as donor–acceptor compounds in which the intramolecular charge transfer (ICT) is modulated by the substitution scheme on TTF and TZ and by chemical or electrochemical oxidation. The TTF-TZ-Cl₂ and (SMe)₂TTF-TZ-Cl₂ derivatives show fully planar structures in the solid state as a consequence of the conjugation between the two units. Electrochemical and photophysical investigations, supported by theoretical calculations, clearly demonstrate that the lowest excited state can be ascribed to the intramolecular charge transfer (ICT) π­(TTF)→π*­(TZ) transition. The tris­(TTF) compound [(SMe)₂TTF]₃-TZ shows fluorescence when excited in the ICT band, and the emission is quenched upon oxidation. The radical cations TTF^+• are easily observed in all of the cases through chemical and electrochemical oxidation by steady-state absorption experiments. In the case of [(SMe)₂TTF]₃-TZ, a low energy band at 5000 cm^–1, corresponding to a coupling between TTF^+• and TTF units, is observed. A crystalline radical cation salt with the TTF-TZ-Cl₂ donor and PF₆^– anion, prepared by electrocrystallization, is described

Ab Initio Molecular Dynamics Study of an Aqueous Solution of [Fe(bpy)₃](Cl)₂ in the Low-Spin and in the High-Spin States

The mechanism of the photoinduced low-spin → high-spin spin crossover is actively being investigated in Fe(II) complexes in solution using ultrafast spectroscopies. These studies accurately inform on the reaction coordinate of the Fe(II) chromophore upon photoexcitation. However, they leave open questions regarding the role of the solvent. Here, we report the description from a fully ab initio molecular dynamics study of the structure of [Fe(bpy)₃]²⁺ in water and of the organization of its solvation shell in the low-spin and the high-spin states. In particular, the low-spin → high-spin change of states is shown to be accompanied (i) by a 0.191 Å lengthening of the Fe−N bond, in agreement with experiment, and (ii) by an increased thermal fluctuation of the molecular edifice, which both result from the weakening of the Fe−N bond. Furthermore, our results suggest that about two water molecules are expelled from the first solvation shell of [Fe(bpy)₃]²⁺, which consists of water molecules intercalated between the bpy ligands

Ab Initio Molecular Dynamics Study of an Aqueous Solution of [Fe(bpy)₃](Cl)₂ in the Low-Spin and in the High-Spin States

The mechanism of the photoinduced low-spin → high-spin spin crossover is actively being investigated in Fe(II) complexes in solution using ultrafast spectroscopies. These studies accurately inform on the reaction coordinate of the Fe(II) chromophore upon photoexcitation. However, they leave open questions regarding the role of the solvent. Here, we report the description from a fully ab initio molecular dynamics study of the structure of [Fe(bpy)₃]²⁺ in water and of the organization of its solvation shell in the low-spin and the high-spin states. In particular, the low-spin → high-spin change of states is shown to be accompanied (i) by a 0.191 Å lengthening of the Fe−N bond, in agreement with experiment, and (ii) by an increased thermal fluctuation of the molecular edifice, which both result from the weakening of the Fe−N bond. Furthermore, our results suggest that about two water molecules are expelled from the first solvation shell of [Fe(bpy)₃]²⁺, which consists of water molecules intercalated between the bpy ligands

Accurate Spin-State Energetics of Transition Metal Complexes. 1. CCSD(T), CASPT2, and DFT Study of [M(NCH)₆]²⁺ (M = Fe, Co)

Highly accurate estimates of the high-spin/low-spin energy difference Δ<i>E</i>_HL^el in the high-spin complexes [Fe­(NCH)₆]²⁺ and [Co­(NCH)₆]²⁺ have been obtained from the results of CCSD­(T) calculations extrapolated to the complete basis set limit. These estimates are shown to be strongly influenced by scalar relativistic effects. They have been used to assess the performances of the CASPT2 method and 30 density functionals of the GGA, meta-GGA, global hybrid, RSH, and double-hybrid types. For the CASPT2 method, the results of the assessment support the proposal [Kepenekian, M.; Robert, V.; Le Guennic, B. <i>J. Chem. Phys</i>. <b>2009</b>, <i>131</i>, 114702] that the ionization potential–electron affinity (IPEA) shift defining the zeroth-order Hamiltonian be raised from its standard value of 0.25 au to 0.50–0.70 au for the determination of Δ<i>E</i>_HL^el in Fe­(II) complexes with a [FeN₆] core. At the DFT level, some of the assessed functionals proved to perform within chemical accuracy (±350 cm^–1) for the spin-state energetics of [Fe­(NCH)₆]²⁺, others for that of [Co­(NCH)₆]²⁺, but none of them simultaneously for both complexes. As demonstrated through a reparametrization of the CAM-PBE0 range-separated hybrid, which led to a functional that performs within chemical accuracy for the spin-state energetics of both complexes, performing density functionals of broad applicability may be devised by including in their training sets highly accurate data like those reported here for [Fe­(NCH)₆]²⁺ and [Co­(NCH)₆]²⁺

Luminescence Saturation via Mn²⁺–Exciton Cross Relaxation in Colloidal Doped Semiconductor Nanocrystals

Colloidal Mn²⁺-doped semiconductor nanocrystals such as Mn²⁺:ZnSe have attracted broad attention for potential applications in phosphor and imaging technologies. Here, we report saturation of the sensitized Mn²⁺ photoluminescence intensity at very low continuous-wave (CW) and quasi-CW photoexcitation powers under conditions that are relevant to many of the proposed applications. Time-resolved photoluminescence measurements and kinetic modeling indicate that this saturation arises from an Auger-type nonradiative cross relaxation between an excited Mn²⁺ ion and an exciton within the same nanocrystal. A lower limit of <i>k</i> = 2 × 10¹⁰ s^–1 is established for the fundamental rate constant of the Mn²⁺(⁴T₁)-exciton cross relaxation

Persistent Bidirectional Optical Switching in the 2D High-Spin Polymer {[Fe(bbtr)₃](BF₄)₂}_∞

In the covalently linked 2D coordination network {[Fe­(bbtr)₃]­(BF₄)₂}_∞, bbtr = 1,4-di­(1,2,3-triazol-1-yl)­butane, the iron­(II) centers stay in the high-spin (HS) state down to 10 K. They can, however, be quantitatively converted to the low-spin (LS) state by irradiating into the near-IR spin allowed ⁵dd band and back again by irradiating into the visible ¹dd band. The compound shows true light-induced bistability below 100 K, thus, having the potential for persistent bidirectional optical switching at elevated temperatures

MOESM2 of Remapping of the belted phenotype in cattle on BTA3 identifies a multiplication event as the candidate causal mutation

Additional file 2. Alignment of CH240-104M22 and the reference sequence. Pairwise alignment of the BAC-clone CH240-104M22 with the bosTaurus6 reference sequence of the 6-kb candidate region showing almost complete identity

MOESM7 of Remapping of the belted phenotype in cattle on BTA3 identifies a multiplication event as the candidate causal mutation

Additional file 7. Gene interaction network. This figure illustrates the interactions between KIT (causal for the belt in pigs), ADAMTS20 (causal for the belt in mice) and TWIST2 (most likely causal for the belt in cattle) in mice. Interaction line colors are as follows: orange: predicted functional relationship, red: physical interactions, purple: co-expression; grey: phenotype (based on mouse genome informatics) and blue: participation in the same reaction within a pathway

MOESM6 of Remapping of the belted phenotype in cattle on BTA3 identifies a multiplication event as the candidate causal mutation

Additional file 6. Alignment of the repetitive elements at the beginning of the 6-kb candidate segment according to bosTaurus6 and bosTaurus8. The pairwise alignment of the reference sequence of the SINE element ART2A (bosTau6) and the LINE element BovB (bosTau8) at the beginning of the 6-kb candidate segment shows that ART2A is part of BovB

MOESM1 of Remapping of the belted phenotype in cattle on BTA3 identifies a multiplication event as the candidate causal mutation

Additional file 1. Inner candidate haplotypes detected by manual analysis of the extended confidence interval. This file shows the 60-SNP haplotypes of the extended candidate interval for all 110 animals that were used for remapping of the belt locus. SNPs that were excluded from the mapping procedure (MAF < 0.025) are marked with grey color in the first line. The black box indicates the 336-kb interval identified by Drögemüller et al. [13]. The first five haplotypes represent the most common and extended haplotypes for Belted Galloway (BGAhap1 and BGAhap2, shown in bright and dark blue), Dutch Belted (DBEhap, shown in beige) and Gurtenvieh (GUVhap1 and GUVhap2, shown in dark and bright green). Red boxes indicate common parts of these five haplotypes and represent the four inner candidate haplotypes (IC-Hap1-4, Table 3). The haplotypes of the animals that were used for remapping are shown below in the following order: (i) Belted Galloway, (ii) Dutch Belted, (iii) Gurtenvieh, (iv) a belted cross between Gurtenvieh and Pinzgauer cattle and (v) non-belted control animals