21 research outputs found

    Bis(trimethyl­ammonium) tetra­chlorido­diphenyl­stannate(IV)

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    The title compound, [(CH3)3NH]2[Sn(C6H5)2Cl4], consists of [(CH3)3NH]+ cations and [SnPh2Cl4]2− anions in which the Sn atom, located on a centre of inversion, is bonded to four Cl atoms and two phenyl rings, giving an octa­hedral geometry with the phenyl rings in trans positions. In the crystal, the cations and the anions are connected by N—H⋯Cl hydrogen bonds and C—H⋯Cl inter­actions

    Dicyclo­hexyl­ammonium trimethyl­bis­(hydrogen phenyl­phospho­nato)stannate(IV)

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    In the title compound, (C12H24N)[Sn(CH3)3(C6H6O3P)2], the SnMe3 residues are axially coordinated by two monodentate [PhPO3H]− anions, leading to a trigonal–bipyramidal geometry for the SnIV atom. The two [SnMe3(PhPO3H)2]− anions in the unit cell are associated into infinite chains along the a axis by O—H⋯O hydrogen bonds involving the hy­droxy group of the hydrogen phenyl­phospho­nate ion. The chains inter­act with one another via O—H⋯O hydrogen bonds along the c axis. These networks of anions assemble with the dicyclo­hexyl­ammonium ion through N—H⋯O hydrogen bonds, forming a three-dimensional network

    Bis(dicyclo­hexyl­ammonium) ÎŒ-oxalato-Îș4 O 1,O 2:O 1â€Č,O 2â€Č-bis­[aqua­(oxalato-Îș2 O 1,O 2)diphenyl­stannate(IV)]

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    The structure of the title compound, (C12H24N)2[Sn2(C6H5)4(C2O4)3(H2O)2], consists of a bischelating oxalate ion, located on an inversion center, which is linked to two SnPh2 groups. The coordination sphere of the Sn(IV) ion is completed by a monochelating oxalate anion and a water mol­ecule. The Sn(IV) atoms are thus seven-coordinated. The discrete binuclear units are further connected by hydrogen bonds, leading to a supra­molecular crystal structure. The asymmetric unit contains one half dianion and one (Cy2NH2)+ cation

    The impact of the alkyne substitution pattern and metalation on the photo-isomerization of azobenzene-based platinum(II) diynes and polyynes

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    Trimethylsilyl-protected dialkynes incorporating azobenzene linker groups, Me<sub>3</sub>SiCî—ŒCRCî—ŒCSiMe<sub>3</sub> (R = azobenzene-3,3â€Č-diyl, azobenzene-4,4â€Č-diyl, 2,5-dioctylazobenzene-4,4â€Č-diyl), and the corresponding terminal dialkynes, HCî—ŒCRCî—ŒCH, have been synthesized and characterized. The CuI-catalyzed dehydrohalogenation reaction between <i>trans</i>-[Ph­(Et<sub>3</sub>P)<sub>2</sub>PtCl] and the deprotected dialkynes in a 2:1 ratio in <sup>i</sup>Pr<sub>2</sub>NH/CH<sub>2</sub>Cl<sub>2</sub> gives the platinum­(II) diynes <i>trans</i>-[Ph­(Et<sub>3</sub>P)<sub>2</sub>PtCî—ŒCRCî—ŒCPt­(PEt<sub>3</sub>)<sub>2</sub>Ph], while the dehydrohalogenation polycondensation reaction between <i>trans</i>-[(<sup>n</sup>Bu<sub>3</sub>P)<sub>2</sub>PtCl<sub>2</sub>] and the dialkynes in a 1:1 molar ratio under similar reaction conditions affords the platinum­(II) polyynes, [−Pt­(P<sup>n</sup>Bu<sub>3</sub>)<sub>2</sub>–Cî—ŒCRCî—ŒC−]<sub><i>n</i></sub>. The materials have been characterized spectroscopically, with the diynes also studied using single-crystal X-ray diffraction. The platinum­(II) diynes and polyynes are all soluble in common organic solvents. Optical-absorption measurements show that the compounds incorporating the <i>para</i>-alkynylazobenzene spacers have a higher degree of electronic delocalisation than their <i>meta</i>-alkynylazobenzene counterparts. Reversible photoisomerization in solution was observed spectroscopically for the alkynyl-functionalized azobenzene ligands and, to a lesser extent, for the platinum­(II) complexes. Complementary quantum-chemical modeling was also used to analyze the optical properties and isomerization energetics

    Analysis of shared heritability in common disorders of the brain

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    ience, this issue p. eaap8757 Structured Abstract INTRODUCTION Brain disorders may exhibit shared symptoms and substantial epidemiological comorbidity, inciting debate about their etiologic overlap. However, detailed study of phenotypes with different ages of onset, severity, and presentation poses a considerable challenge. Recently developed heritability methods allow us to accurately measure correlation of genome-wide common variant risk between two phenotypes from pools of different individuals and assess how connected they, or at least their genetic risks, are on the genomic level. We used genome-wide association data for 265,218 patients and 784,643 control participants, as well as 17 phenotypes from a total of 1,191,588 individuals, to quantify the degree of overlap for genetic risk factors of 25 common brain disorders. RATIONALE Over the past century, the classification of brain disorders has evolved to reflect the medical and scientific communities' assessments of the presumed root causes of clinical phenomena such as behavioral change, loss of motor function, or alterations of consciousness. Directly observable phenomena (such as the presence of emboli, protein tangles, or unusual electrical activity patterns) generally define and separate neurological disorders from psychiatric disorders. Understanding the genetic underpinnings and categorical distinctions for brain disorders and related phenotypes may inform the search for their biological mechanisms. RESULTS Common variant risk for psychiatric disorders was shown to correlate significantly, especially among attention deficit hyperactivity disorder (ADHD), bipolar disorder, major depressive disorder (MDD), and schizophrenia. By contrast, neurological disorders appear more distinct from one another and from the psychiatric disorders, except for migraine, which was significantly correlated to ADHD, MDD, and Tourette syndrome. We demonstrate that, in the general population, the personality trait neuroticism is significantly correlated with almost every psychiatric disorder and migraine. We also identify significant genetic sharing between disorders and early life cognitive measures (e.g., years of education and college attainment) in the general population, demonstrating positive correlation with several psychiatric disorders (e.g., anorexia nervosa and bipolar disorder) and negative correlation with several neurological phenotypes (e.g., Alzheimer's disease and ischemic stroke), even though the latter are considered to result from specific processes that occur later in life. Extensive simulations were also performed to inform how statistical power, diagnostic misclassification, and phenotypic heterogeneity influence genetic correlations. CONCLUSION The high degree of genetic correlation among many of the psychiatric disorders adds further evidence that their current clinical boundaries do not reflect distinct underlying pathogenic processes, at least on the genetic level. This suggests a deeply interconnected nature for psychiatric disorders, in contrast to neurological disorders, and underscores the need to refine psychiatric diagnostics. Genetically informed analyses may provide important "scaffolding" to support such restructuring of psychiatric nosology, which likely requires incorporating many levels of information. By contrast, we find limited evidence for widespread common genetic risk sharing among neurological disorders or across neurological and psychiatric disorders. We show that both psychiatric and neurological disorders have robust correlations with cognitive and personality measures. Further study is needed to evaluate whether overlapping genetic contributions to psychiatric pathology may influence treatment choices. Ultimately, such developments may pave the way toward reduced heterogeneity and improved diagnosis and treatment of psychiatric disorders

    Di-&amp;#956;-hydroxido-bis[dimethyl(thiocyanato-&amp;#954;N)tin(IV)]

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    The SnIV atom in the centrosymmetric title complex, [Sn2(CH3)4(NCS)2(OH)2], adopts a distorted trigonal&amp;#8211;bipyramidal coordination environment defined by two methyl C atoms and one bridging hydroxide group in the equatorial plane while the other bridging hydroxide group and the N atom of the thiocyanate anion are in the apical &amp;gt;positions. The dinuclear species are linked through O&amp;#8212;H...S and C&amp;#8212;H... S hydrogen-bonding interactions into a three-dimensional network

    Dichloridodiphenylbis(thiourea-&#954;S)tin(IV)

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    The title compound, [Sn(C6H5)2Cl2(CH4N2S)2], has been obtained from the reaction between Sn(C6H5)2Cl2 and SC(NH2)2. The asymmetric unit consists of one half of the molecular unit, the remainder generated by a twofold rotation axis located along the Cl&#8212;Sn&#8212;Cl bonds. The SnIV atom is coordinated by two phenyl groups, two Cl atoms and two thiourea ligands in an all trans octahedral C2Cl2S2 environment. Individual molecules are connected through N&#8212;H...Cl hydrogen bonds, leading to a three-dimensional network structure. Intramolecular N&#8212;H...Cl hydrogen bonds are also present

    Tetramethylammonium aquatrichloridooxalatostannate(IV) monohydrate

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    The SnIV atom in the title compound, [(CH3)4N][Sn(C2O4)Cl3(H2O)]&#183;H2O, obtained from the reaction between SnCl4 and [(CH3)4N]2C2O4&#183;2H2O, is six-coordinated by three Cl atoms, an O atom of a water molecule and two O atoms from an asymmetrically chelating oxalate anion. The environment around the SnIV atom is distorted octahedral. The anions are connected by the lattice water molecule through O&#8212;H...O hydrogen bonds, leading to a layered structure parallel to (010). The cations are located between these layers and besides Coulombic forces are connected to the anionic layers through weak C&#8212;H...O and C&#8212;H...Cl interactions

    Experimental and Theoretical Investigation for the Level of Conjugation in Carbazole-Based Precursors and Their Mono‑, Di‑, and Polynuclear Pt(II) Complexes

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    A series of trimethylsilyl-protected monoalkynes (Me<sub>3</sub>SiCî—ŒC–R) and bis-alkynes (Me<sub>3</sub> SiCî—ŒC–R–Cî—ŒCSiMe<sub>3</sub>) incorporating carbazole spacer groups (R = carbazole-2-yl, carbazole-3-yl, carbazole-2,7-diyl, <i>N</i>-(2-ethylhexyl)­carbazole-2,7-diyl, carbazole-3,6-diyl, <i>N</i>-(2-ethylhexyl)­carbazole-3,6-diyl), together with the corresponding terminal monoalkynes (H–Cî—ŒC–R) and bis-alkynes (H–Cî—ŒC–R–Cî—ŒC–H), have been synthesized and characterized. The CuI-catalyzed dehydrohalogenation reaction between <i>trans</i>-[(Ph)­(Et<sub>3</sub>P)<sub>2</sub>PtCl], <i>trans</i>-[(Et<sub>3</sub>P)<sub>2</sub>PtCl<sub>2</sub>], and <i>trans</i>-[(P<sup><i>n</i></sup>Bu<sub>3</sub>)<sub>2</sub>PtCl<sub>2</sub>] and the terminal alkynes in <sup><i>i</i></sup>Pr<sub>2</sub>NH/CH<sub>2</sub>Cl<sub>2</sub> affords a series of Pt­(II) mono- and diynes, while the dehydrohalogenation polycondensation reactions with <i>trans</i>-[(P<sup><i>n</i></sup>Bu<sub>3</sub>)<sub>2</sub>PtCl<sub>2</sub>] under similar reaction conditions yields four Pt­(II) poly-ynes of the form <i>trans</i>-[(P<sup><i>n</i></sup>Bu<sub>3</sub>)<sub>2</sub>Pt–Cî—ŒC–R–Cî—ŒC−]<sub><i>n</i></sub>. The acetylide-functionalized carbazole ligands and the mono-, di-, and polynuclear Pt­(II) σ-acetylide complexes have been characterized spectroscopically, with a subset analyzed using single-crystal X-ray diffraction. The Pt­(II) mono-, di-, and poly-ynes incorporating the carbazole spacers are soluble in common organic solvents, and solution absorption spectra show a consistent red-shift between the 2- and 2,7- as well as 3- and 3,6-carbazole complexes. Computational modeling is used to explain the observed spectral shifts, which are related to the enhanced electronic delocalization in the latter systems. These results also indicate that the inclusion of carbazole-2,7-diyl units into rigid-rod organometallic polymers should enhance electronic transport along the chains

    Long-Range Intramolecular Electronic Communication in Bis(ferrocenylethynyl) Complexes Incorporating Conjugated Heterocyclic Spacers: Synthesis, Crystallography, and Electrochemistry

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    A new series of bis­(ferrocenylethynyl) complexes, <b>3</b>–<b>7</b>, and a mono­(ferrocenylethynyl) complex, <b>8</b>, have been synthesized incorporating conjugated heterocyclic spacer groups, with the ethynyl group facilitating an effective long-range intramolecular interaction. The complexes were characterized by NMR, IR, and UV–vis spectroscopy as well as X-ray crystallography. The redox properties of these complexes were investigated using cyclic voltammetry and spectroelectrochemistry. Although there is a large separation of ∌14 Å between the two redox centers, Δ<i>E</i><sub>1/2</sub> values in this series of complexes ranged from 50 to 110 mV. The appearance of intervalance charge-transfer bands in the UV–vis–near-IR region for the monocationic complexes further confirmed effective intramolecular electronic communication. Computational studies are presented that show the degree of delocalization across the Fc–Cî—ŒC–Cî—ŒC–Fc (Fc = C<sub>5</sub>H<sub>5</sub>FeC<sub>5</sub>H<sub>4</sub>) highest occupied molecular orbital
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