21 research outputs found
Bis(trimethylÂammonium) tetraÂchloridoÂdiphenylÂstannate(IV)
The title compound, [(CH3)3NH]2[Sn(C6H5)2Cl4], consists of [(CH3)3NH]+ cations and [SnPh2Cl4]2â anions in which the Sn atom, located on a centre of inversion, is bonded to four Cl atoms and two phenyl rings, giving an octaÂhedral geometry with the phenyl rings in trans positions. In the crystal, the cations and the anions are connected by NâHâŻCl hydrogen bonds and CâHâŻCl interÂactions
DicycloÂhexylÂammonium trimethylÂbisÂ(hydrogen phenylÂphosphoÂnato)stannate(IV)
In the title compound, (C12H24N)[Sn(CH3)3(C6H6O3P)2], the SnMe3 residues are axially coordinated by two monodentate [PhPO3H]â anions, leading to a trigonalâbipyramidal geometry for the SnIV atom. The two [SnMe3(PhPO3H)2]â anions in the unit cell are associated into infinite chains along the a axis by OâHâŻO hydrogen bonds involving the hyÂdroxy group of the hydrogen phenylÂphosphoÂnate ion. The chains interÂact with one another via OâHâŻO hydrogen bonds along the c axis. These networks of anions assemble with the dicycloÂhexylÂammonium ion through NâHâŻO hydrogen bonds, forming a three-dimensional network
Bis(dicycloÂhexylÂammonium) ÎŒ-oxalato-Îș4 O 1,O 2:O 1âČ,O 2âČ-bisÂ[aquaÂ(oxalato-Îș2 O 1,O 2)diphenylÂstannate(IV)]
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 molÂecule. The Sn(IV) atoms are thus seven-coordinated. The discrete binuclear units are further connected by hydrogen bonds, leading to a supraÂmolecular 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
Trimethylsilyl-protected
dialkynes incorporating azobenzene linker groups, Me<sub>3</sub>SiCîŒCRCîŒCSiMe<sub>3</sub> (R = azobenzene-3,3âČ-diyl, azobenzene-4,4âČ-diyl,
2,5-dioctylazobenzene-4,4âČ-diyl), and the corresponding terminal
dialkynes, HCîŒCRCîŒCH, have been synthesized and characterized.
The CuI-catalyzed dehydrohalogenation reaction between <i>trans</i>-[PhÂ(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 platinumÂ(II) diynes <i>trans</i>-[PhÂ(Et<sub>3</sub>P)<sub>2</sub>PtCîŒCRCîŒCPtÂ(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 platinumÂ(II) polyynes, [âPtÂ(P<sup>n</sup>Bu<sub>3</sub>)<sub>2</sub>âCîŒCRCîŒCâ]<sub><i>n</i></sub>. The materials have been characterized spectroscopically,
with the diynes also studied using single-crystal X-ray diffraction.
The platinumÂ(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 platinumÂ(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
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-&#956;-hydroxido-bis[dimethyl(thiocyanato-&#954;N)tin(IV)]
The SnIV atom in the centrosymmetric title complex, [Sn2(CH3)4(NCS)2(OH)2], adopts a distorted trigonal&#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 &gt;positions. The dinuclear species are linked through O&#8212;H...S and C&#8212;H... S hydrogen-bonding interactions into a three-dimensional network
Dichloridodiphenylbis(thiourea-κS)tin(IV)
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—Sn—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—H...Cl hydrogen bonds, leading to a three-dimensional network structure. Intramolecular N—H...Cl hydrogen bonds are also present
Tetramethylammonium aquatrichloridooxalatostannate(IV) monohydrate
The SnIV atom in the title compound, [(CH3)4N][Sn(C2O4)Cl3(H2O)]·H2O, obtained from the reaction between SnCl4 and [(CH3)4N]2C2O4·2H2O, 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—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—H...O and C—H...Cl interactions
Experimental and Theoretical Investigation for the Level of Conjugation in Carbazole-Based Precursors and Their Monoâ, Diâ, and Polynuclear Pt(II) Complexes
A series of trimethylsilyl-protected
monoalkynes (Me<sub>3</sub>SiCîŒCâR) and bis-alkynes
(Me<sub>3</sub> SiCîŒCâRâCîŒCSiMe<sub>3</sub>) incorporating carbazole spacer groups (R = carbazole-2-yl, carbazole-3-yl,
carbazole-2,7-diyl, <i>N</i>-(2-ethylhexyl)Âcarbazole-2,7-diyl,
carbazole-3,6-diyl, <i>N</i>-(2-ethylhexyl)Âcarbazole-3,6-diyl),
together with the corresponding terminal monoalkynes (HâCîŒCâR)
and bis-alkynes (HâCîŒCâRâCîŒCâH),
have been synthesized and characterized. The CuI-catalyzed dehydrohalogenation
reaction between <i>trans</i>-[(Ph)Â(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 PtÂ(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 PtÂ(II) poly-ynes
of the form <i>trans</i>-[(P<sup><i>n</i></sup>Bu<sub>3</sub>)<sub>2</sub>PtâCîŒCâRâCîŒCâ]<sub><i>n</i></sub>. The acetylide-functionalized carbazole
ligands and the mono-, di-, and polynuclear PtÂ(II) Ï-acetylide
complexes have been characterized spectroscopically, with a subset
analyzed using single-crystal X-ray diffraction. The PtÂ(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
A new series of bisÂ(ferrocenylethynyl)
complexes, <b>3</b>â<b>7</b>, and a monoÂ(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 UVâvis 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 âŒ14 Ă
between
the two redox centers, Î<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 UVâvisânear-IR
region for the monocationic complexes further confirmed effective
intramolecular electronic communication. Computational studies are
presented that show the degree of delocalization across the FcâCîŒCâCîŒCâFc
(Fc = C<sub>5</sub>H<sub>5</sub>FeC<sub>5</sub>H<sub>4</sub>) highest
occupied molecular orbital