Slater Carlton (applefuel3)

Triply-bridging bis-hydrido(borylene) and bis-borylene species of groups 6, 8 and 9 transition metals are reported. Mild thermolysis of [Fe2 (CO)9 ] with an in situ produced intermediate, generated from the low-temperature reaction of [Cp*WCl4 ] (Cp*=η5 -C5 Me5 ) and [LiBH4 ⋅THF] afforded triply-bridging bis-hydrido(borylene), [(μ3 -BH)2 H2 Cp*W(CO)2 2 Fe(CO)2 ] (1) and bis-borylene, [(μ3 -BH)2 Cp*W(CO)2 2 Fe(CO)3 ] (2). The chemical bonding analyses of 1 show that the B-H interactions in bis-hydrido (borylene) species is stronger as compared to the M-H ones. Frontier molecular orbital analysis shows a significantly larger energy gap between the HOMO-LUMO for 2 as compared to 1. In an attempt to synthesize the ruthenium analogue of 1, a similar reaction has been performed with [Ru3 (CO)12 ]. Although we failed to get the bis-hydrido(borylene) species, the reaction afforded triply-bridging bis-borylene species [(μ3 -BH)2 WCp*(CO)2 2 Ru(CO)3 ] (2'), an analogue of 2. In search for the isolation of bridging bis-borylene species of Rh, we have treated [Co2 (CO)8 ] with nido-[(RhCp*)2 (B3 H7 )], which afforded triply-bridging bis-borylene species [(μ3 -BH)2 (RhCp*)2 Co2 (CO)4 (μ-CO)] (3). All the compounds have been characterized by means of single-crystal X-ray diffraction study; 1 H, 11 B, 13 C NMR spectroscopy; IR spectroscopy and mass spectrometry. © 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.Building framework materials with desirable properties and enhanced functionalities with nanocluster/superatom complexes as building blocks remains a challenge in the field of nanomaterials. In this study, the chiral [Au1 Ag22 (S-Adm)12 ]3+ nanocluster/superatom complex (SC, in which S-Adm=1-adamantanethiol) was employed as a building block to construct the three-dimensional (3D) superatom complex inorganic framework (SCIF) materials SCIF-1 and SCIF-2 through inorganic SbF6 - linkers. SCIF-1 is racemic due to the assembly of two SC enantiomers in a single crystal. In SCIF-2, the SC enantiomers are packed in separate crystals, thus producing larger channels and a circularly polarized luminescence (CPL) response. These two 3D SCIF materials exhibit unique sensitive photoluminescence (PL) in protic solvents. Our study provides a new pathway for creating novel open-framework materials with superatom complexes and a foundation for the further development of 3D framework materials for sensing and other applications. © 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.BACKGROUND Headache after traumatic brain injury (TBI) is frequent and persistent over the first year after injury. Providers may need to focus on different symptom presentations depending on their patient's TBI severity. OBJECTIVE We evaluated headache symptoms in patients with moderate-to-severe TBI compared to patients with mild TBI and examined our data from two perspectives (1) from providers who treat individuals after TBI and manage multiple postinjury symptoms including headache, and (2) from headache specialists who see individuals after TBI to manage headache. DESIGN Prospective enrollment of individuals after TBI with telephone follow-up at 1-year postinjury. SETTING Enrollment from hospital and then community followup. PARTICIPANTS Three hundred forty-six individuals with moderate-to-severe TBI were enrolled during acute inpatient rehabilitation across seven TBI Model System Centers. One hundred eighty-nine individuals with mild TBI were enrolled within 1 week of injury at a single center. INTERVEcs. Ongoing assessment of headache and depression over time is important following TBI of any severity. © 2020 American Academy of Physical Medicine and Rehabilitation.When considered as a group, children with type 1 diabetes have subtle cognitive deficits relative to neurotypical controls. However, the neural correlates of these differences remain poorly understood. Using functional near-infrared spectroscopy (fNIRS), we investigated the brain functional activation