Abstract The chemical dynamics of the elementary reaction of ground state atomic silicon (Si;3P) with germane (GeH4; X1A1) were unraveled in the gas phase under single collision condition at a collision energy of 11.8±0.3 kJ mol−1exploiting the crossed molecular beams technique contemplated with electronic structure calculations. The reaction follows indirect scattering dynamics and is initiated through an initial barrierless insertion of the silicon atom into one of the four chemically equivalent germanium‐hydrogen bonds forming a triplet collision complex (HSiGeH3;3i1). This intermediate underwent facile intersystem crossing (ISC) to the singlet surface (HSiGeH3;1i1). The latter isomerized via at least three hydrogen atom migrations involving exotic, hydrogen bridged reaction intermediates eventually leading to the H3SiGeH isomeri5. This intermediate could undergo unimolecular decomposition yielding the dibridged butterfly‐structured isomer1p1(Si(μ‐H2)Ge) plus molecular hydrogen through a tight exit transition state. Alternatively, up to two subsequent hydrogen shifts toi6andi7, followed by fragmentation of each of these intermediates, could also form1p1(Si(μ‐H2)Ge) along with molecular hydrogen. The overall non‐adiabatic reaction dynamics provide evidence on the existence of exotic dinuclear hydrides of main group XIV elements, whose carbon analog structures do not exist.
more »
« less
Approaching Rapid, High‐Resolution, Large‐Area Patterning of Semiconducting Polymers Using Projection Photothermal Lithography
Abstract Patterned semiconductors are essential for the fabrication of nearly all electronic devices. Over the last two decades, semiconducting polymers (SPs) have received enormous attention due to their potential for creating low‐cost flexible electronic devices, while development of scalable patterning methods capable of producing sub‐μm feature sizes has lagged. A novel method for patterning SPs termed Projection Photothermal Lithography (PPL) is presented. A lab scale PPL microscope is built and it is demonstrated that rapid (≈4 cm2h−1) and large single exposure area (≈0.69 mm2) sub‐μm patterns can be obtained optically. Polymer domains are selectively removed via a photo‐induced temperature gradient that enables dissolution. It is hypothesized that commercial‐scale patterning with a throughput of≈5 m2h−1and resolution of<1μm could be realized through optimization of optical components.
more »
« less
- Award ID(s):
- 1636385
- PAR ID:
- 10445344
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Advanced Materials Technologies
- Volume:
- 7
- Issue:
- 6
- ISSN:
- 2365-709X
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Abstract Anionic ancillary ligands play a critical role in the construction of rare earth (RE) metal complexes due to the large influence on the stability of the molecule and engendering emergent electronic properties that are of interest in a plethora of applications. Supporting ligands comprising oxygen donor atoms are highly pursued in RE chemistry owing to the high oxophilicity innate to these ions. The scarcely employed bis(acyl)phosphide (BAP) ligands feature oxygen coordination sites and contain a phosphide backbone rendering it attractive for RE‐coordination chemistry. Here, we integrate bis(mesitoyl)phosphide (mesBAP) as an ancillary ligand into REIIIchemistry to generate the first dinuclear trivalent RE complexes containing BAP ligands; [{mesBAP}2RE(THF)(μ‐Cl)]2(RE=Y, (1), Gd (2), and Dy (3); THF=tetrahydrofuran). Each RE center is ligated to two monoanionicmesBAP ligands, one THF molecule and one chloride ion. All three molecules were characterized through single‐crystal X‐ray diffraction,31P NMR, IR and UV‐Vis spectroscopy.31P,1H and13C NMR on the diamagnetic yttrium congener1confirm asymmetric ligand coordination. DFT calculations conducted on2provided insight into the electronic structure. The magnetic properties of2and3were investigated via SQUID magnetometry. The GdIIIions exhibit weak antiferromagnetic coupling, corroborated by DFT results.more » « less
-
Abstract Three binuclear species [LCoIII2(μ‐Pz)2](ClO4)3(1), [LNiII2(CH3OH)2Cl2]ClO4(2), and [LZnII2Cl2]PF6(3) supported by the deprotonated form of the ligand 2,6‐bis[bis(2‐pyridylmethyl) amino‐methyl]‐4‐methylphenol were synthesized, structurally characterized as solids and in solution, and had their electrochemical and spectroscopic behavior established. Species1–3had their water reduction ability studied aiming to interrogate the possible cooperative catalytic activity between two neighboring metal centers. Species1and2reduced H2O to H2effectively at an applied potential of −1.6 VAg/AgCl, yielding turnover numbers of 2,820 and 2,290, respectively, after 30 minutes. Species3lacked activity and was used as a negative control to eliminate the possibility of ligand‐based catalysis. Pre‐ and post‐catalytic data gave evidence of the molecular nature of the process within the timeframe of the experiments. Species1showed structural, rather than electronic cooperativity, while species2displayed no obvious cooperativity. DFT methods complemented the experimental results determining plausible mechanisms.more » « less
-
Abstract Metalation of the polynucleating ligandF,tbsLH6(1,3,5‐C6H9(NC6H3−4‐F−2‐NSiMe2tBu)3) with two equivalents of Zn(N(SiMe3)2)2affords the dinuclear product (F,tbsLH2)Zn2(1), which can be further deprotonated to yield (F,tbsL)Zn2Li2(OEt2)4(2). Transmetalation of2with NiCl2(py)2yields the heterometallic, trinuclear cluster (F,tbsL)Zn2Ni(py) (3). Reduction of3with KC8affords [KC222][(F,tbsL)Zn2Ni] (4) which features a monovalent Ni centre. Addition of 1‐adamantyl azide to4generates the bridging μ3‐nitrenoid adduct [K(THF)3][(F,tbsL)Zn2Ni(μ3‐NAd)] (5). EPR spectroscopy reveals that the anionic cluster possesses a doublet ground state (S=). Cyclic voltammetry of5reveals two fully reversible redox events. The dianionic nitrenoid [K2(THF)9][(F,tbsL)Zn2Ni(μ3‐NAd)] (6) was isolated and characterized while the neutral redox isomer was observed to undergo both intra‐ and intermolecular H‐atom abstraction processes. Ni K‐edge XAS studies suggest a divalent oxidation state for the Ni centres in both the monoanionic and dianionic [Zn2Ni] nitrenoid complexes. However, DFT analysis suggests Ni‐borne oxidation for5.more » « less
-
Abstract Reaction of Tl(OTf) with 2 equiv of bis(diisopropylamino)cyclopropenylidene (BAC) in THF results in formation of [Tl(BAC)2(OTf)] (1) in moderate yields. Subsequent reaction of1with [K][H2‐9‐BBN] ([H2‐9‐BBN]− = dihydrido 9‐boratabicyclo[3.3.1]nonane) in THF results in formation of [Tl(BAC)(μ‐H2‐9‐BBN)]2(3), also in moderate yield. Complex3is the first reported thallium borohydride. We attribute its thermal stability to the strong donor ability of the BAC co‐ligand. Both1and3exhibit trigonal pyramidal geometries about Tl+in the solid‐state, indicative of the presence of stereochemically active lone pairs. The hydride environment in3is calculated to exhibit a 3.9 ppm downfield shift attributed to spin‐orbit effects from the adjacent Tl center.more » « less
An official website of the United States government
