ABSTRACT
Perovskite-derived hybrid platinum iodides with the general formula A2PtIVI6 (A = formamidinium FA and guanidinium GUA) accommodate excess I2 to yield hydrogen-bond-stabilized compounds where the I2 forms catenates with I- anions on the PtI6 octahedra.
ABSTRACT
We describe the solid-state structural evolution in four hybrid hexaiodoplatinate(IV) compounds, demonstrating the increasingly important role that extended hydrogen bonding plays in directing the structure across the series. The compounds are A2PtI6, where A is one of the following amines: ammonium, NH4+; methylammonium, CH3NH3+; formamidinium, CH(NH2)2+; guanidinium, C(NH2)3+. These are closely related in structure and properties to the hybrid halide perovskites of lead(II) that have recently established their prowess in optoelectronics. The first three of these compounds crystallize in the vacancy-ordered double perovskite A2Ptâ¡I6 (â¡ indicates a vacant site) structure in the K2PtCl6 archetype, despite the relatively large perovskite tolerance factors involved. The last compound, (GUA)2PtI6, crystallizes in a vacancy-ordered variant of the hexagonal CsNiCl3 structure: the K2MnF6 structure. A combination of solid-state 195Pt and 1H NMR spectroscopy and detailed density functional theory calculations helps to reveal structural trends and establish the hydrogen-bonding tendencies. The calculations and measured optical properties support the surprising observation in these iodosalt compounds that, for smaller A cations, the conduction bands are considerably disperse, despite lacking extended I-Pt-I connectivity.
ABSTRACT
We demonstrate a novel crosslinked disulfide system as a cathode material for Li-S cells that is designed with the two criteria of having only a single point of S-S scission and maximizing the ratio of S-S to the electrochemically inactive framework. The material therefore maximizes theoretical capacity while inhibiting the formation of polysulfide intermediates that lead to parasitic shuttle. The material we report contains a 1:1 ratio of S:C with a theoretical capacity of 609â mAh g-1 . The cell gains capacity through 100â cycles and has 98 % capacity retention thereafter through 200â cycles, demonstrating stable, long-term cycling. Raman spectroscopy confirms the proposed mechanism of disulfide bonds breaking to form a S-Li thiolate species upon discharge and reforming upon charge. Coulombic efficiencies near 100 % for every cycle, suggesting the suppression of polysulfide shuttle through the molecular design.
ABSTRACT
Main-group halide perovskites have generated much excitement of late because of their remarkable optoelectronic properties, ease of preparation, and abundant constituent elements, but these curious and promising materials differ in important respects from traditional semiconductors. The distinguishing chemical, structural, and electronic features of these materials present the key to understanding the origins of the optoelectronic performance of the well-studied hybrid organic-inorganic lead halides and provide a starting point for the design and preparation of new functional materials. Here we review and discuss these distinguishing features, among them a defect-tolerant electronic structure, proximal lattice instabilities, labile defect migration, and, in the case of hybrid perovskites, disordered molecular cations. Additionally, we discuss the preparation and characterization of some alternatives to the lead halide perovskites, including lead-free bismuth halides and hybrid materials with optically and electronically active organic constituents.
ABSTRACT
Two new compounds containing tetrathiafulvalene (TTF) cations with extended and discrete anions based on Bi and I are reported. The compound (TTF)BiI4 comprises [BiI2I4/2]- chains of edge-shared octahedra that are interspersed with stacks of TTF+â¢. The compound (TTF)4BiI6 has mixed-valence stacks of TTF and TTF+⢠and discrete molecules of TTF+⢠separated by discrete [BiI6]-3 anions. The optical and electrical transport properties of these compounds are reported. Due to the mixed-valence stacks of TTF, (TTF)4BiI6 is the significantly better electrical conductor than (TTF)BiI4, despite the discrete nature of the inorganic moiety.
ABSTRACT
We report the preparation and X-ray crystallographic characterization of the first crystalline homoatomic polymer chain, which is part of a semiconducting pyrroloperylene-iodine complex. The crystal structure contains infinite polyiodide I∞ (δ-) . Interestingly, the structure of iodine within the insoluble, blue starch-iodine complex has long remained elusive, but has been speculated as having infinite chains of iodine. Close similarities in the low-wavenumber Raman spectra of the title compound and starch-iodine point to such infinite polyiodide chains in the latter as well.
ABSTRACT
We report the interface energetics of decacyclene trianhydride (DTA) monolayers on top of two distinct model surfaces, namely, Au(111) and Ag(111). On the latter, combined valence band photoemission and X-ray absorption measurements that access the occupied and unoccupied molecular orbitals, respectively, reveal that electron transfer from substrate to surface sets in. Density functional theory calculations confirm our experimental findings and provide an understanding not only of the photoemission and X-ray absorption spectral features of this promising organic semiconductor but also of the fingerprints associated with the interface charge transfer.
ABSTRACT
FDT and FDT-Br diradicaloids with stable coexisting close-shell and open-shell forms exhibit unconventional self-doping behavior in solid-state electronic devices that is temperature (T) tunable and reversible. The doping is strengthened by the increased T, leading to the absence of off-states (I(off)) in the transistors.
ABSTRACT
An in-depth discussion of the properties of perylene is presented. Tuning the properties of perylene by introducing nitrogens is also explored. Finally, we do not discuss the synthesis and properties of oligorylenes functionalized with dicarboxyimide bonds.
ABSTRACT
The regioselective synthesis of easily isolable pure bismethano derivatives of C60 and C70 with high steric congestion is described using 1,3-dibenzoylpropane bis-p-toluenesulfonyl hydrazone as the addend precursor. When the addition occurs at two [6,6] ring junctions within the same hexagon, bisadducts with mirror symmetry are obtained for both C60 and C70. When the addition occurs at two [5,6] ring junctions in C60, a symmetrical adduct is formed, which readily undergoes photo-oxygenation and ring opening to yield a fullerene with a hole in the cage. In this work, we also propose a simple and general system to name all of the possible [6,6] bisadduct isomers on C70.
Subject(s)
Fullerenes/chemistry , Isomerism , Models, Molecular , Molecular StructureABSTRACT
A high-yielding synthesis of a series of polyimide dendrimers, including decacyclene- and perylene-containing dendrimer D6, in which two types of polyimide dyes are present, is reported. In these constructs, the branching unit is represented by trisphenylamine, and the solubilizing chains by N-9-heptadecanyl-substituted perylene diimides. The photophysical properties of the dendrimers have been studied by absorption, steady-state, and time-resolved emission spectroscopy and pump-probe transient absorption spectroscopy. Photoinduced charge-separated (CS) states are formed on the femtosecond timescale upon visible excitation. In particular, in D6, two different CS states can be formed, involving different subunits that decays independently with different lifetimes (ca. 10-100â ps).
ABSTRACT
A stable organic diradicaloid with an intermolecular quintet at room temperature as a polycrystalline solid is studied. The conclusion is supported by the observation of the ΔMs = ±2 forbidden transition, electron spin resonance (ESR) simulations, and density functional theory (DFT) calculations. In addition, the molecule, as the active component of a device, is an outstanding near-infrared photodetector with detectivity over 10(11) cm Hz(1/2) W(-1) at 1200 nm.
ABSTRACT
While recent improvements in the reported peak power conversion efficiency (PCE) of hybrid organic-inorganic perovskite solar cells have been truly astonishing, there are many fundamental questions about the electronic behavior of these materials. Here we have studied a set of electronic devices employing methylammonium lead iodide ((MA)PbI3) as the active material and conducted a series of temperature-dependent measurements. Field-effect transistor, capacitor, and photovoltaic cell measurements all reveal behavior consistent with substantial and strongly temperature-dependent polarization susceptibility in (MA)PbI3 at temporal and spatial scales that significantly impact functional behavior. The relative PCE of (MA)PbI3 photovoltaic cells is observed to reduce drastically with decreasing temperature, suggesting that such polarization effects could be a prerequisite for high-performance device operation.
ABSTRACT
This Introductory Lecture is intended to provide a background to Faraday Discussion 174: "Organic Photonics and Electronics" and will consist of a chronological, subjective review of organic electronics. Starting with "ancient history" (1888) and history (1950-present), the article will take us to the present. The principal developments involved the processes of charge carrier generation and charge transport in molecular solids, starting with insulators (photoconductors) and moving to metals, to semiconductors and ending with the most popular semiconductor devices, such as organic light-emitting diodes (OLEDs), organic field effect transistors (OFETs) and organic photovoltaics (OPVs). The presentation will be from an organic chemistry/materials point of view.
ABSTRACT
We report the synthesis, characterization, and application of novel zwitterions. The zwitterionic structures consist of a positively charged cyanine and negatively charged dienolate moieties, confirmed by experimental observations and theoretical calculations. Single crystal X-ray studies revealed that BIT-(NPh)2 is a coplanar molecule that forms 1-D chains via π-π interactions. In contrast, BIT-(NHexyl)2 is a twisted molecule with a dihedral angle of 78° between the charged planes. In charge transport studies, thin films of the flat zwitterion show semiconducting properties, with a hole mobility of 2.1 × 10(-4) cm(2) V(-1) s(-1) while the twisted zwitterion is a high resistivity insulator.