0-D and 1-D Perovskite-like Hybrid Bismuth(III) Iodides.

Low-dimensional hybrid bismuth halide perovskites have recently emerged as a class of non-toxic alternative to lead perovskites with promising optoelectronic properties. Here, we report three hybrid bismuth(III)-iodides: 0-D (H2DAC)2Bi2I10 ⋅ 6H2O (H2DAC_Bi_I), 0-D (H2DAF)4Bi2I10 ⋅ 2I3 ⋅ 2I ⋅ 6H2O (H2DAF_Bi_I), and 1-D (H2DAP)BiI5 (H2DAP_Bi_I) (where H2DAC=trans-1,4-diammoniumcyclohexane; H2DAF=2,7-diammoniumfluorene and H2DAP=1,5-diammoniumpentane). Their synthesis, single-crystal X-ray structures, and photophysical properties are reported. The first two compounds comprise edge-sharing [Bi2I10]4- dimers, while the last compound has cis-corner-sharing 1-D chains of [BiI6]3- octahedra. Intercalation of triiodide (I3 -) and iodide (I-) ions enhance electronic coupling between the [Bi2I10]4- of H2DAF_Bi_I, leading to enhanced optical absorption, compared to H2DAC_Bi_I which lacks such intercalants. Furthermore, calorimetric and variable temperature X-ray diffraction measurements suggest a centrosymmetric to non-centrosymmetric phase transition (monoclinic P212121↔orthorhombic Pnma) of H2DAP_Bi_I at 448 K (in heating step) and at 443 K (in cooling step).

[NH3(CH2)4NH3]SnX4 (X = Br, I): Dion-Jacobson type 2-D perovskites with short interlayer spacing.

Two-dimensional tin(II) halide perovskites stand as an environmentally benign alternative to Pb(II) halide perovskites. However, they are often challenging to make due to the oxidation of Sn(II) ion to more stable Sn(IV) ion. Here we report hybrid tin bromide and iodide perovskites: (1,4-BDA)Sn(IV)Br6 and (1,4-BDA)Sn(II)X4 (where X = Br, I; 1,4-BDA = 1,4-diammoniumbutane) with 0D and 2D structures, respectively. Their synthesis, structural characterization and photophysical properties are reported. They show bandgaps in the 1.94-2.70 eV range.

Conformational Studies of ß-Azapeptoid Foldamers: A New Class of Peptidomimetics with Confined Dihedrals.

Controlling amide bond geometries and the secondary structures of ß-peptoids is a challenging task as they contain several rotatable single bonds in their backbone. Herein, we describe the synthesis and conformational properties of novel "ß-azapeptoids" with confined dihedrals. We discuss how the acylhydrazide sidechains in these molecules enforce trans amide geometries (ω ~180°) via steric and stereoelectronic effects. We also show that the Θ(Cα -Cß ) and Ψ(OC-Cα ) backbone torsions of ß-azapeptoids occupy a narrow range (170-180°) that can be rationalized by the staggered conformational preference of the backbone methylene carbons and a novel backbone nO →σ*Cß-N interaction discovered in this study. However, the ϕ (Cß -N) torsion remains freely rotatable and, depending on ϕ, the sidechains can be parallel, perpendicular, and anti-parallel relative to each other. In fact, we observed parallel and perpendicular relative orientations of sidechains in the crystal geometries of ß-azapeptoid dimers. We show that ϕ of ß-azapeptoids can be controlled by incorporating a bulky substituent at the backbone ß-carbon, which could provide complete control over all the backbone dihedrals. Finally, we show that the ϕ and Ψ dihedrals of ß-azapeptoids resemble that of a PPII helix and they retain PPII structure when incorporated in Host-guest proline peptides.

Hybrid Iodide Perovskites of Divalent Alkaline Earth and Lanthanide Elements.

Hybrid halide perovskites AMIIX3 (A = ammonium cation, MII = divalent cation, X = Cl, Br, I) have been extensively studied but have only previously been reported for the divalent carbon group elements Ge, Sn, and Pb. While they have displayed an impressive range of optoelectronic properties, the instability of GeII and SnII and the toxicity of Pb have stimulated significant interest in finding alternatives to these carbon group-based perovskites. Here, we describe the low-temperature solid-state synthesis of five new hybrid iodide perovskites centered around divalent alkaline earth and lanthanide elements, with the general formula AMIII3 (A = methylammonium, MA; MII = Sr, Sm, Eu, and A = formamidinium, FA; MII = Sr, Eu). Structural, calorimetric, optical, photoluminescence, and magnetic properties of these materials are reported.

Elusive Double Perovskite Iodides: Structural, Optical, and Magnetic Properties.

Halide double perovskites [A2 MI MIII X6 ] are an important class of materials that have garnered substantial interest as non-toxic alternatives to conventional lead iodide perovskites for optoelectronic applications. While numerous studies have examined chloride and bromide double perovskites, reports of iodide double perovskites are rare, and their definitive structural characterization has not been reported. Predictive models have aided us here in the synthesis and characterization of five iodide double perovskites of general formula Cs2 NaLnI6 (Ln=Ce, Nd, Gd, Tb, Dy). The complete crystal structures, structural phase transitions, optical, photoluminescent, and magnetic properties of these compounds are reported.

Correction: Molybdenum chloride double perovskites: dimensionality control of optical and magnetic properties.

[This corrects the article DOI: 10.1039/D3SC00132F.].

Synergistic n → π* and nN → π*Ar interactions in C-terminal modified prolines: effect on Xaa-Pro cis/trans equilibrium.

Carbonyl-carbonyl (CO⋯CO) n → π* interaction often coexists with a hydrogen bond (HB) or another n → π* interaction. Although the interplay between HB and n → π* interaction was previously studied, there is no systematic investigation that shows a synergistic relationship of n → π* with another noncovalent interaction. Herein, we have studied a set of proline-diacylhydrazine (Pro-DAH) molecules and observed that increase in the strength of the nN → π*Ar interaction on their DAH side strengthened the n → π* interaction on the Pro side, which was experimentally determined by measuring the Ktrans/cis of the Xaa-Pro amide bond. Overall, we describe a simple C-terminal modification strategy to stabilize the trans-Pro geometry that could be useful to stabilize PPII helices and collagen triple helices that require Pro to adopt the trans amide geometry.

Molybdenum chloride double perovskites: dimensionality control of optical and magnetic properties.

Halide double perovskites are a promising class of semiconducting materials for applications in solar cells and other optoelectronic devices. Recently, there has been a surge of interest in these materials to study phenomena beyond optoelectronics, especially magnetism. Here, we report three new Mo3+ (4d3) based chloride double perovskites: a 3-D rock-salt ordered Cs2NaMoCl6, a 1-D chain (MA)2AgMoCl6 and a Dion-Jacobson type 2-D layered (1,4-BDA)2AgMoCl8 (MA = methylammonium; 1,4-BDA = 1,4-butanediammonium). Their structures and dimensionalities can be tuned by means of the A-cation. The measured bandgaps are relatively narrow (2.0-2.1 eV) which show a blueshift on reducing the dimensionality. At low temperatures, we observe antiferromagnetic coupling between the nearest-neighbour Mo3+ ions in all these systems. Cs2NaMoCl6 shows stronger coupling with a frustration index f of 5 which we attribute to the geometrically frustrating fcc lattice of Mo3+ ions. This work expands the scope of halide double perovskites beyond main group metals and beyond optoelectronics, and we hope that it will lead to future developments in magnetic halide perovskites.

Sidechain-Backbone Tetrel Bonding Interactions Provide a General Mechanism for trans-Peptoid Stabilization.

Cis-trans isomerization of amide bonds impedes de novo design of folded peptoids (poly-N-substituted glycines) with precise secondary structures and affects peptoid-biomolecule binding affinity. Herein, from X-ray, NMR and DFT studies of azapeptoids, we have discovered a tetrel bonding interaction that stabilizes trans-peptoids. We show that peptoids having α-heteroatoms and N-aryl groups in the sidechain adopt trans-amide geometries due to the presence of a nX /πAr →σ*Cα-N tetrel bonding interaction between the sidechain α-heteroatom lone pair (nX ) or π-electrons (πAr ) and the σ* orbital of the backbone Cα -N bond. Further, CD spectroscopic studies of oligo-proline host-guest model peptides showed that azapeptoid residues stabilize polyproline II helical conformation. These data indicate that the sidechain-backbone tetrel bonding could be leveraged to design peptoids with precise secondary structures for a wide range of biological and material applications.

Hybrid Layered Double Perovskite Halides of Transition Metals.

Hybrid layered double perovskite (HLDP) halides comprise hexacoordinated 1+ and 3+ metals in the octahedral sites within a perovskite layer and organic amine cations between the layers. Progress on such materials has hitherto been limited to compounds containing main group 3+ ions isoelectronic with PbII (such as SbIII and BiIII). Here, we report eight HLDP halides from the A2MIMIIIX8 family, where A = para-phenylenediammonium (PPDA), 1,4-butanediammonium (1,4-BDA), or 1,3-propanediammonium (1,3-PDA); MI = Cu or Ag; MIII = Ru or Mo; X = Cl or Br. The optical band gaps, which lie in the range 1.55 to 2.05 eV, are tunable according to the layer composition, but are largely independent of the spacer. Magnetic measurements carried out for (PPDA)2AgIRuIIICl8 and (PPDA)2AgIMoIIICl8 show no obvious evidence of a magnetic ordering transition. While the t2g3 MoIII compound displays Curie-Weiss behavior for a spin-only d3 ion, the t2g5 RuIII compound displays marked deviations from the Kotani theory.

Chemical Control of Spin-Orbit Coupling and Charge Transfer in Vacancy-Ordered Ruthenium(IV) Halide Perovskites.

Vacancy-ordered double perovskites are attracting significant attention due to their chemical diversity and interesting optoelectronic properties. With a view to understanding both the optical and magnetic properties of these compounds, two series of RuIV halides are presented; A2 RuCl6 and A2 RuBr6 , where A is K, NH4 , Rb or Cs. We show that the optical properties and spin-orbit coupling (SOC) behavior can be tuned through changing the A cation and the halide. Within a series, the energy of the ligand-to-metal charge transfer increases as the unit cell expands with the larger A cation, and the band gaps are higher for the respective chlorides than for the bromides. The magnetic moments of the systems are temperature dependent due to a non-magnetic ground state with Jeff =0 caused by SOC. Ru-X covalency, and consequently, the delocalization of metal d-electrons, result in systematic trends of the SOC constants due to variations in the A cation and the halide anion.

Li5VF4(SO4)2: A Prototype High-Voltage Li-Ion Cathode.

A Li-rich polyanionic compound based on V3+ with a previously unknown structure, Li5VF4(SO4)2, has been developed as a high-voltage cathode material for Li-ion batteries. The solvothermal preparation of this material, crystal structure solution, and initial electrochemical characterization are presented. An analysis based on density functional theory electronic structure calculations suggests that a high voltage close to 5 V is required to extract two Li ions and to reach the oxidation state of V5+. However, the use of conventional carbonate-based electrolytes, which exhibit increasing degradation above a potential of 4.3 V, does not permit the full capacity of this compound to be achieved at this time.

Tunable Luminescence in Hybrid Cu(I) and Ag(I) Iodides.

Hybrid materials are increasingly demonstrating their utility across several optical, electrical, and magnetic applications. Cu(I) halide-based hybrids have attracted attention due to their strong luminescence in the absence of rare-earths. Here, we report three Cu(I) and Ag(I) hybrid iodides with 1,5-naphthyridine and additional triphenylphosphine (Ph3P) ligands. The compounds are built on (Cu/Ag)-I staircase chains or on a rhomboid Cu2I2 dimer and display intense and tunable luminescence. Replacing Cu with Ag, and adding the second kind of organic ligand (Ph3P) tunes the emission color from red to yellow and results in significantly enhanced quantum yield. Density functional theory-based electronic structure calculations reveal the separate effects of the inorganic module and organic ligand on the electronic structure, confirming that bandgap, optical absorption, and emission properties of these phosphors can be systemically and deliberately tuned by metal substitution and organic ligands cooperation. The emerging understanding of composition-structure-property relations in this family provides powerful design tools toward new compounds for general lighting applications.

Structural Diversity and Magnetic Properties of Hybrid Ruthenium Halide Perovskites and Related Compounds.

There has been a great deal of recent interest in extended compounds containing Ru3+ and Ru4+ in light of their range of unusual physical properties. Many of these properties are displayed in compounds with the perovskite and related structures. Here we report an array of structurally diverse hybrid ruthenium halide perovskites and related compounds: MA2 RuX6 (X=Cl or Br), MA2 MRuX6 (M=Na, K or Ag; X=Cl or Br) and MA3 Ru2 X9 (X=Br) based upon the use of methylammonium (MA=CH3 NH3 + ) on the perovskite A site. The compounds MA2 RuX6 with Ru4+ crystallize in the trigonal space group R 3 ‾ m and can be described as vacancy-ordered double-perovskites. The ordered compounds MA2 MRuX6 with M+ and Ru3+ crystallize in a structure related to BaNiO3 with alternating MX6 and RuX6 face-shared octahedra forming linear chains in the trigonal P 3 ‾ m space group. The compound MA3 Ru2 Br9 crystallizes in the orthorhombic Cmcm space group and displays pairs of face-sharing octahedra forming isolated Ru2 Br9 moieties with very short Ru-Ru contacts of 2.789 Å. The structural details, including the role of hydrogen bonding and dimensionality, as well as the optical and magnetic properties of these compounds are described. The magnetic behavior of all three classes of compounds is influenced by spin-orbit coupling and their temperature-dependent behavior has been compared with the predictions of the appropriate Kotani models.

Covalently Linked Heterostructures of Phosphorene with MoS2/MoSe2 and Their Remarkable Hydrogen Evolution Reaction Activity.

Hydrogen production by photochemical and electrochemical means is an important area of research related to renewable energy. 2D nanomaterials such as C3N4 and MoS2 have proven to be active for the hydrogen evolution reaction (HER). Phosphorene, a mono-elemental 2D layer of phosphorus, is known to catalyze the HER, but the activity is marginal. The use of phosphorene is also limited by its ambient instability. We have been able to prepare covalently cross-linked nanocomposites of phosphorene with MoS2 as well as MoSe2. The phosphorene-MoS2 nanocomposite shows excellent photochemical HER activity yielding 26.8 mmol h-1 g-1 of H2, while only a negligible amount is produced by the physical mixture of phosphorene and MoS2. The phosphorene-MoS2 composite also displays high electrochemical HER activity with an onset overpotential of 110 mV, close to that of Pt. The enhanced HER activity of the phosphorene-MoS2 nanocomposite can be attributed to the ordered cross-linking of the 2D sheets, increasing the interfacial area as well as the charge-transfer interaction between phosphorene and MoS2 layers. The phosphorene-MoSe2 nanocomposite also exhibits good photochemical HER activity.

A covalently conjugated MoS2/Fe3O4 magnetic nanocomposite as an efficient & reusable catalyst for H2 production.

Quick and easy recovery without the loss of the photocatalytic activity of the catalysing agent is an effective way to meet the challenges associated with the high cost of hazard-free hydrogen production. A '2D/0D' covalently conjugated nanocomposite of MoS2/Fe3O4 has shown efficient catalyzing ability for five cycles of dye-sensitized H2 evolution.

1,3,5-Triphenylbenzene: a versatile photoluminescent chemo-sensor platform and supramolecular building block.

Fluorescence chemo-sensors for species of environmental and biological significance have emerged as a major research area in recent years. In this account, we describe fluorescence quenching as well as enhancement-based chemo-sensors obtained by employing C 3-symmetric 1,3,5-triphenylbenzene (1,3,5-TPB) as the fluorescence signalling unit. 1,3,5-TPB is a thermally and photochemically stable fluorescent platform with π-electron-rich characteristics. Starting from this platform, supramolecular, discrete, triphenylbenzene-carbazole, covalent-organic framework, covalent-organic polymer and conjugated polymer based sensors have been developed for the selective detection of polynitroaromatic compounds, trinitrotoluene (TNT), dinitrotoluene (DNT) and picric acid (PA). Tris-salicylaldimine Schiff bases have been synthesized for the selective sensing of fluoride ions through a fluorescence turn-on mechanism. It is likely that it should be possible to develop other highly selective and sensitive chemo-sensors by incorporating 1,3,5-TPB as the fluorophore unit.

Doping Phosphorene with Holes and Electrons through Molecular Charge Transfer.

An important aspect of phosphorene, the novel two-dimensional semiconductor, is whether holes and electrons can both be doped in this material. Some reports found that only electrons can be preferentially doped into phosphorene. There are some theoretical calculations showing charge-transfer interaction with both tetrathiafulvalene (TTF) and tetracyanoethylene (TCNE). We have carried out an investigation of chemical doping of phosphorene by a variety of electron donor and acceptor molecules, employing both experiment and theory, Raman scattering being a crucial aspect of the study. We find that both electron acceptors and donors interact with phosphorene by charge-transfer, with the acceptors having more marked effects. All the three Raman bands of phosphorene soften and exhibit band broadening on interaction with both donor and acceptor molecules. First-principles calculations establish the occurrence of charge-transfer between phosphorene with donors as well as acceptors. The absence of electron-hole asymmetry is noteworthy.

Triphenylbenzene Sensor for Selective Detection of Picric Acid.

A C 3-symmetric triphenylbenzene based photoluminescent compound, 1,3,5-tris(4'-(N-methylamino)phenyl) benzene ([NHMe]3TAPB), has been synthesized by mono-N-methylation of 1,3,5-tris(4'-aminophenyl) benzene (TAPB) and structurally characterized. [NHMe]3TAPB acts as a selective fluorescent sensor for picric acid (PA) with a detection limit as low as 2.25 ppm at a signal to noise ratio of 3. Other related analytes (i.e. TNT, DNT and DNB) show very little effect on the fluorescence intensity of [NHMe]3TAPB. The selectivity is triggered by proton transfer from picric acid to the fluorophore and ground-state complex formation between the protonated fluorophore and picrate anion through hydrogen bonding interactions. The fluorescence lifetime measurements reveal static nature of fluorescence quenching.

Covalent Functionalization of Nanosheets of MoS2 and MoSe2 by Substituted Benzenes and Other Organic Molecules.

Covalent functionalization has been effectively employed to attach benzene functionalities to MoS2 and MoSe2 nanosheets by the reaction with para-substituted iodobenzenes bearing -OCH3 , -H, and -NO2 as the substituents, where the electron-donating and electron-withdrawing power of the para substituent varies significantly. The functionalization is based on the formation of a C-S or C-Se linkage at the expense of the C-I bond on reaction of the iodobenzene with electron-rich 1T-MoS2 or 1T-MoSe2 . The degree of functionalization is in the range 4-24 % range, the value increases with the electron-withdrawing power of the para substituent. Semiconducting 2H-MoS2 and 2H-MoSe2 nanosheets can also be functionalized with iodobenzene by carrying out the reaction in the presence of a Pd0 catalyst. We have also carried out functionalization of 1T-MoS2 with pyrene, coumarin, and porphyrin derivatives. By using first-principles density functional calculations, we show that the bonding of the functional groups with the 1T phase is stronger than with the 2H phase. This is reflected in notable changes in the electronic structure of the former upon functionalization; a gap opens up in the electronic spectrum of the 1T phase. Functionalization with para-substituted benzenes leads to a change in the work function.