The crystal structure of 2-(2,2,3,3,3-pentafluoropropoxy) ethylammonium iodide (5F-EA-HI) was determined by using single-crystal X-ray diffraction at 100 K. The compound crystallized in the orthorhombic space group Pccn with unit-cell parameters a = 23.911(7) Å, b = 8.880(2) Å, c = 9.451(2) Å, and V = 2006.740(9) Å3 (Z = 8). Its cation, 5F-EAH⁺, adopts an extended conformation in which the pentafluoropropoxy tail is directed away from the ammonium head group, stabilized by a weak intramolecular non-classical C–H···F and an intramolecular classical N–H···O hydrogen bonding. The iodide anion serves as the principal supramolecular acceptor, forming three charge-assisted N–H···I classical hydrogen bondings that assemble the molecules into dimers and rhombic cyclic motifs. In addition, short intermolecular C–F···F–C interactions between neighbouring fluorinated tails generate both Type I and Type II halogen bond geometries, linking adjacent molecules into closed cyclic tetrameric assemblies. Hirshfeld surface analysis quantitatively confirms these intermolecular interactions with percentage contributions. A space-filling analysis of the crystal packing revealed the clear spatial segregation of fluorous, organic and inorganic (iodide-rich) phases, which are usually observed in fluorinated halide perovskites, but not in the organic spacer. These findings demonstrate how weak non-covalent interactions cooperate to direct the solid-state organization of a highly fluorinated ethylammonium salt and suggest that 5F-EA-HI may serve as a structurally well-defined model spacer for the design of moisture-resistant and thermally stable 2D halide perovskites. The 5F-EA-HI salt exhibits, in the solid state, a rich network of non-covalent interactions which include classical N–H···I and N–H···O hydrogen bonds (HBs), a non-classical C–H···F HB, a tetrel bond (TB), and Type I Type II C–F···F–C halogen bonds (XBs).

Protective low-dimensional interphases can improve perovskite solar-cell stability, but they often compromise charge extraction because of unfavorable interfacial packing and transport barriers. Herein, we report a scaffold-directed strategy to construct an interwoven tilted 1D/3D heterointerface on inverted perovskite absorbers. By depositing PbI2 onto a tilt-oriented 3D perovskite scaffold and inducing solvent-assisted reconstruction, a compact near-surface interphase composed of edge-sharing 1D PbI2 and face-sharing 1D δ-FAPbI3 is formed with an oblique orientation guided by the crystallographic texture of the underlying 3D framework. Unlike conventional laterally aligned low-dimensional overlayers, this tilted 1D interphase preserves out-of-plane interfacial connectivity while providing a robust barrier against defect propagation and ion migration. We further identify 7F-EA-HI, a flexible polyfluorinated ammonium iodide, as an effective crystallization regulator that suppresses reconstruction-induced defects and favorably modulates interfacial energetics through its large molecular dipole. As a result, the optimized inverted PSCs deliver a power conversion efficiency (PCE) of 24.94%, with an open-circuit voltage (VOC) of 1.188 V, a short-circuit current density (JSC) of 24.67 mA cm-2, and a fill factor (FF) of 85.11%, along with markedly improved ambient and thermal stability. This work demonstrates tilted 1D/3D interfacial engineering as a viable route toward high-voltage and durable perovskite optoelectronics.

Three fluorinated Zn complexes were synthesized and characterized. Their single crystals were grown and studied via X-ray and neutron diffraction methods. These fluorinated metal complexes tend to form two special noncovalent interactions: an intramolecular tetrel bond (TB) and an intramolecular blueshifting hydrogen bond (HB). In 4FH-ZnCl2 [2,6-(HCF2CF2CH2OCH2)2-py-ZnCl2], an intramolecular TB induces significant elongation of a C-H bond in a methylene group, H1A-C1-H1B, to 1.108(2) Å, whereas the intramolecular C1-H1A···F2 blueshifting HB shortens the C1-H1A bond to 1.092(1) Å. Thus, C1-H1B is longer than C1-H1A by 16(2) mÅ such that either one of the C1-H1 stretches becomes a methine-like stretch with a peak appearing at 3020 or 2688 cm-1. A peak corresponding to a lengthened sp3 C1-H1B bond is greatly redshifted and appears at 2688 cm-1. When this 2688 cm-1 peak is compared with its other methylene C-H peak (3020 cm-1), their C-H vibrational stretches then differ by 332 cm-1, which is likely the largest ever sp3 C-H bond stretching difference reported between two methylene C-H bonds. Additionally, two C-D bonds of deuterated 4FH-ZnCl2, which has an intramolecular C···F TB that induces very different lengths of the two C-D bonds in a D-C-D group, become a local mode, as proven by Hooke's law. Thus, Badge's rule has been extended by using both neutron and spectroscopic studies.

Paracetamol (PCT), a widely used analgesic and antipyretic drug, has become a significant contaminant in water bodies due to pharmaceutical waste. This study introduces a novel electrochemical sensor based on coffeeground-derived carbon quantum dots doped with copper oxide and integrated with graphene nanoribbons (Cu2O3-CCQDs/GNRs) for the sensitive and selective detection of PCT. The synthesized Cu2O3-CCQDs/GNRs composite was thoroughly characterized using various analytical and spectroscopic techniques. The sensor exhibited excellent electrochemical performance, achieving a low detection limit of 0.016 mu M, a broad linear range from 0.0125 to 1433.26 mu M, and a high sensitivity of 0.4215 mu A mu M- 1 cm- 2 for PCT detection. Furthermore, the sensor demonstrated remarkable selectivity (10-interferent), stability (40-segments), and reproducibility (4-electrodes). Real-time monitoring of environmental samples, including drinking water, tap water, pond water, and river water, confirmed the sensor's practical applicability. Additionally, Density Functional Theory calculations were employed to analyze the frontier molecular orbitals and electrostatic potential distribution of PCT and its oxidized form, revealing the probable electron transfer sites involved in the electrochemical oxidation mechanism. This work presents a cost-effective and efficient method for PCT detection in environmental samples, highlighting the synergistic effects of Cu2O3-CCQDs and GNRs.

The sp3-based C−F⋯F − C halogen bonds (XBs) and blue-shifting C−H⋯X (X = F, Cl) hydrogen bonds (HBs) are a relatively unusual phenomenon in chemistry, due to their uncommonness and the challenges associated with their direct observations. To investigate these interactions, a novel fluorinated trans-[2-(HCF2(CF2)3CH2OCH2)2-py-PdCl2], abbreviated as 2-(8FH-py)2PdCl2 complex, has been synthesized and structurally characterized. The incorporation of a fluorinated ponytail on the pyridyl ring in the 2-(8FH-py)2PdCl2 complex allows us to explore rare sp3-based type II C9−F4⋯F6−C10 and C8−F2⋯F6−C10 XBs dimers. These findings suggest, for the first time, the formation of halogen bonding dimers through C−F⋯F−C interactions, to our knowledge. Additionally, the 2-(8FH-py)2PdCl2 reveals interesting blue-shifting C−H⋯X hydrogen bonding interactions in the crystal packing. These C−H⋯F interactions connect adjacent molecules in a head-to-tail manner, resulting in the continuation of R22(9) synthons along the crystallographic a-axis. These hydrophobic interactions, which are expected to be very different from the typical hydrophilic interactions, play a crucial role in enhancing the self-assembly and stability of the crystal structure. In addition, the presence of blue-shifting C−H⋯X hydrogen bonding interactions affirmed by the FT-IR studies. Furthermore, the high positive values of electron density (ρ) and Laplacian density (∇2ρ) from quantum theory of atoms in molecule (QTAIM) analyses suggest the presence of electrostatic and weak interactions between atoms. We believe that this discovery will open up new opportunities for exploring and utilizing fluorinated complexes in various scientific fields, fluoro-pharmaceuticals and crystal engineering.

The development of a dual Z-scheme Dy2Sn2O7/MoS2/Ag@g-C3N4 heterostructure represents an effective strategy for enhancing photocatalytic performance. The photocatalytic efficiency of the synthesized materials was assessed through experiments examining tetracycline degradation under visible light and persulfate (PS) activation. The rational-engineered dual Z-scheme Dy2Sn2O7/MoS2/Ag@g-C3N4 system achieved a remarkable 95.01 % photodegradation efficiency of tetracycline within 70 min under the PS activation. The reaction kinetics followed a first order model, exhibiting a kinetic constant of 0.09235 min(-1) with a correlation coefficient (R-2) of 0.9920. Additionally, Work function analysis verifies the presence of a dual Z-scheme charge transfer mechanism in the Dy2Sn2O7/MoS2/Ag@g-C3N4 system. Band structure and density of states (DOS) analyses provided insights into the electronic properties of the proposed materials. A combination of theoretical calculations and experimental findings elucidated the photocatalytic mechanism, recognized intermediate species, and photodegradation pathways. The degradation pathways of tetracycline were further explored using GC-MS analysis and DFT studies. In this work, biotoxicity evaluations indicated a decrease in the toxicity of the degraded tetracycline byproduct, as evidenced by Vigna radiata seeds germination and E. coli growth experiments. Moreover, the Dy2Sn2O7/MoS2/Ag@g-C3N4 ternary system is a potential candidate for eco-friendly water purification and enhanced water treatment efficiency.

The sp 3-based C-F center dot center dot center dot F- C halogen bonds (XBs) and blue-shifting C-H center dot center dot center dot X (X = F , Cl) hydrogen bonds (HBs) are a relatively unusual phenomenon in chemistry, due to their uncommonness and the challenges associated with their direct observations. To investigate these interactions, a novel fluorinated trans-[2-(HCF2(CF2)3CH2OCH2)2- py-PdCl2], abbreviated as 2-(8FH-py)2PdCl2 complex, has been synthesized and structurally characterized. The incorporation of a fluorinated ponytail on the pyridyl ring in the 2-(8FH-py)2PdCl2 complex allows us to explore rare sp3-based type II C9-F4 center dot center dot center dot F6-C10 and C8-F2 center dot center dot center dot F6-C10 XBs dimers. These findings suggest, for the first time, the formation of halogen bonding dimers through C-F center dot center dot center dot F-C interactions, to our knowledge. Additionally, the 2-(8FH-py)2PdCl2 reveals interesting blue-shifting C-H center dot center dot center dot X hydrogen bonding interactions in the crystal packing. These C-H center dot center dot center dot F interactions connect adjacent molecules in a head-to-tail manner, resulting in the continuation of R22(9) synthons along the crystallographic a-axis. These hydrophobic interactions, which are expected to be very different from the typical hydrophilic interactions, play a crucial role in enhancing the self- assembly and stability of the crystal structure. In addition, the presence of blue-shifting C-H center dot center dot center dot X hydrogen bonding interactions affirmed by the FT-IR studies. Furthermore, the high positive values of electron density (rho) and Laplacian density (O2 rho) from quantum theory of atoms in molecule (QTAIM) analyses suggest the presence of electrostatic and weak interactions between atoms. We believe that this discovery will open up new opportunities for exploring and utilizing fluorinated complexes in various scientific fields, fluoro-pharmaceuticals and crystal engineering.

The development of a dual Z-scheme Dy₂Sn₂O₇/MoS₂/Ag@g-C₃N₄ heterostructure represents an effective strategy for enhancing photocatalytic performance. The photocatalytic efficiency of the synthesized materials was assessed through experiments examining tetracycline degradation under visible light and persulfate (PS) activation. The rational-engineered dual Z-scheme Dy₂Sn₂O₇/MoS₂/Ag@g-C₃N₄ system achieved a remarkable 95.01 % photodegradation efficiency of tetracycline within 70 min under the PS activation. The reaction kinetics followed a first order model, exhibiting a kinetic constant of 0.09235 min⁻¹ with a correlation coefficient (R²) of 0.9920. Additionally, Work function analysis verifies the presence of a dual Z-scheme charge transfer mechanism in the Dy₂Sn₂O₇/MoS₂/Ag@g-C₃N₄ system. Band structure and density of states (DOS) analyses provided insights into the electronic properties of the proposed materials. A combination of theoretical calculations and experimental findings elucidated the photocatalytic mechanism, recognized intermediate species, and photodegradation pathways. The degradation pathways of tetracycline were further explored using GC-MS analysis and DFT studies. In this work, biotoxicity evaluations indicated a decrease in the toxicity of the degraded tetracycline byproduct, as evidenced by Vigna radiata seeds germination and E. coli growth experiments. Moreover, the Dy₂Sn₂O₇/MoS₂/Ag@g-C₃N₄ ternary system is a potential candidate for eco-friendly water purification and enhanced water treatment efficiency.

Driven by the structural versatility and magnetic tunability of Cu(II) complexes and the unique supramolecular properties of fluorinated ligands, we report the synthesis and structural characterization of a novel fluorinated CuCl2 dimer complex [((C2F5CH2OCH2)2py)CuCl2]2 [or abbreviated as [(5F-CuCl2)2]. Its single crystal X-ray diffraction reveals a centrosymmetric dimeric structure with distorted square-pyramidal Cu(II) centers bridged by chloride ligands. The fluorinated complex crystallizes in the triclinic space group P-1, with each Cu(II) adopting a tau = 0.15 geometry. Its structural analysis reveals a network of rare non-covalent interactions including C-H center dot center dot center dot F, C-H & ctdot;Cl (-Cu) blue-shifting hydrogen bonds (HBs), sp3 C-F & ctdot;F-C halogen bonds etc. stabilize the crystal lattice. Hirshfeld surface analysis and fingerprint plots further affirm the significance of these interactions in stabilizing its lattice. The observed C-H & ctdot;X and C-F & ctdot;F-C motifs, rarely reported for sp3-hybridized fluorine systems, demonstrate the capability of fluorine to modulate coordination environments and induce unique assembly patterns. Furthermore, the magnetic susceptibility of (5F-CuCl2)2 dimer has been measured. Additionally, the Bent's rule has also used to explain the C-C and C-O bond length changes. These findings are believed to enrich our understanding of fluorine-driven supramolecular chemistry, application of fluorinated complex and offer new design principles for the fluorinated pincer-like metal complexes with the short-chains.

For the first time, we report a trifluoromethyl group-incorporated aliphatic linearly-chained 2D (3F-PAH)2PbI4 halide perovskite (HP) with a low bandgap of 2.28 eV, minimal Pb-I-Pb bond angle distortion (similar to 153.5 degrees) and a unique fluorous phase. The photodetector (PD) demonstrates good responsivity (600 mA W-1) and fast response/recovery times (74/98 ms) at 5 V under 450 nm light, making it ideal for next-generation optoelectronic devices.

Ruddlesden-Popper (RP) two-dimensional (2D) halide perovskite (HP), with attractive structural and optoelectronic properties, has shown great potential in optoelectrical devices. However, the relatively wide bandgap (E g) and stability, which cause inferior efficiency, prevent its feasibility from further applications. To tackle these issues, for the first time, a novel fluorine-containing piperidinium spacer, (3-HCF2CF2CH2OCH2-PPH+), abbreviated as (4FH-PPH+), has been designed for the stable and efficient n = 1 2D HPs. Its fluorophobicity can significantly enhance the noncovalent interactions between cations and [PbI6]4- octahedra. The observed E g of the fluorinated (4FH-PPH)2PbI4 perovskite is found to be 2.22 eV, which is the lowest value among all fluorinated perovskites reported so far. Interestingly, this fluorinated film-based 2D perovskite photodetector (PD) exhibits the outstanding responsivity of 502 mA W-1, photodetectivity of 5.73 x 1010 cm Hz1/2 W-1, and impressive response/recovery time of 42/46 ms under 450 nm at 20 V. To the best of our knowledge, it is found for the first time that the 2D HP, with the fluorinated short-chained segment included into the organic spacer, shows remarkable stability for up to 49 days. These results strongly demonstrate the potential of the 2D fluorinated short-chained (4FH-PPH)2PbI4 HP with a low E g as a promising candidate for next-generation optoelectronic devices.

In order to better understand the effect of non-covalent weak interactions on molecules, we have explored a variety of weak interactions, such as improper H-bonding (HB), tetrel bonds (TBs) and halogen bonds, in fluorinated chiral zinc complexes. High resolution neutron diffraction studies revealed a methylene carbon-hydrogen bond elongation and shortening due to TB and improper HB interactions, respectively. To show the accumulative effects of multiple weak interactions on the C−H bond, three types of tetrel bonds have been carefully examined. We have also shown how C−H bond elongation can be easily offset by forming an improper HB with the H atom from this C−H bond. Non-covalent interaction and electrostatic potential analysis investigations have been used to affirm the nature of the interactions based on density functional theory (DFT) and other related calculations.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

The reaction of [PdCl 2 (CH 3 CN) 2 ] and bis-5,5'-(R f CH 2 OCH 2 )-2,2'-bpy ( 1 ), where R f = n -C 4 F 8 H, in the presence of dichloromethane (CH 2 Cl 2 ) resulted in the synthesis of low fluorine content Pd complex, [PdCl 2 [5,5'-bis-(R f CH 2 OCH 2 )-2,2'-bpy] ( 2 ). The Pd-catalyzed Suzuki-Miyaura and Sonogashira coupling reactions of several aryl iodides with their respective reagents were selected to demonstrate the feasibility of recycling usage with 2 as the catalyst by using dibutyl ether (DBE) as the solvent at 140-145 o C under the thermomorphic mode. The Pd complex 2 -catalyzed Suzuki-Miyaura reactions of different aryl iodides with phenylboronic acid derivatives have showed good recycling results though its activity was observed to decrease after the fifth cycle. Similarly, 2 -catalyzed Sonogashira reactions of several aryl iodides with phenyl acetylene have also displayed good recycling results for a total of up to 8 cycles, with a high yield and TON. The electronic effect studies from substituents in both Suzuki-Miyaura and Sonogashira coupling reactions showed that electron withdrawing groups on the aryl iodide speed up the reaction rate. To our knowledge, this is the first example of recoverable low fluorine content Pd-catalyzed Suzuki-Miyaura and Sonogashira reactions under the thermomorphic mode.

In this present investigation, a hydrated single crystal of new , 6-amino-2-methoxypyrimidin-4(3H)one (AMP) has been grown using slow solvent evaporation technique. The single crystal X-ray diffraction technique has been used to study the structure of pyrimidinone derivative, which discloses the role of two lattice waters molecules in the crystal packing called hydrated 6-amino-2-methoxypyrimidin-4(3H)one (HAMP). These kinds of hydrated forms incorporate noticeable improvements in the crucial physical properties of API molecules, like stability and bioavailability. The crystal structure of HAMP is greatly stabilized by the significant O-H center dot center dot center dot O, N-H center dot center dot center dot O, and N-H center dot center dot center dot N H-bonding (HB) interactions. With the help of DFT computational analysis, molecular geometry and global reactive parameters have been calculated to better understand the molecular properties of HAMP. The Hirshfeld surface (HS) and accompanying 2D fingerprint plots have been used to explore the nature of all of these non-classical HB interactions, as well as their relative roles in creating supramolecular structures. The energy difference between HOMO-LUMO is found to be 5.414 eV which indicates the possibility of a charge transfer in the HAMP molecule. The molecular electrostatic potential (MEP) has been plotted to understand the charge distribution, electrophilic and nucleophilic sites in the HAMP molecule. Moreover, the quantum theory of atoms in molecules (QTAIM) framework, non-covalent interactions (NCI), reduced density gradient (RDG), electron localization function (ELF), and electron density have been used to describe the nature of non-covalent interactions and electron clouds present in the HAMP crystal. (C) 2022 Published by Elsevier B.V.

The rational molecular design of non-fullerene acceptors (NFAs) in organic solar cells (OSCs) can profoundly influence the photovoltaic (OPV) performance.

Phospha-Michael addition, which is the addition reaction of a phosphorus-based nucleophile to an acceptor-substituted unsaturated bond, certainly represents one of the most versatile and powerful tools for the formation of P-C bonds, since many different electrophiles and P nucleophiles can be combined with each other. This offers the possibility to access many diversely functionalized products. In this work, two kinds of basic pyridine-based organo-catalysts were used to efficiently catalyze phospha-Michael addition reactions, the 4-N,N-dimethylaminopyridinium saccharinate (DMAP·Hsac) salt and a fluorous long-chained pyridine (4-Rf-CH2OCH2-py, where Rf = C11F23). These catalysts have been synthesized and characterized by Lu’s group. The phospha-Michael addition of diisopropyl, dimethyl or triethyl phosphites to α, β-unsaturated malonates in the presence of those catalysts showed very good reactivity with high yield at 80–100 °C in 1–4.5 h with high catalytic recovery and reusability. With regard to significant catalytic recovery, sometimes more than eight cycles were observed for DMAP·Hsac adduct by using non-polar solvents (e.g., ether) to precipitate out the catalyst. In the case of the fluorous long-chained pyridine, the thermomorphic method was used to efficiently recover the catalyst for eight cycles in all the reactions. Thus, the easy separation of the catalysts from the products revealed the outstanding efficacy of our systems. To our knowledge, these are good examples of the application of recoverable organo-catalysts to the DMAP·Hsac adduct by using non-polar solvent and a fluorous long-chained pyridine under the thermomorphic mode in phospha-Michael addition reactions.

Homogeneous catalysts PtCl2[5,5′-bis-(n-ClCF2(CF2)3CH2OCH2)-2,2′-bpy] (2A) and PtCl2[5,5′-bis-(n-HCF2(CF2)3CH2OCH2)-2,2′-bpy] (2B), which contained short fluorous chains, were synthesized and used in catalysis of hydrosilylation of alkynes. In these reactions the thermomorphic mode was effectively used to recover these catalysts from the reaction mixture up to eight cycles by taking advantage of heterogeneous phase separation at ice temperature. This kind of catalysis had previously been observed in fluorous catalysts of platinum containing about 50% F-content, but in this work the percentage of F-content is decreased to only about 30%, by which we termed them as “very light fluorous”. Our new type of catalyst with limited number of F-content is considered as the important discovery in the fluorous technology field as the reduced number of fluorine atoms will help to be able to comply the EPA 8-carbon rule. The metal leaching after the reaction has been examined by ICP-MS, and the testing results show the leaching of residual metal to be minimal. Additionally, comparing these results to our previous work, fluorous chain assisted selectivity has been observed when different fluorous chain lengths of the catalysts are used. It has been found that there exists fluorous chain assisted better selectivity towards β-(E) form in the Pt-catalyzed hydrosilylation of non-symmetric terminal alkyne when the Pt catalyst contains short fluorous chain (i.e., 4 Cs). Phenyl acetylenes showed the opposite regioselectivity due to pi-pi interaction while using the same catalyst via Markovnikov’s addition to form terminal vinyl silane, which is then a major product for Pt-catalyzed hydrosilylation of terminal aryl acetylene with triethylsilane. Finally, the kinetic studies indicate that the insertion of alkyne into the Pt-H bond is the rate-determining step.