The π‐expansion of non‐fullerene acceptors is a promising method for boosting the organic photovoltaic performance by allowing the fine‐tuning of electronic structures and molecular packing. In this ...work, highly efficient organic solar cells (OSCs) are fabricated using a 2D π‐expansion strategy to design new non‐fullerene acceptors. Compared with the quinoxaline‐fused cores of AQx‐16, the π‐expanded phenazine‐fused cores of AQx‐18 induce more ordered and compact packing between adjacent molecules, affording an optimized morphology with rational phase separation in the blend film. This facilitates efficient exciton dissociation and inhibited charge recombination. Consequently, a power conversion efficiency (PCE) of 18.2% with simultaneously increasing Voc, Jsc, and fill factor is achieved in the AQx‐18‐based binary OSCs. Significantly, AQx‐18‐based ternary devices fabricated via a two‐in‐one alloy acceptor strategy exhibit a superior PCE of 19.1%, one of the highest values ever reported for OSCs, along with a high Voc of 0.928 V. These results indicate the importance of the 2D π‐expansion strategy for the delicate regulation of the electronic structures and crystalline behaviors of the non‐fullerene acceptors to achieve superior photovoltaic performance, aimed at significantly promoting further development of OSCs.
The π‐expansion of phenazine‐fused core on AQx‐18 affords a 2D‐congjugated non‐fullerene acceptor with favorable electronic and aggregation structures. AQx‐18‐based devices exhibit a PCE of 19.1%, which is among the highest value ever reported for organic solar cells (OSCs) with a high Voc of 0.928 V. Such a 2D π‐expansion strategy is promising for next‐generation high‐performance OSCs.
Side‐chain tailoring is a promising method to optimize the performance of organic solar cells (OSCs). However, asymmetric alkyl chain‐based small molecular acceptors (SMAs) are still difficult to ...afford. Herein, we adopted a novel asymmetric n‐nonyl/undecyl substitution strategy and synthesized two A‐D1A′D2‐A double asymmetric isomeric SMAs with asymmetric selenophene‐based central core for OSCs. Crystallographic analysis indicates that AYT9Se11‐Cl forms a more compact and order intermolecular packing compared to AYT11Se9‐Cl, which contributed to higher electron mobility in neat AYT9Se11‐Cl film. Moreover, the PM6 : AYT9Se11‐Cl blend film shows a better morphology with appropriate phase separation and distinct face‐on orientation than PM6 : AYT11Se9‐Cl. The OSCs with PM6 : AYT9Se11‐Cl obtain a superior PCE of 18.12 % compared to PM6 : AYT11Se9‐Cl (17.52 %), which is the best efficiency for the selenium‐incorporated SMAs in binary BHJ OSCs. Our findings elucidate that the promising double asymmetric strategy with isomeric alkyl chains precisely modulates the crystal packing and enhances the photovoltaic efficiency of selenophene‐incorporated SMAs.
Two isomeric A‐D1A′D2‐A type double asymmetric selenophene‐based small molecule acceptors (SMAs) were synthesized by a n‐nonyl/undecyl regioisomeric strategy to optimize single‐crystal packing, improve film morphology, and boost device performance. PM6 : AYT9Se11‐Cl achieved a superior PCE of 18.12 % compared to PM6 : AYT11Se9‐Cl.
•Synthesis of two 2‑hydroxy-1-naphthaldehyde based Schiff base zwitterions reported.•Various non-covalent interactions responsible for their structural stabilities.•Calculated structures in good ...agreement with the experimentally reported.•Global reactivity parameters confirmed noticeable stability of both compounds.•The compound 3b shown to be more reactive in redox processes.
The 2‑hydroxy-1-naphthaldehyde based Schiff base zwitterions: (E)-1-(((4-methoxyphenyl)-iminio)methyl)naphthalen-2-olate (3a) and (E)-1-(((2‑methoxy-4-nitrophenyl)iminio)methyl)-naphthalen-2-olate (3b) have been obtained from the condensation reaction of 2‑hydroxy-1-naphthaldehyde and substituted aniline. The structures of these Schiff base zwitterions have been verified unambiguously by the single-crystal X-ray diffraction analysis. The SC-XRD (single crystal X-ray diffraction) exploration revealed that both compounds have same crystal system, i.e., monoclinic, and same space group, i.e., P21/c. Also, there are intermolecular attractive forces that are responsible for the stabilization of these organic frameworks. Additionally, these structures have been thoroughly explored by the density functional theory (DFT) calculations. The optimized geometries were found to be close to the experimental structures. The analysis of frontier molecular orbitals (FMOs) suggested that 3a would be more stable towards redox reactions than 3b. Therefore, modifying the imine-zwitterion structure with the nitro group and changing the position of methoxy group would increase the reactivity of the resulting species. This is further supported by the computed global reactivity parameters (GRPs): both compounds should be considered as noticeably stable, both from thermodynamic and kinetic points of view, with 3a showing even higher stability. The compound 3b was shown to be more reactive in redox processes, being more prone to be reduced rather than oxidized. The higher stability of 3a was further supported by the NBO analysis results.
The synthesis of 5,13-dimethyl-9-aza7helicene is reported. A new method to access optically pure helicene with methyl substituent is established. The diastereomeric helical diamine is prepared from ...5,13-diformyl-9-aza7helicene by attaching a chiral auxiliary and its isomers were physically separated by column chromatography. This diastereomeric diamine with two different benzyl bonds were subjected to Pd–C catalyzed hydrogenation at ambient condition, resulting in the hydrogenolysis at the less substituted site. The enantiomers of 5,13-dimethyl-9-aza7helicene were accessed, and their chiroptical properties were investigated.
For Table of Contents:A new approach towards the synthesis of methyl substituted optically pure helicene was established, where the selective hydrogenolysis of diastereomeric benzylamine was carried out. The structural aspects of the helical system are investigated by single crystal X-ray diffraction analysis of 5,13-diformyl-9-aza7helicene. Display omitted
•Novel organic salt of Pyrimethamine drug was synthesized and characterized•Chemical properties were assessed using DFT approach•High chemical reactivity and electrophilicity of drug compound
The ...antimalarial drug, pyrimethamine is not used any more for the treatment of malaria due to the resistance phenomenon, though, it can be modified for the potential reuse in medicinal chemistry. The current research article is about the possibility of obtaining novel form of the drug with better drug delivery properties by the preparation of new pyrimethamine-based organic salt: 2,4-diamino-5-(4-chlorophenyl)-6-ethylpyrimidin-1-ium 2,4-dichlorobenzoate (1:1) (DECB). The salt was prepared via neutralization reaction utilizing pyrimethamine and 2,4-dichlorobenzoic acid as the base and acid components respectively. The structure of the salt was confirmed by the single crystal analysis. The single crystal X-ray diffraction (SC-XRD) investigation shows that strong N-H…O and comparatively weak C-H…π bonding are responsible for crystal packing forming the infinite 3D network. Hirshfeld surface analysis proposes high reactivity due to unequal distribution of the intermolecular interactions. The high chemical reactivity was confirmed by performing the density functional theory (DFT) calculations that showed high electrophilic properties of the DECB.
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The synthesis of 2-amino-5-aza6helicene and its derivatives is reported. The diastereomeric (R)-menthylcarbamate derivative of this aza6helicene is prepared and its isomers were physically separated ...by column chromatography and their optical properties were measured. Optically pure isomer (P)-2-amino-5-aza6helicene was generated and its Boc-derivative was prepared.
Optically active derivatives of 2-amino-5-aza6helicene are synthesized and characterized. Their chiroptical properties, SOR and CD, were measures. The structural aspects of the helical system are investigated by single crystal X-ray diffraction analysis. Display omitted
•A Lead complex is synthesized and single crystal XRD showed that crystal structure of the synthesized compound is of dimeric nature.•Hirshfeld surface analysis inferred that H⋯H followed by H⋯C and ...H⋯S contacts have higher contribution in the supramolecular assembly stabilization as compare to other contacts.•Void analysis showed that the compound will have good response to an applied stress.•Computational study results are consistent with the corresponding ones of single crystal XRD.
The current work describes the synthesis of a new Pb(II) complex PbROMLIP2 with a thiourea derivative. The synthesized complex was characterized by FT-IR, elemental analysis, and single crystal X-ray diffraction (XRD) analysis. The spectroscopic data confirmed that the thiourea ligands coordinate with the Pb center in a way that forms a dimeric structure with a distorted square pyramidal coordination geometry. Hirshfeld surface analysis was used to elaborate on the numerous intermolecular interactions responsible for the stabilization of the supramolecular assembly of the complex. Voids analysis was used to predict the crystal response to an applied stress. Geometry optimization of the synthesized complex was also explored through density functional theory (DFT) analysis. The structural parameters obtained through the DFT study at B3LYP/6-311g(d,p) level of theory with basis set 6-311G(d,p) are in good match with X-ray diffraction analysis. Additionally, the electronic energy band gap of the prepared complex was explored, which revealed the electronic transition during excitation from the ground state to the excited state.
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Recently, syntheses and quantum chemical insights in the structures and properties of crystalline organic compounds have attracted significant attention of the scientific community. In the current ...work we report the synthesis of two arylsulfonylated 2-amino-6-methylpyrimidin derivatives, A and B. X-ray diffraction technique confirmed the structures of both compounds. The single-crystal analysis showed the presence of various non-covalent interactions that are responsible for their structural stabilities. Theoretical calculations of A and B were performed at the B3LYP/6–311++G(d,p) level. The calculated structures of both compounds were found to be in good agreement with the experimentally reported structural parameters. Frontier molecular orbital (FMO) analysis showed that employing different moieties to bind with the 2-amino-6-methylpyrimidin-4-ol group causes certain changes to the FMOs energies and energy gaps, thus affecting the stability, reactivity, and other properties of the resulting compounds. The Natural Bond Order (NBO) analysis showed high stabilization energies within the molecules of both compounds. The calculated global reactivity parameters (GRP) confirmed noticeable stability of both compounds, showing the compound B to be more stable than the compound A.
•Synthesis of two arylsulfonylated 2-amino-6-methylpyrimidin derivatives reported.•Various non-covalent interactions responsible for their structural stabilities.•Calculated structures in good agreement with the experimentally reported.•NBO analysis showed high stabilization energies within the molecules of both compounds.•Global reactivity parameters confirmed noticeable stability of both compounds.
•Effective production of the novel 2-amino-6-methylpyridine co-crystal salt.•Salt stabilization by ionic interactions, hydrogen bonds and stacking interactions.•DFT study supports the existence of ...quite strong intracomplex hydrogen bonding.•Current compound can have potential future applications in pharmacology.
The current work reports the formation methodology of the co-crystal between 2-amino-6-methylpyridine and succinic acid, its single-crystal characterization, and the computational study. The single-crystal analysis showed that the co-crystal molecules are interlinked by N···H‒O and O···H‒O bonds to form R22 (8) loop and D22 (5) and D22 (8) finite pattern along with the formation of infinite 2D network in the (1 0 1¯) plane having base vectors 1 0 1 and 0 1¯ 0. Moreover, the weak interactions of the π-π stacking type and CO-Cg interactions are found in the title compound helping in further strengthening of the crystal structure. The Hirshfeld surface analysis confirmed that H···H interatomic contacts are the largest contributor to entire interatomic contacts with contribution of 45.8%. The computational studies supported the presence of significantly strong hydrogen bonds within the title complex. The molecular orbital analysis suggested that both HOMO/HOMO-1 and LUMO/LUMO+1 would be able to participate in oxidative-reductive processes of the complex. The HOMO has dominating contributions from one succinate unit along with minor contributions from the H-bonded NH2-group of the neighboring 2-amino-6-methylpyridin-1-ium moiety. The calculated values of the global reactivity parameters suggest noticeable stability of the title complex. It was also shown to possess quite pronounced nonlinear optical properties.
Designing new Low molecular weight gelators (LMOGs) which can congeal organic/aqueous solvents is a daunting task, especially those capable of selective organogelation in presence of oil/water ...systems. Phase selective organogelation (PSOG) offers various advantages over conventional methods for oil spill remediation, viz. programmability, responsiveness and biocompatibility. Molecules with multiple fragments such as one-dimensional hydrogen bonding groups, terminal bulky group and a variable organic moiety (aromatic, aliphatic, alicyclic) appear to be good candidates for design of new LMOGs. In this work, a new series of pivalic acid based amides (1A–13A) having aromatic, aliphatic and alicyclic backbones were synthesized and characterized by various physicochemical methods. All the compounds were exploited for their ability to congeal various organic solvents including crude oil fractions, fuels and oils. Out of 13 newly synthesized compounds, six turned out to be excellent organogelators. Multifunctional properties of these compounds were observed such as selective gelation of aliphatic solvents in presence of water and removal of dyes from aqueous medium with good efficiencies. A detailed study is undertaken to establish the cause of gelation/non-gelation of solvents based on structure-property correlation using single-crystal X-ray diffraction, powder X-ray diffraction, Hirshfeld surface analysis, etc. Moreover, these compounds represent a class of one of the smallest molecules explored for the application of phase selective organogelation of fuel for containing oil-spills and dye adsorbing materials for water pollution control.
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