Showing papers on "Planarity testing published in 2022"

Design strategies for improving the crystallinity of covalent organic frameworks and conjugated polymers: a review

Abstract: Highly crystalline covalent organic frameworks (COFs) or conjugated polymers (CPs) are very important and highly desirable because these materials would display better performance in diverse devices and provide more structure–property related information. However, how to achieve highly crystalline or single-crystal COFs and CPs is very challenging. Recently, many research studies have demonstrated the possibility of enhancing the crystallinity of COFs and CPs. Thus, it is timely to offer an overview of the important progress in improving the crystallinity of COFs and CPs from the viewpoint of design strategies. These strategies include polycondensation reaction optimization, improving the planarity, fluorine substitution, side chain engineering, and so on. Furthermore, the challenges and perspectives are also discussed to promote the realization of highly crystalline or single-crystal COFs and CPs.

Design strategies for improving the crystallinity of covalent organic frameworks and conjugated polymers: a review

Abstract: Highly crystalline covalent organic frameworks (COFs) or conjugated polymers (CPs) are very important and highly desirable because these materials would display better performance in diverse devices and provide more structure-property related information. However, how to achieve highly crystalline or single-crystal COFs and CPs is very challenging. Recently, many research studies have demonstrated the possibility of enhancing the crystallinity of COFs and CPs. Thus, it is timely to offer an overview of the important progress in improving the crystallinity of COFs and CPs from the viewpoint of design strategies. These strategies include polycondensation reaction optimization, improving the planarity, fluorine substitution, side chain engineering, and so on. Furthermore, the challenges and perspectives are also discussed to promote the realization of highly crystalline or single-crystal COFs and CPs.

Cyclobutanes in Small‐Molecule Drug Candidates

Abstract: Cyclobutanes are increasingly used in medicinal chemistry in the search for relevant biological properties. Important characteristics of the cyclobutane ring include its unique puckered structure, longer C−C bond lengths, increased C−C π‐character and relative chemical inertness for a highly strained carbocycle. This review will focus on contributions of cyclobutane rings in drug candidates to arrive at favorable properties. Cyclobutanes have been employed for improving multiple factors such as preventing cis/trans‐isomerization by replacing alkenes, replacing larger cyclic systems, increasing metabolic stability, directing key pharmacophore groups, inducing conformational restriction, reducing planarity, as aryl isostere and filling hydrophobic pockets.

Toward High-Efficiency Organic Photovoltaics: Perspectives on the Origin and Role of Energetic Disorder.

Abstract: The power conversion efficiency of organic photovoltaics is strongly limited by relatively large energy loss, which is partially due to the disordered nature of organic semiconductors. This disordered nature not only hinders the rational design of molecules with excellent photophysical properties but also prevents a more thorough understanding of the inherent link between microscopic parameters and physical phenomena. In this Perspective, we demonstrate that the injection-dependent emission line-shape in organic semiconductors is primarily associated with a state-filling effect, where the extent of spectral blue-shift can be a strong indicator for energetic disorder. Molecular geometry with rigidity and coplanarity not only promotes preferential face-on stacking that narrows the energetic distribution of subgap states but also impedes torsional deformations of the conjugated backbone away from planarity, thereby facilitating larger π-electron delocalization. These structural characteristics explain the seemingly contradictory high radiative efficiency of low-bandgap nonfullerene molecules, providing promising molecular design strategies to realize high-efficiency organic photovoltaics.

A novel orange-red thermally activated delayed fluorescence emitter with high molecular rigidity and planarity realizing 32.5% external quantum efficiency in organic light-emitting diodes.

Abstract: Simultaneous optimization of photoluminescence quantum yield (ΦPL) and horizontally oriented dipoles (Θ‖) is considerably challenging for orange and red thermally activated delayed fluorescence (TADF) emitters, due to the conflicts between enhancing molecular rigidity and improving molecular planarity. Herein, a novel orange-red TADF emitter 10-(dipyrido[3,2-a:2',3'-c]phenazin-11-yl)-10H-spiro[acridine-9,9'-fluorene] (SAF-2NP) was constructed with a donor-acceptor structure. The highly rigid donor and acceptor segments ensure the overall rigidity of the emitter. More importantly, the quasi-coplanar structure between the acceptor and the fluorene moiety in the donor unit enlarges the molecular plane without weakening rigidity. Consequently, SAF-2NP exhibited extremely high ΦPL and Θ‖ of 99% and 85%, respectively. The optimal organic light-emitting diode using SAF-2NP as the emitter and 4,4'-di(9H-carbazol-9-yl)-1,1'-biphenyl (CBP) as the host demonstrated an unparalleled external quantum efficiency of 32.5% and a power efficiency of 85.2 lm W-1 without any extra light extraction structure. This work provides a feasible strategy to establish efficient orange and red TADF emitters with both high rigidity and planarity.

Furan-based Organic Cathode Material for High-performance Sodium Ion Batteries

Abstract: Organic materials are potential to be applied as electrode materials for Sodium Ion Batteries, due to the easily tunable molecular structures and low costs. However, the dissolution of the organic...

Nonfused Ring Electron Acceptors for Efficient Organic Solar Cells Enabled by Multiple Intramolecular Conformational Locks

Abstract: Nonfused ring electron acceptors (NFREAs) have become a research hotspot of organic solar cells (OSCs) due to their facile synthesis. However, efficient NFREAs not only need to maintain the advantages of FREAs but also need to optimize the molecular structure of the conjugate backbone to achieve good planarity. Therefore, choosing the appropriate building blocks is a prerequisite for achieving efficient OSCs. Here, two simple NFREAs 2T2CSi-4F and 4T2CSi-4F, based on diester-thieno[3,2-b]thiophene (2T2C) as the central core unit and 4,4-di-2-ethylhexyl-dithieno[3,2-b:2′,3′-d]silole (DTSi) or thieno[3,2-b]thiophene (TT) as the conjugated linking unit, were designed and synthesized. The density function theory results manifest that the oxygen atom of the thiophene ester group can form O···S interaction with the sulfur atom. Introducing noncovalent interactions can form multiple intramolecular conformational locks, which greatly enhance the molecular planarity. In addition, 2T2CSi-4F with a symmetrical structure exhibits red-shifted absorption, shallower lowest unoccupied molecular orbital energy levels, and stronger crystallinity than 4T2CSi-4F. Therefore, the PBDB-T:2T2CSi-4F device with favorable molecular packing and morphology achieves a higher power conversion efficiency of 10.04%. Our work demonstrates that the 2T2C unit and multimolecular conformational lock strategy are conducive to the development of efficient NFREAs.

Recent Structural Engineering of Polymer Semiconductors Incorporating Hydrogen Bonds

Abstract: Highly planar, extended π‐electron organic conjugated polymers have been increasingly attractive for achieving high‐mobility organic semiconductors. In addition to the conventional strategy to construct rigid backbone by covalent bonds, hydrogen bond has been employed extensively to increase the planarity and rigidity of polymer via intramolecular noncovalent interactions. This review provides a general summary of high‐mobility semiconducting polymers incorporating hydrogen bonds in field‐effect transistors over recent years. The structural engineering of the hydrogen bond‐containing building blocks and the discussion of theoretical simulation, microstructural characterization, and device performance are covered. Additionally, the effects of the introduction of hydrogen bond on self‐healing, stretchability, chemical sensitivity, and mechanical properties are also discussed. The review aims to help and inspire design of new high‐mobility conjugated polymers with superiority of mechanical flexibility by incorporation of hydrogen bond for the application in flexible electronics.

Smartphone LiDAR Technologies for Surveying and Reality Modelling in Urban Scenarios: Evaluation Methods, Performance and Challenges

Abstract: The aim of the research was to evaluate the performance of smartphone depth sensors (Time of Flight Camera(ToF) and Light Detection and Ranging (LiDAR)) from Android (Huawei P30 Pro) and iOS (iPhone 12 Pro and iPAD 2021 Pro) devices in order to build a 3D point cloud. In particular, the smartphones were tested in several case studies involving the scanning of several objects: 10 building material samples, a statue, an interior room environment and the remains of a Doric column in a major archaeological site. The quality of the point clouds was evaluated through visual analysis and using three eigenfeatures: surface variation, planarity and omnivariance. Based on this approach, some issues with the point clouds generated by smartphones were highlighted, such as surface splitting, loss of planarity and inertial navigation system drift problems. In addition, it can finally be deduced that, in the absence of scanning problems, the accuracies achievable from this type of scanning are ~1–3 cm. Therefore, this research intends to describe a method of quantifying anomalies occurring in smartphone scans and, more generally, to verify the quality of the point cloud obtained with these devices.

P3Depth: Monocular Depth Estimation with a Piecewise Planarity Prior

Abstract: Monocular depth estimation is vital for scene understanding and downstream tasks. We focus on the supervised setup, in which ground-truth depth is available only at training time. Based on knowledge about the high regularity of real 3D scenes, we propose a method that learns to selectively leverage information from coplanar pixels to improve the predicted depth. In particular, we introduce a piecewise planarity prior which states that for each pixel, there is a seed pixel which shares the same planar 3D surface with the former. Motivated by this prior, we design a network with two heads. The first head outputs pixel-level plane coefficients, while the second one outputs a dense off-set vector field that identifies the positions of seed pixels. The plane coefficients of seed pixels are then used to predict depth at each position. The resulting prediction is adaptively fused with the initial prediction from the first head via a learned confidence to account for potential deviations from precise local planarity. The entire architecture is trained end-to-end thanks to the differentiability of the proposed modules and it learns to predict regular depth maps, with sharp edges at occlusion boundaries. An extensive evaluation of our method shows that we set the new state of the art in supervised monocular depth estimation, surpassing prior methods on NYU Depth-v2 and on the Garg split of KITTI. Our method delivers depth maps that yield plausible 3D reconstructions of the input scenes. Code is available at: https://github.com/SysCV/P3Depth

Vibronic States and Edge-On Oriented π-Stacking in Poly(3-alkylthiophene) Thin Films

Abstract: The influence of alkyl side-chain length [CnH2n+1 (A), where n = 6 (hexyl), 8 (octyl), 12 (dodecyl)] and thermal annealing (TA) and the definite roles of these in the quantity and quality of π-stacked crystallinity and edge-on orientated (EO) ordering of spin-coated poly(3-alkylthiophene) [P3AT] thin films, which are of massive significance in their optoelectronic properties, were investigated using complementary optical absorption spectroscopy and X-ray reflectivity (XR) techniques. The energy-band diagram, corresponding to the vibronic levels, obtained from the optical absorption spectrum provides information about the percentage, planarity, local order, and average conjugation length of the crystalline aggregates, while the electron density profile obtained from the XR provides unique information about the EO ordering and its variation along the depth. A prominent EO ordering near the substrate with a gradually decreased ordering toward the top surface is observed in each film. An as-cast P3HT film of shorter side-chain (having a natural nucleation tendency and rigidity) shows a slightly higher crystallinity and weaker excitonic coupling, while as-cast P3DDT film (having longer side-chain flexibility) shows a slightly better EO ordering. After the TA, the planarity of the unfolded backbone improves in each film; however, the effect is maximum in the P3DDT film. The EO ordering also improves throughout the film (by a thermal energy-induced reorientation of crystallites) but more toward the top surface (by increasing the decay length), preserving the exponential decay nature. The P3HT film (with the better initial crystallinity and planarity) shows an appreciable improvement, while the P3DDT film (where the crystallinity increases and crystallites have a better reorientational ability) shows the maximum improvement in the EO ordering. The improvement of the crystallinity (in quantity and quality) and the EO ordering of P3AT in thin films (as active layers), especially near the film–substrate interfaces, are of immense importance for their better in-plane charge carrier mobility in a thin-film transistor.

Hexagonal Planar [B6H6] within a [B6H12] Borate complex; Structure and Bonding of [(Cp*Ti)2(µ-ɳ6:ɳ6-B6H6)(µ-H)6].

Abstract: Isolation of planar [B6H6] is a long-awaited goal in boron chemistry. Several attempts in the past to stabilize [B6H6] were unsuccessful due to the domination of polyhedral geometries. Herein, we report the synthesis of a triple-decker sandwich complex of titanium [(Cp*Ti)2(μ-η6:η6-B6H6)(μ-H)6] (1), which features the first-ever experimentally achieved nearly planar six-membered [B6H6] ring, albeit within a [B6H12] borate. The small deviation from planarity is a direct consequence of predicted structural pattern of middle ring in 24 Valence Electron Count (VEC) triple-decker complexes. The large ring size of [B6H6] in 1 brings the metal-metal distance into the bonding range. However, significant electron delocalization from M-M bonding orbital to the bridging hydrogen and B-B skeleton in the middle decreases its bond strength.

Planar 2D wireframe DNA origami

Abstract: Two-dimensional (2D) DNA origami is widely used for applications ranging from excitonics to single-molecule biophysics. Conventional, single-layer 2D DNA origami exhibits flexibility and curvature in solution; however, that may limit its suitability as a 2D structural template. In contrast, 2D wireframe DNA origami rendered with six-helix bundle edges offers local control over duplex orientations with enhanced in-plane rigidity. Here, we investigate the 3D structure of these assemblies using cryo–electron microscopy (cryo-EM). 3D reconstructions reveal a high degree of planarity and homogeneity in solution for polygonal objects with and without internal mesh, enabling 10-Å resolution for a triangle. Coarse-grained simulations were in agreement with cryo-EM data, offering molecular structural insight into this class of 2D DNA origami. Our results suggest that these assemblies may be valuable for 2D material applications and geometries that require high structural fidelity together with local control over duplex orientations, rather than parallel duplex assembly.

A planarity estimate for pinched solutions of mean curvature flow

Abstract: We show that the blow-ups of compact solutions to the mean curvature flow in $\mathbb{R}^N$ initially satisfying the pinching condition $|A|^2 < c |H|^2$ for a suitable constant $c = c(n)$ must be codimension one.

Recent advances in the synthesis of 2,3-fused quinazolinones.

Abstract: As one of the most important structural units in pharmaceuticals and medicinal chemistry, quinazolinone and its derivatives exhibit a wide range of biological and pharmacological activities, including anti-inflammatory, antitubercular, antiviral, and anticancer activities, etc. In particular, 2,3-fused quinazolinones have attracted much attention because the rings fused to the 2,3-positions of quinazolinones improve their rigidity and planarity. Their synthetic strategies have made great advances in recent years. Therefore, this review focuses on novel strategies for the synthesis of 2,3-fused quinazolinone derivatives from 2017 to 2022, such as the difunctionalization of alkenes, the ring-opening of easily available small rings, dehydrogenative cross-coupling reactions, transition-metal catalyzed cyclizations, cycloadditions, and other cascade reactions.

Structural study of 1- and 2-naphthol: new insights into the non-covalent H-H interaction in cis-1-naphthol.

Abstract: Previous microwave studies of naphthol monomers were supplemented by measuring spectra of all 13C mono-substituted isotopologues of the cis- and trans-conformers of 1-naphthol and 2-naphthol in their natural abundances. The resulting data were utilized to determine substitution structures and so-called semi-experimental effective structures. Results from electronic structure calculations show that the OH group of cis-1-naphthol points ≈6° out of plane, which is consistent with the inertial defect data of cis- and trans-1-naphthol. The non-planarity of cis-1-naphthol is a result of a close-contact H-atom-H-atom interaction. This type of H-H interaction has been the subject of much controversy in the past and we provide here an in-depth theoretical analysis of it. The naphthol system is particularly well-suited for such analysis as it provides internal standards with its four different isomers. The methods used include quantum theory of atoms in molecules, non-covalent interactions, independent gradient model, local vibrational mode, charge model 5, and natural bond orbital analyses. We demonstrate that the close-contact H-H interaction is neither a purely attractive nor repulsive interaction, but rather a mixture of the two.

Solid-State Luminescent Materials Containing Both Indole and Pyrimidine Moieties: Design, Synthesis, and Density Functional Theory Calculations

Abstract: Heterocyclic compounds with effective solid-state luminescence offer a wide range of uses. It has been observed that combining pyrimidine and indole moieties in a single molecule can enhance material behavior dramatically. Here, different heterocyclic compounds with indole and pyrimidine moieties have been synthesized effectively, and their structures have been validated using NMR, IR, and mass spectroscopy. The photoluminescence behavior of two substances was investigated in powder form and solutions of varying concentrations. After aggregation, one molecule displayed a redshifted luminescence spectrum, whereas another homolog showed a blueshift. Thus, density functional theory calculations were carried out to establish that introducing a terminal group allows modifying of the luminescence behavior by altering the molecular packing. Because of the non-planarity, intermolecular interactions, and tiny intermolecular distances within the dimers, the materials demonstrated a good emission quantum yield (Φem) in the solid state (ex. 25.6%). At high temperatures, the compounds also demonstrated a stable emission characteristic.

Atomic Embeddability, Clustered Planarity, and Thickenability

Abstract: We study the atomic embeddability testing problem, which is a common generalization of clustered planarity ( c-planarity , for short) and thickenability testing, and present a polynomial-time algorithm for this problem, thereby giving the first polynomial-time algorithm for c-planarity. C-planarity was introduced in 1995 by Feng, Cohen, and Eades as a variant of graph planarity, in which the vertex set of the input graph is endowed with a hierarchical clustering and we seek an embedding (crossing free drawing) of the graph in the plane that respects the clustering in a certain natural sense. Until now, it has been an open problem whether c-planarity can be tested efficiently. The thickenability problem for simplicial complexes emerged in the topology of manifolds in the 1960s. A 2-dimensional simplicial complex is thickenable if it embeds in some orientable 3-dimensional manifold. Recently, Carmesin announced that thickenability can be tested in polynomial time. Our algorithm for atomic embeddability combines ideas from Carmesin’s work with algorithmic tools previously developed for weak embeddability testing. We express our results purely in terms of graphs on surfaces, and rely on the machinery of topological graph theory. Finally, we give a polynomial-time reduction from atomic embeddability to thickenability thereby showing that both problems are polynomially equivalent, and show that a slight generalization of atomic embeddability to the setting in which clusters are toroidal graphs is NP-complete.

Crucial Factors Regulating Intramolecular Charge-Transfer-Based Radiative Efficiency in ortho-Carboranyl Luminophores: Planarity between Substituted Biphenyl Rings

Abstract: o-Carboranyl compounds contain specific geometries, ranging from planar to orthogonally distorted biphenyl rings. Herein, 13 o-carboranyl compounds, 1HF–13PP, were synthesized and fully characterized to determine the impact of structural formation of the aromatic group appended with the o-carborane to estimate the efficiency of their radiative decay process. All the compounds exhibited significant intramolecular charge transfer (ICT)-based emission in the crystalline state at 298 K. Remarkably, increasing the distorted dihedral angles between biphenyl rings gradually decreased the emission efficiencies. Furthermore, their radiative decay constants decreased linearly with increasing dihedral angles, which demonstrated the inversely proportional relationship between these two factors. These findings distinctly suggest that the planar or distorted geometry of substituted aryl groups can strongly affect the efficiency of the ICT-based radiative process in o-carboranyl luminophores.

Advancing the Am Extractant Design through the Interplay among Planarity, Preorganization, and Substitution Effects.

Abstract: Advancing the field of chemical separations is important for nearly every area of science and technology. Some of the most challenging separations are associated with the americium ion Am(III) for its extraction in the nuclear fuel cycle, 241Am production for industrial usage, and environmental cleanup efforts. Herein, we study a series of extractants, using first-principle calculations, to identify the electronic properties that preferentially influence Am(III) binding in separations. As the most used extractant family and because it affords a high degree of functionalization, the polypyridyl family of extractants is chosen to study the effects of the planarity of the structure, preorganization of coordinating atoms, and substitution of various functional groups. The actinyl ions are used as a structurally simplified surrogate model to quickly screen the most promising candidates that can separate these metal ions. The down-selected extractants are then tested for the Am(III)/Eu(III) system. Our results show that π interactions, especially those between the central terpyridine ring and Am(III), play a crucial role in separation. Adding an electron-donating group onto the terpyridine backbone increases the binding energies to Am(III) and stabilizes Am-terpyridine coordination. Increasing the planarity of the extractant increases the binding strength as well, although this effect is found to be rather weak. Preorganizing the coordinating atoms of an extractant to their binding configuration as in the bound metal complex speeds up the binding process and significantly improves the kinetics of the separation process. This conclusion is validated by the synthesized 1,2-dihydrodipyrido[4,3-b;5,6-b]acridine (13) extractant, a preorganized derivative of the terpyridine extractant, which we experimentally showed was four times more effective than terpyridine at separating Am3+ from Eu3+ (SFAm/Eu ∼ 23 ± 1).

Planar Panels and Planar Supporting Beams in Architectural Structures

Abstract: In this article, we investigate geometric properties and modeling capabilities of quad meshes with planar faces whose mesh polylines enjoy the additional property of being contained in a single plane. This planarity is a major benefit in architectural design and building construction: If a structural element is contained in a plane, it can be manufactured on the ground without scaffolding and put into place as a whole. Further, the plane it is contained in serves as part of a so-called support structure. We discuss design of meshes under the requirement that one half of mesh polylines are planar (“P meshes”), and we also investigate the geometry and design of meshes where all polylines enjoy this property (“PP meshes”). We work in the space of planes and with appropriate transformations of that space. We also incorporate further properties relevant for architectural design, such as near-rectangular panels and repetitive nodes. We provide geometric insights, give explicit constructions, and show an approach to geometric modeling of both P meshes and PP meshes, in particular, the case of nearly rectangular panels.