Accounts of Chemical Research最新文献

{"title":"Quantum Chemical Interrogation of Reactions Promoted by Dirhodium Tetracarboxylate Catalysts─Mechanism, Selectivity, and Nonstatistical Dynamic Effects.","authors":"Dean J Tantillo","doi":"10.1021/acs.accounts.4c00214","DOIUrl":"https://doi.org/10.1021/acs.accounts.4c00214","url":null,"abstract":"<p><p>ConspectusRh₂L₄ catalysts have risen in popularity in the world of organic synthesis, being used to accomplish a variety of reactions, including C-H insertion and cyclopropanation, and often doing so with high levels of stereocontrol. While the mechanisms and origins of selectivity for such reactions have been examined with computational quantum chemistry for decades, only recently have detailed pictures of the dynamic behavior of reacting Rh₂L₄-complexed molecules become accessible. Our computational studies on Rh₂L₄ catalyzed reactions are described here, with a focus on C-H insertion reactions of Rh₂L₄-carbenes. Several issues complicate the modeling of these reactions, each providing an opportunity for greater understanding and each revealing issues that should be incorporated into future rational design efforts. First, the fundamental mechanism of C-H insertion is discussed. While early quantum chemical studies pointed to transition structures with 3-center [C-H-C] substructures and asynchronous hydride transfer/C-C bond formation, recent examples of reactions with particularly flat potential energy surfaces and even discrete zwitterionic intermediates have been found. These reactions are associated with systems bearing π-donating groups at the site of hydride transfer, allowing for an intermediate with a carbocation substructure at that site to be selectively stabilized. Second, the possible importance of solvent coordination at the Rh atom distal to the carbene is discussed. While effects on reactivity and selectivity were found to be small, they turn out not to be negligible in some cases. Third, it is shown that, in contrast to many other transition metal promoted reactions, many Rh₂L₄ catalyzed reactions likely involve dissociation of the Rh₂L₄ catalyst before key chemical steps leading to products. When to expect dissociation is associated with specific features of substrates and the product-forming reactions in question. Often, dissociation precedes transition structures for pericyclic reactions that involve electrons that would otherwise bind to Rh₂L₄. Finally, the importance of nonstatistical dynamic effects, characterized through ab initio molecular dynamics studies, in some Rh₂L₄ catalyzed reactions is discussed. These are reactions where transition structures are shown to be followed by flat regions, very shallow minima, and/or pathways that bifurcate, all allowing for trajectories from a single transition state to form multiple different products. The likelihood of encountering such a situation is shown to be associated again with the likelihood of formation of zwitterionic structures along reaction paths, but ones for which pathways to <i>multiple</i> products are expected to be associated with very low or no barriers. The connection between these f","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":null,"pages":null},"PeriodicalIF":16.4,"publicationDate":"2024-06-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141448948","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Reaction Templates: Bridging Synthesis Knowledge and Artificial Intelligence.","authors":"Shuan Chen, Juhwan Noh, Jidon Jang, Seongmin Kim, Geun Ho Gu, Yousung Jung","doi":"10.1021/acs.accounts.4c00261","DOIUrl":"https://doi.org/10.1021/acs.accounts.4c00261","url":null,"abstract":"<p><p>ConspectusThe field of chemical research boasts a long history of developing software to automate synthesis planning and reaction prediction. Early software relied heavily on expert systems, requiring significant effort to encode vast amounts of synthesis knowledge into a computer-readable format. However, recent advancements in deep learning have shifted the focus toward AI models, offering improved prediction capabilities. Despite these advancements, current AI models often lack the integration of known synthesis rules and intuitions, creating a gap that hinders interpretability and future development of the models. To bridge them, our research group has been actively working on incorporating reaction templates into deep learning models, achieving promising results across various applications.In this Account, we present our latest works to incorporate the known synthesis knowledge into the deep learning models through the utilization of reaction templates. We begin by highlighting the limitations of early computer programs heavily reliant on hand-coded rules. These programs, while providing a foundation for the field, presented limitations in scalability and adaptability. We then introduce SMARTS (SMILES arbitrary target specification), a popular Python-readable format for representing chemical reactions. This format of reaction encoding facilitates the quick integration of synthesis knowledge into AI models built using the Python language. With the SMARTS-based reaction templates, we introduce our recent efforts of developing an AI model for reaction-based molecule optimization. Subsequently, we discuss the recent efforts to automate the extraction of reaction templates from vast chemical reaction databases. This approach eliminates the previously required manual effort of encoding knowledge, a process that could be time-consuming and prone to error when dealing with large data sets. By customizing the automated extraction algorithm, we have developed powerful AI models for specific tasks such as retrosynthesis (LocalRetro), reaction outcome prediction (LocalTransform), and atom-to-atom mapping (LocalMapper). These models, aligned with the intuition of chemists, demonstrate the effectiveness of incorporating reaction templates into deep learning frameworks.Looking toward the future, we believe that utilizing reaction templates to connect known chemical knowledge and AI models holds immense potential for various applications. Not only can this approach significantly benefit future AI models focused on challenging tasks like reaction mechanism labeling and prediction, but we anticipate it can also extend its reach to the realm of inorganic synthesis. By integrating synthesis knowledge, we can not only achieve improved performance but also enhance the interpretability of AI models, paving the way for further advancements in AI-powered chemical synthesis.</p>","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":null,"pages":null},"PeriodicalIF":16.4,"publicationDate":"2024-06-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141453670","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Insights into the Optimization of Catalytic Active Sites in Lithium-Sulfur Batteries.","authors":"Peng Wang, Baojuan Xi, Shenglin Xiong","doi":"10.1021/acs.accounts.4c00244","DOIUrl":"https://doi.org/10.1021/acs.accounts.4c00244","url":null,"abstract":"<p><p>ConspectusLithium-sulfur batteries (LSBs), recognized for their high energy density and cost-effectiveness, offer significant potential for advancement in energy storage. However, their widespread deployment remains hindered by challenges such as sluggish reaction kinetics and the shuttle effect of lithium polysulfides (LiPSs). By the introduction of catalytic materials, the effective adsorption of LiPSs, smooth surface migration behavior, and significantly reduced conversion energy barriers are expected to be achieved, thereby sharpening electrochemical reaction kinetics and fundamentally addressing the aforementioned challenges. However, driven by practical application targets, the demand for higher loadings and reduced electrolyte parameters inevitably exacerbates the burden on catalytic materials during their service. Additionally, given that catalytic materials contribute negligible electrochemical capacity, their incorporation inevitably increases the mass of nonactive components for reducing the energy density of LSBs. A meticulous insight into the lithium-sulfur catalytic reaction reveals that the conversion of LiPSs is dominated by active sites on the surfaces of catalytic materials. These microregions provide the necessary electron and ion transport for the conversion reaction of LiPSs, with their efficacy and quantity directly impacting the conversion efficiency. In light of these considerations, the strategic optimization of active sites emerges as a paramount pathway toward promoting the performance of LSBs while concurrently mitigating unnecessary mass. Here, we outline three strategies developed by our group to optimize active sites of catalytic materials: (1) Augmenting active sites by customizing structural modulation and precise dimensional control to maximize exposure. Emphasis has been placed on the approaches for material synthesis and the essence of reactions for achieving this strategy. (2) Regulating the microenvironment of active sites by integrating the coordination refinement, long-range atomic interactions, metal-support interactions, and other electronic regulation strategies, thereby providing an elevation in the intrinsic catalytic performance. (3) Implementing a self-cleaning mechanism for active sites to counteract deactivation by designing a tandem adsorption-migration-transformation pathway of sulfur contained within the molecular domain. Throughout this process, the intrinsic mechanisms driving performance enhancement through active site optimization strategies have been prominently emphasized, which encompass aspects such as electronic structure, atomic composition, and molecular configuration and significantly expand the comprehension of Li-S catalytic chemistry. Subsequently, considerations demanding heightened attention in future processes of active site optimization for catalytic materials have been delineated, including the in situ evolution patterns and resistance to the poisoning of active sites. ","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":null,"pages":null},"PeriodicalIF":16.4,"publicationDate":"2024-06-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141453671","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Quantitative Chemical Imaging of Organelles.","authors":"JoAnn Tinker, Palapuravan Anees, Yamuna Krishnan","doi":"10.1021/acs.accounts.4c00191","DOIUrl":"https://doi.org/10.1021/acs.accounts.4c00191","url":null,"abstract":"<p><p>ConspectusDNA nanodevices are nanoscale assemblies, formed from a collection of synthetic DNA strands, that may perform artificial functions. The pioneering developments of a DNA cube by Nadrian Seeman in 1991 and a DNA nanomachine by Turberfield and Yurke in 2000 spawned an entire generation of DNA nanodevices ranging from minimalist to rococo architectures. Since our first demonstration in 2009 that a DNA nanodevice can function autonomously inside a living cell, it became clear that this molecular scaffold was well-placed to probe living systems. Its water solubility, biocompatibility, and engineerability to yield molecularly identical assemblies predisposed it to probe and program biology.Since DNA is a modular scaffold, one can integrate independent or interdependent functionalities onto a single assembly. Work from our group has established a new class of organelle-targeted, DNA-based fluorescent reporters. These reporters comprise three to four oligonucleotides that each display a specific motif or module with a specific function. Given the 1:1 stoichiometry of Watson-Crick-Franklin base pairing, all modules are present in a fixed ratio in every DNA nanodevice. These modules include an ion-sensitive dye or a detection module and a normalizing dye for ratiometry that along with detection module forms a \"measuring module\". The third module is an organelle-targeting module that engages a cognate protein so that the whole assembly is trafficked to the lumen of a target organelle. Together, these modules allow us to measure free ion concentrations with accuracies that were previously unattainable, in subcellular locations that were previously inaccessible, and at single organelle resolution. By revealing that organelles exist in different chemical states, DNA nanodevices are providing new insights into organelle biology. Further, the ability to deliver molecules with cell-type and organelle level precision in animal models is leading to biomedical applications.This Account outlines the development of DNA nanodevices as fluorescent reporters for chemically mapping or modulating organelle function in real time in living systems. We discuss the technical challenges of measuring ions within endomembrane organelles and show how the unique properties of DNA nanodevices enable organelle targeting and chemical mapping. Starting from the pioneering finding that an autonomous DNA nanodevice could map endolysosomal pH in cells, we chart the development of strategies to target organelles beyond the endolysosomal pathway and expanding chemical maps to include all the major ions in physiology, reactive species, enzyme activity, and voltage. We present a series of vignettes highlighting the new biology unlocked with each development, from the discovery of chemical heterogeneity in lysosomes to identifying the first protein importer of Ca²⁺ into lysosomes. Finally, we discuss the broader applicability of targeting DNA nanodevices organelle-spe","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":null,"pages":null},"PeriodicalIF":16.4,"publicationDate":"2024-06-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141445488","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"The Duality of Raman Scattering.","authors":"Wei Min, Xin Gao","doi":"10.1021/acs.accounts.4c00159","DOIUrl":"https://doi.org/10.1021/acs.accounts.4c00159","url":null,"abstract":"<p><p>ConspectusFirst predicted more than 100 years ago, Raman scattering is a cornerstone of photonics, spectroscopy, and imaging. The conventional framework of understanding Raman scattering was built on Raman cross section σ_Raman. Carrying a dimension of area, σ_Raman characterizes the interaction strength between light and molecules during inelastic scattering. The numerical values of σ_Raman turn out to be many orders of magnitude smaller in comparison to the linear absorption cross sections σ_Absorption of similar molecular systems. Such an enormous gap has been the reason for researchers to believe the extremely feeble Raman scattering ever since its discovery. However, this prevailing picture is conceptually problematic or at least incomplete due to the fact that Raman scattering and linear absorption belong to different orders of light-matter interaction.In this Account, we will summarize an alternate way to think about Raman scattering, which we term stimulated response formulation. To capture the third-order interaction nature of Raman scattering, we introduced stimulated Raman cross section, σ_SRS, defined as the <i>intrinsic</i> molecular property in response to the external photon fluxes. Foremost, experimental measurement of σ_SRS turns out to be not weak at all or even larger when fairly compared with electronic counterparts of the same order. The analytical expression for σ_SRS derived from quantum electrodynamics also supports the measurement and proves that σ_SRS is intrinsically strong. Hence, σ_Raman and σ_SRS can be extremely small and large, respectively, for the same molecule at the same time. Our subsequent theoretical studies show that stimulated response formulation can unify spontaneous emission, stimulated emission, spontaneous Raman, and stimulated Raman via eq 10, in a coherent and symmetric way. In particular, an Einstein-coefficient-like equation, eq 12a, was derived, showing that σ_Raman can be explicitly expressed as σ_SRS multiplied by an effective photon flux arising from zero-point fluctuation of the vacuum. The feeble vacuum fluctuation hence explains how σ_SRS can be intrinsically strong while, at the same time, σ_Raman ends up being many orders of magnitude smaller when both compared to the electronic counterparts. These two sides of the same coin prompted us to propose \"the duality of Raman scattering\" (Table 1). Finally, this formulation naturally leads to a quantitative treatment of stimulated Raman scattering (SRS) microscopy, providing an intuitive, molecule-centric explanation as to how SRS microscopy can outperform regular Raman microscopy. Hence, as unveiled by the new formulation, a duality of Raman scattering has emerged, with implications for both fundamental science and practical technology.</p>","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":null,"pages":null},"PeriodicalIF":16.4,"publicationDate":"2024-06-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141448947","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Toward the Next Generation of Density Functionals: Escaping the Zero-Sum Game by Using the Exact-Exchange Energy Density.","authors":"Martin Kaupp, Artur Wodyński, Alexei V Arbuznikov, Susanne Fürst, Caspar J Schattenberg","doi":"10.1021/acs.accounts.4c00209","DOIUrl":"https://doi.org/10.1021/acs.accounts.4c00209","url":null,"abstract":"<p><p>ConspectusKohn-Sham density functional theory (KS DFT) is arguably the most widely applied electronic-structure method with tens of thousands of publications each year in a wide variety of fields. Its importance and usefulness can thus hardly be overstated. The central quantity that determines the accuracy of KS DFT calculations is the exchange-correlation functional. Its exact form is unknown, or better \"unknowable\", and therefore the derivation of ever more accurate yet efficiently applicable approximate functionals is the \"holy grail\" in the field. In this context, the simultaneous minimization of so-called delocalization errors and static correlation errors is the greatest challenge that needs to be overcome as we move toward more accurate yet computationally efficient methods. In many cases, an improvement on one of these two aspects (also often termed fractional-charge and fractional-spin errors, respectively) generates a deterioration in the other one. Here we report on recent notable progress in escaping this so-called \"zero-sum-game\" by constructing new functionals based on the exact-exchange energy density. In particular, local hybrid and range-separated local hybrid functionals are discussed that incorporate additional terms that deal with static correlation as well as with delocalization errors. Taking hints from other coordinate-space models of nondynamical and strong electron correlations (the B13 and KP16/B13 models), position-dependent functions that cover these aspects in real space have been devised and incorporated into the local-mixing functions determining the position-dependence of exact-exchange admixture of local hybrids as well as into the treatment of range separation in range-separated local hybrids. While initial functionals followed closely the B13 and KP16/B13 frameworks, meanwhile simpler real-space functions based on ratios of semilocal and exact-exchange energy densities have been found, providing a basis for relatively simple and numerically convenient functionals. Notably, the correction terms can either increase or decrease exact-exchange admixture locally in real space (and in interelectronic-distance space), leading even to regions with negative admixture in cases of particularly strong static correlations. Efficient implementations into a fast computer code (Turbomole) using seminumerical integration techniques make such local hybrid and range-separated local hybrid functionals promising new tools for complicated composite systems in many research areas, where simultaneously small delocalization errors and static correlation errors are crucial. First real-world application examples of the new functionals are provided, including stretched bonds, symmetry-breaking and hyperfine coupling in open-shell transition-metal complexes, as well as a reduction of static correlation errors in the computation of nuclear shieldings and magnetizabilities. The newest versions of range-separated local hybrids (e.g., ωLH","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":null,"pages":null},"PeriodicalIF":16.4,"publicationDate":"2024-06-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141436463","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Organic Synthesis Away from Equilibrium: Contrathermodynamic Transformations Enabled by Excited-State Electron Transfer.","authors":"Angela Lin, Sumin Lee, Robert R Knowles","doi":"10.1021/acs.accounts.4c00227","DOIUrl":"https://doi.org/10.1021/acs.accounts.4c00227","url":null,"abstract":"<p><p>ConspectusChemists have long been inspired by biological photosynthesis, wherein a series of excited-state electron transfer (ET) events facilitate the conversion of low energy starting materials such as H₂O and CO₂ into higher energy products in the form of carbohydrates and O₂. While this model for utilizing light-driven charge transfer to drive catalytic reactions thermodynamically \"uphill\" has been extensively adapted for small molecule activation, molecular machines, photoswitches, and solar fuel chemistry, its application in organic synthesis has been less systematically developed. However, the potential benefits of these approaches are significant, both in enabling transformations that cannot be readily achieved using conventional thermal chemistry and in accessing distinct selectivity regimes that are uniquely enabled by excited-state mechanisms. In this Account, we present work from our group that highlights the ability of visible light photoredox catalysis to drive useful organic transformations away from their equilibrium positions, addressing a number of long-standing synthetic challenges.We first discuss how excited-state ET enabled the first general methods for the catalytic anti-Markovnikov hydroamination of unactivated alkenes with alkyl amines. In these reactions, an excited-state iridium(III) photocatalyst reversibly oxidizes secondary amine substrates to their corresponding aminium radical cations (ARCs). These electrophilic <i>N</i>-centered radicals can then react with olefins to furnish valuable tertiary amine products with complete anti-Markovnikov regioselectivity. Notably, some of these products are less thermodynamically stable than their corresponding amine and alkene starting materials. We next present a strategy for light-driven C-C bond cleavage within various aliphatic alcohols mediated by homolytic activation of alcohol O-H bonds by excited-state proton-coupled electron transfer (PCET). The resulting alkoxy radical intermediates then undergo C-C β-scission to ultimately provide isomeric linear carbonyl products that are often higher in energy than their cyclic alcohol precursors. Applications of this chemistry for the light-driven depolymerization of lignin biomass, commercial phenoxy resin, hydroxylated polyolefin derivatives, and thermoset polymers are presented as well. We then describe a method for the contrathermodynamic positional isomerization of highly substituted olefins by means of cooperative photoredox and chromium(II) catalysis. In this work, generation of an allylchromium(III) species that can undergo highly regioselective <i>in situ</i> protodemetalation enables access to a less substituted and thermodynamically less stable positional isomer. Product selectivity in this reaction is determined by the large differential in oxidation potentials between differently substituted olefin isomers. Lastly, we discuss a light-driven deracemization reaction developed in col","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":null,"pages":null},"PeriodicalIF":16.4,"publicationDate":"2024-06-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141436349","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Porous Crystalline Materials Based on Tetrathiafulvalene and Its Analogues: Assembly, Charge Transfer, and Applications.","authors":"Hai-Ying Wang, Jian Su, Jing-Lin Zuo","doi":"10.1021/acs.accounts.4c00228","DOIUrl":"https://doi.org/10.1021/acs.accounts.4c00228","url":null,"abstract":"<p><p>ConspectusThe directed synthesis and functionalization of porous crystalline materials pose significant challenges for chemists. The synergistic integration of different functionalities within an ordered molecular material holds great significance for expanding its applications as functional materials. The presence of coordination bonds connected by inorganic and organic components in molecular materials can not only increase the structural diversity of materials but also modulate the electronic structure and band gap, which further regulates the physical and chemical properties of molecular materials. In fact, porous crystalline materials with coordination bonds, which inherit the merits of both organic and inorganic materials, already showcase their superior advantages in optical, electrical, and magnetic applications. In addition to the inorganic components that provide structural rigidity, organic ligands of various types serve as crucial connectors in the construction of functional porous crystalline materials. In addition, redox activity can endow organic linkers with electrochemical activity, thereby making them a perfect platform for the study of charge transfer with atom-resolved single-crystal structures, and they can additionally serve as stimuli-responsive sites in sensor devices and smart materials.In this Account, we introduce the synthesis, structural characteristics, and applications of porous crystalline materials based on the famous redox-active units, tetrathiafulvalene (TTF) and its analogues, by primarily focusing on metal-organic frameworks (MOFs) and covalent organic frameworks (COFs). TTF, a sulfur-rich conjugated molecule with two reversible and easily accessible oxidation states (i.e., radical TTF^•+ cation and TTF²⁺ dication), and its analogues boast special electrical characteristics that enable them to display switchable redox activity and stimuli-responsive properties. These inherent properties contribute to the enhancement of the optical, electrical, and magnetic characteristics of the resultant porous crystalline materials. Moreover, delving into the charge transfer phenomena, which is key for the electrochemical process within these materials, uncovers a myriad of potential functional applications. The Account is organized into five main sections that correspond to the different properties and applications of these materials: optical, electrical, and magnetic functionalities; energy storage and conversion; and catalysis. Each section provides detailed discussions of synthetic methods, structural characteristics, the physical and chemical properties, and the functional performances of highlighted examples. The Account also discusses future directions by emphasizing the exploration of novel organic units, the transformation between radical cation TTF^•+ and dication TTF²⁺, and the integration of multifunctionalities within these frameworks to foster the development of ","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":null,"pages":null},"PeriodicalIF":16.4,"publicationDate":"2024-06-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141430835","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Porous Organic Nanotubes: Chemistry of One-Dimensional Space","authors":"Kaushik Dey, Kalipada Koner, Rahul Dev Mukhopadhyay, Dinesh Shetty, Rahul Banerjee","doi":"10.1021/acs.accounts.4c00224","DOIUrl":"https://doi.org/10.1021/acs.accounts.4c00224","url":null,"abstract":"One-dimensional organic nanotubes feature unique properties, such as confined chemical environments and transport channels, which are highly desirable for many applications. Advances in synthetic methods have enabled the creation of different types of organic nanotubes, including supramolecular, hydrogen-bonded, and carbon nanotube analogues. However, challenges associated with chemical and mechanical stability along with difficulties in controlling aspect ratios remain a significant bottleneck. The fascination with structured porous materials has paved the way for the emergence of reticular solids such as metal–organic frameworks (MOFs), covalent organic frameworks (COFs), and organic cages. Reticular materials with tubular morphology promise architectural stability with the additional benefit of permeant porosity. Despite this, the current synthetic approaches to these reticular nanotubes focus more on structural design resulting in less reliable morphological uniformity. This Account, highlights the design motivation behind various classes of organic nanotubes, emphasizing their porous interior space. We explore the strategic assembly of organic nanotubes based on their bonding characteristics, from weak supramolecular to robust covalent interactions. Special attention is given to reticular nanotubes, which have gained prominence over the past two decades due to their distinctive micro and mesoporous structures. We examine the synergy of covalent and noncovalent interactions in constructing assembly of these nanotube structures.","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":null,"pages":null},"PeriodicalIF":18.3,"publicationDate":"2024-06-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141334500","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Evolution of a Synthetic Strategy toward the Syntheses of Bis-tetrahydroisoquinoline Alkaloids.","authors":"Aurapat Ngamnithiporn, Eric R Welin, Gerit Pototschnig, Brian M Stoltz","doi":"10.1021/acs.accounts.4c00262","DOIUrl":"https://doi.org/10.1021/acs.accounts.4c00262","url":null,"abstract":"<p><p>ConspectusThe bis-tetrahydroisoquinoline (bis-THIQ) natural products represent a medicinally important class of isoquinoline alkaloids that exhibit broad biological activities with particularly potent antitumor properties, as exemplified by the two U.S. FDA approved molecules trabectidin and lurbinectedin. Accordingly, other members within the bis-THIQ family have emerged as prime targets for synthetic chemists, aiming to innovate an orthogonal chemical production of these compounds. With the ability of these complementary strategies to reliably and predictably manipulate molecular structures with atomic precision, this should allow the preparation of synthetic derivatives not existing in nature as new drug leads in the development of novel medicines with desired biological functions.Beyond the biological perspective, bis-THIQ natural products also possess intricate and unique structures, serving as a source of intellectual stimulation for synthetic organic chemists. Within our laboratory, we have developed an integrated program that combines reaction development and target-directed synthesis, leveraging the architecturally complex molecular framework of bis-THIQ natural products as a driving force for the advancement of novel reaction methodologies. In this Account, we unveil our synthetic efforts in a comprehensive story, describing how our synthetic strategy toward bis-THIQ natural products, specifically jorunnamycin A and jorumycin, has evolved over the course of our studies through our key transformations comprising (a) the direct functionalization of isoquinoline <i>N</i>-oxide to prepare the bis-isoquinoline (bis-IQ) intermediate, (b) the diastereoselective and enantioselective isoquinoline hydrogenation to forge the pentacyclic skeleton of the natural product, and (c) the late-stage oxygenation chemistry to adjust the oxidation states of the A- and E-rings. First, we detail our plan in utilizing the aryne annulation strategy to prepare isoquinoline fragments for the bis-THIQ molecules. Faced with unpromising results in the direct C-H functionalization of isoquinoline <i>N</i>-oxide, we lay out in this Account our rationale behind the design of each isoquinoline coupling partner to overcome these challenges. Additionally, we reveal the inspiration for our hydrogenation system, the setup of our pseudo-high-throughput screening, and the extension of the developed hydrogenation protocols to other simplified isoquinolines.In the context of non-natural bis-THIQ molecules, we have successfully adapted this tandem coupling/hydrogenation approach in the preparation of perfluorinated bis-THIQs, representing the first set of electron-deficient non-natural analogues. Finally, we include our unsuccessful late-stage oxygenation attempts prior to the discovery of the Pd-catalyzed C-O cross-coupling reaction. With this full disclosure of the chemistry developed for the syntheses of bis-THIQs, we hope our orthogonal synthetic tactics will provide us","PeriodicalId":1,"journal":{"name":"Accounts of Chemical Research","volume":null,"pages":null},"PeriodicalIF":18.3,"publicationDate":"2024-06-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141315975","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}