N-Heterocyclic Carbenes: A Door Open to Supramolecular Organometallic Chemistry

Accounts of Chemical Research, Journal Year: 2020, Volume and Issue: 53(7), P. 1401 - 1413

Published: July 9, 2020

ConspectusThe field of metallosupramolecular chemistry is clearly dominated by the use O-, N-, and P-donor Werner-type polydentate ligands. These molecular architectures are high interest because their wide range applications, which include encapsulation, stabilization reactive species, supramolecular catalysis, drug delivery, among others. Only recently, organometallic ligands have allowed preparation a variety coordination complexes, term complexes (SOCs) gaining space within chemistry. While early examples SOCs referred to mostly containing bisalkenyl, diphenyl, or bisalkynyl linkers, development during past decade has been boosted parallel multidentate N-heterocyclic carbene (NHC) The first NHC-based assemblies based on NHC bound group 11 metals. However, last 10 years, several planar poly-NHC extended π-conjugated systems facilitated formation large in can contain metals other than Cu, Ag, Au. Such Janus di-NHCs trigonal-planar tris-NHCs—most them prepared our research group—which vast compounds with interesting host–guest properties. Although number increased few for purposes still its earliest infancy. In this Account, we describe achievements that made 4 years toward broadening applications organometallic-based structures, including as hosts some selected organic inorganic guests, together catalytic properties displayed inclusion complexes. Our contribution describes design Ni-, Pd-, Au-based metallorectangles metalloprisms, used encapsulation substrates, such polycyclic aromatic hydrocarbons (PAHs) fullerenes. binding affinities found ascribed incorporation two cofacial panels systems, provide optimum conditions guest recognition π–π-stacking interactions. We also series digold(I) metallotweezers substrates. were "naked" metal cations hydrocarbons. these highly dependent nature rigid connector ancillary constitute arms tweezer. A peculiar balance between self-aggregation tweezer ability encapsulate guests observed.

Language: Английский

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Pd(II) Coordination Sphere Engineering: Pyridine Cages, Quinoline Bowls, and Heteroleptic Pills Binding One or Two Fullerenes

Journal of the American Chemical Society, Journal Year: 2019, Volume and Issue: 141(22), P. 8907 - 8913

Published: May 8, 2019

Fullerenes and their derivatives are of tremendous technological relevance. Synthetic access application still hampered by tedious purification protocols, peculiar solubility, limited control over regioselective derivatization. We present a modular self-assembly system based on new low-molecular-weight binding motif, appended two palladium(II)-coordinating units different steric demands, to either form [Pd2L14]4+ cage or an unprecedented [Pd2L23(MeCN)2]4+ bowl (with L1 = pyridyl, L2 quinolinyl donors). The former was used as selective induced-fit receptor for C60. latter, owing its more open structure, also allows C70 fullerene derivatives. By exposing only fraction the bound guests' surface, acts protecting group functionalization, demonstrated exclusive monoaddition anthracene. In hierarchical manner, sterically low-demanding dicarboxylates were found bridge pairs bowls into pill-shaped dimers, able host fullerenes. hosts allow transferring fullerenes variety organic solvents, extending scope possible derivatization processing methodologies.

Language: Английский

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Recent advances in supramolecular fullerene chemistry

Chemical Society Reviews, Journal Year: 2023, Volume and Issue: 53(1), P. 47 - 83

Published: Oct. 18, 2023

We review recent work at the interface of supramolecular chemistry and fullerene chemistry. focus on selective functionalization, host–guest chemistry, non-covalent dyads, mechanically interlocked architectures 2D/3D assemblies.

Language: Английский

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Water-Soluble Self-Assembled Cage with Triangular Metal–Metal-Bonded Units Enabling the Sequential Selective Separation of Alkanes and Isomeric Molecules

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(35), P. 16191 - 16198

Published: Aug. 16, 2022

The selective separation of structurally similar aliphatic/aromatic hydrocarbons is an essential goal in industrial processes. In this study, we report the synthesis a water-soluble (Tr2M3)4L4 (Tr = cycloheptatrienyl ring; M metal; L organosulfur ligand) molecular cage (1) via self-assembly acceptor tripalladium sandwich species [(Tr2Pd3)(CH3CN)][NO3]2 and attachment onto solubilizing methoxyethoxy appendants to be utilized energy-friendly alternative approach molecules under ambient conditions. Cage 1, comprising hydrophobic inner cavity, exhibited good solubility stability aqueous media. It also demonstrated excellent performance sequential alkanes (C6–C9), xylene, other disubstituted benzene isomers cis/trans-decalin.

Language: Английский

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Flexible electrode materials for emerging electronics: materials, fabrication and applications

Journal of Materials Chemistry A, Journal Year: 2024, Volume and Issue: 12(32), P. 20606 - 20637

Published: Jan. 1, 2024

This paper reviews the progress of flexible electrodes in recent years, including substrates, active materials, manufacturing methods, and their latest applications sensors, energy storage, medical healthcare.

Language: Английский

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A Strategy for the Construction of Triply Interlocked Organometallic Cages by Rational Design of Poly-NHC Precursors

Journal of the American Chemical Society, Journal Year: 2020, Volume and Issue: 142(31), P. 13614 - 13621

Published: July 9, 2020

Three-dimensional (3D) triply interlocked catenanes are a family of chemical topologies that consist two identical, mechanically coordination cage components with intriguingly complex structures. Although only few successful constructions 3D have been achieved to date via metal-mediated assembly, these structures thus far targeted by metal–nitrogen/oxygen techniques. Here, taking advantage rational ligand design, we report the efficient construction series [2]catenanes formula [Ag3L2]2, wherein metal ions exclusively form bonds N-heterocyclic carbene (NHC) units, and their subsequent transmetalation corresponding [Au3L2]2 gold analogues. The formation reactions proceed under mild conditions generally applicable. A characterization techniques were applied confirm structure desired architectures: multinuclear NMR spectroscopy, ESI-MS, single-crystal X-ray diffraction analysis. solid-state [Ag3(1a)2]2(PF6)6 unambiguously confirms existence catenane consists trinuclear hexacarbene components. interlocking cages into [2]catenane is driven π···π stacking triazine–triazine stacks cooperative interactions between imidazo[1,5-a]pyridine subunits. Notably, organometallic exhibit good stability toward various organic solvents, concentrations, temperatures, no disassembly occurred in presence coronene or pyrene. future architectures using metal–carbene rather than metal–nitrogen may provide assemblies interesting properties for as-yet-unimagined applications fields such as sensors molecular electrical conductors.

Language: Английский

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Self-Assembled Perylene Bisimide-Cored Trigonal Prism as an Electron-Deficient Host for C₆₀ and C₇₀ Driven by “Like Dissolves Like”

Journal of the American Chemical Society, Journal Year: 2020, Volume and Issue: 142(37), P. 15950 - 15960

Published: Aug. 26, 2020

Poor processability of fullerenes is a major remaining drawback for them to be studied monomolecularly and find real-life applications. One the strategies tackle this problem encapsulate within host, which however quite often, accompanied by significant alteration their physical/chemical properties as encountered in chemical modification. To minimize effect, an electron-deficient entities-based, dissolvable, fluorescence active supramolecular host was designed constructed via coordination-driven self-assembly o-tetrapyridyl perylene bisimide (PBI) with cis-(PEt3)2Pt(OTf)2. The trigonal prism 1 possesses trigonal-prismatic inner cavity 14.7 Å diameter its inscribed circle. Host-guest chemistry investigations revealed that both C60 C70 could quantitatively encapsulated 1:1 ratio. Further studies demonstrated produced host-guest complex 1⊃C70 significantly more stable than 1⊃C60, allowing complete transformation latter former separation from mixture C60. inclusion state rotate freely cavity. Electrochemistry spectroscopy disclosed encapsulation guests shows little effect upon reduction properties. Thus, "like dissolves like" believed main driving force formation complexes. Moreover, complexes can fabricated into monomolecular membranes using conventional Langmuir-Blodgett technique. We propose these unique used model ensembles further single molecular 2D membrane states. In addition, reversible four-electron property may allow applications photo/electrocatalysis, organic electronics, etc.

Language: Английский

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A Self‐Assembled Palladium(II) Barrel for Binding of Fullerenes and Photosensitization Ability of the Fullerene‐Encapsulated Barrel

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(25), P. 14109 - 14116

Published: April 9, 2021

Fullerene extracts obtained from fullerene soot lack their real application due to poor solubility in common solvents and difficulty purification. Encapsulation of these a suitable host is an important approach address issues. We present new Pd6 barrel (1), which composed three 1,4-dihydropyrrolo[3,2-b]pyrrole panels, clipped through six cis-PdII acceptors. Large open windows cavity make it efficient for large guest. Favorable interactions between the ligand (C60 C70 ) allows encapsulate efficiently. Thorough investigation reveals that 1 has stronger binding affinity towards over C60 , resulting predominant extraction mixture two. Finally, encapsulated barrels ⊂1 were found be visible-light-induced singlet oxygen generation. Such preferential photosensitizing ability are noteworthy.

Language: Английский

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Cooperativity of steric bulk and H-bonding in coordination sphere engineering: heteroleptic Pd^II cages and bowls by design

Chemical Science, Journal Year: 2022, Volume and Issue: 13(6), P. 1829 - 1834

Published: Jan. 1, 2022

Recently developed self-assembly strategies allow to rationally reduce the symmetry of metallosupramolecular architectures. In addition, combination multiple ligand types without creating compound mixtures has become possible. Among several approaches realize non-statistical heteroleptic assembly, Coordination Sphere Engineering (CSE) makes use secondary repulsive or attractive interactions in direct vicinity metal nodes. Previously, we used steric congestion turn dinuclear [Pd

Language: Английский

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Isoreticular Preparation of Tetraphenylethylene‐based Multicomponent Metallacages towards Light‐Driven Hydrogen Production

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(40)

Published: Aug. 19, 2023

Abstract Multicomponent metallacages can integrate the functions of their different building blocks to achieve synergetic effects for advanced applications. Herein, based on metal‐coordination‐driven self‐assembly, we report preparation a series isoreticular tetraphenylethylene‐based metallacages, which are well characterized by multinuclear NMR, ESI‐TOF‐MS and single‐crystal X‐ray diffraction techniques. The suitable integration photosensitizing tetraphenylethylene units as faces Re catalytic complexes pillars into single metallacage offers high photocatalytic hydrogen production rate 1707 μmol g −1 h , is one highest values among reported metallacages. Femtosecond transient absorption DFT calculations reveal that serve platform precise organized arrangement two blocks, enabling efficient directional electron transfer highly performance. This study provides general strategy multifunctional ligands certain improve efficiency production, will guide future design towards photocatalysis.

Language: Английский

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