From covalent to noncovalent: The role of metals in activating ligand sites toward noncovalent interactions (NCIs)

Coordination Chemistry Reviews, Год журнала: 2025, Номер 529, С. 216440 - 216440

Опубликована: Янв. 15, 2025

Язык: Английский

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Substituent and Heteroatom Effects on π–π Interactions: Evidence That Parallel-Displaced π-Stacking is Not Driven by Quadrupolar Electrostatics

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Янв. 17, 2025

Stacking interactions are a recurring motif in supramolecular chemistry and biochemistry, where persistent theme is preference for parallel-displaced aromatic rings rather than face-to-face π-stacking. This typically explained terms of quadrupole–quadrupole between the arene moieties but that interpretation inconsistent with accurate calculations, which reveal quadrupolar picture qualitatively wrong. At typical π-stacking distances, electrostatics may differ sign from an exact calculation based on charge densities interacting arenes. We apply symmetry-adapted perturbation theory to dimers composed substituted benzene various heterocycles, display wide range electrostatic interactions, we investigate interplay Pauli repulsion, dispersion, as it pertains Profiles energy components along cofacial slip-stacking coordinates support prominent role "van der Waals model" (dispersion competition repulsion), even polar monomers significant. While necessary explain optimal distance account relative orientation one respect another, find no evidence continued invocation basis Our results suggest driving force offset-stacking exists absence interactions. Consequently, tuning via functionalization does not guarantee can be avoided. has implications rational design soft materials other architectures.

Язык: Английский

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Engineering Perfluoroarenes for Enhanced Molecular Barrier Effect and Chirality Transfer in Solutions

Chemical Science, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

In diluted solution-based assemblies, the derivatives of perfluoroarenes perform as efficient molecular barriers to perylene building units, lighting up luminescence.

Язык: Английский

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Selective Benzene Recognition in Competitive Solvent System (Cyclohexene, Cyclohexane, Tri- and Hexafluorobenzenes) Using Perfluorinated Dinuclear Cu(II) Complex

Crystals, Год журнала: 2025, Номер 15(4), С. 322 - 322

Опубликована: Март 28, 2025

The selective adsorption and separation of benzene from structurally similar six-membered hydrocarbons fluorocarbons remain a significant challenge due to their comparable physical properties. In this study, we investigated the molecular recognition properties perfluorinated triketonate Cu(II) complex (1) as Nonporous Adaptive Crystal (NAC). addition previously reported (2)-encapsulated crystal 1•(2)3, report here structures guest-free 1 cyclohexene (3)-encapsulated 1•(O)2•3, where (O)2 represents two water molecules. Single-crystal analysis demonstrated that selectively encapsulates 2 while excluding other hydrocarbons, including 3, cyclohexane (4), trifluorobenzene (5), hexafluorobenzene (6). Gas experiments confirmed high affinity for 2, reflected in its preferential behavior mixed solvent vapor environments. selectivity was attributed strong π-hole···π metal···π interactions, which favor electron-rich aromatic guests. Additionally, crystallization competitive systems consistently led formation reinforcing 2. These findings highlight unique capabilities NACs, providing valuable insights into rational design advanced materials industrial applications involving hydrocarbons. Hirshfeld surface revealed contribution F···F interactions packing decreased upon guest (48.8% 1, 34.2% 22.2% 1•(2)3), F···H/H···F increased (8.6% 35.4% 1•(2)3). Regarding Cu self-assembled columnar structure results close contacts at coordination sites, Cu···Cu (0.1%), Cu···O (0.7%), Cu···C (1.3%). However, guest-incorporated 1•(O)2•3 disappears; instead, exhibits increase (1.2%), corresponding coordination, 1•(2)3 shows an (1.5%), indicative benzene.

Язык: Английский

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Structural Rigidification Strategy Based on Self-Assembly Enabled Reversible Excited-State Conversion of Iridium(III) Complexes for Multiple-Stimulus-Responsive Data Encryption

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(43), С. 29955 - 29963

Опубликована: Окт. 15, 2024

Stimulus-responsive chromic materials exhibit color-switching properties under specific external stimuli and have been widely used in various fields. Transition-metal complexes show great potential applications as promising candidates for stimulus-responsive materials, their excited states not only depend on the chemical composition but are also affected by intermolecular stacking modes. Owing to intrinsic difficulty ordered of octahedral configuration, changing modes iridium(III) multiple-stimulus responsiveness remains a significant challenge. In this work, we propose structural rigidification strategy based self-assembly reversibly regulate complexes, therefore achieving color switch different stimulus conditions. We prepare cationic using tetrakis(perfluorophenyl)-borate ([B(PhF5)4]−) counterion, whose matching tetrahedral configuration electron-deficient aromaticity enables polar-π interaction with cations, inducing form rigidification. The rigidity restricts large conformational changes metal-to-ligand charge transfer (3MLCT) state, facilitates conversion from 3MLCT ligand-center (3LC) state aggregated states. excited-state results 54 nm blue shift (from yellow sky blue) photoluminescence spectra. As result, report series responses low temperature, vapor fuming, mechanical force, multiple-stimulus-responsive data encryption. Our work provides novel achieve shows deeper understanding photophysical processes transition-metal offers new perspective develop materials.

Язык: Английский

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Formal Metal-Dependent (M = Pt, Pd) Switching between Arene π-Hole and σ-(Te)-Hole in the Arenetellurium(II) Noncovalent Binding

Crystal Growth & Design, Год журнала: 2024, Номер 24(22), С. 9581 - 9589

Опубликована: Ноя. 7, 2024

The diketonate complexes M(acac)2 (M = Pd (1), Pt (2)) were cocrystallized with bis(perfluoropyridin-4-yl)tellane (PyF2Te). Single-crystal X-ray studies of the resulting adducts revealed that binding mode and stoichiometry between coformers dramatically depend on identity metal sites. Pd(acac)2 formed adduct 13·(PyF2Te)2 where Te···Cacac πhole···Pd noncovalent interactions detected. In contrast to 1, Pt(acac)2 2·PyF2Te Te···Pt metal-involving chalcogen bond was observed. Various DFT methods, including calculation fully optimized dimeric assemblies their mutated dimers, allowed for a detailed examination corresponding interactions. Our findings support notion are primary structure-determining factors, formal transition can be attributed increased dz2-nucleophilicity platinum atom compared palladium site.

Язык: Английский

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Efficient synthesis of fluorinated triphenylenes with enhanced arene–perfluoroarene interactions in columnar mesophases

Beilstein Journal of Organic Chemistry, Год журнала: 2024, Номер 20, С. 3263 - 3273

Опубликована: Дек. 16, 2024

The high potential of non-covalent arene–fluoroarene intermolecular interactions in the design liquid crystals lies their ability to strongly promote self-assembly, improve order and stability supramolecular mesophases, enable tuneability optical electronic properties, which can potentially be exploited for advanced applications display technologies, photonic devices, sensors, organic electronics. We recently successfully reported straightforward synthesis several mesogens containing four lateral aliphatic chains derived from classical triphenylene core self-assembling columnar mesophases based on this paradigm. These mesogenic compounds were simply obtained good yields by nucleophilic substitution (S N FAr) various types commercially available fluoroarenes with electrophilic organolithium derivatives 2,2'-dilithio-4,4',5,5'-tetraalkoxy-1,1'-biphenyl (2Li- BP n ). In a continuation study, aiming at testing limits reaction providing large diversity structures, structurally related series is here, namely 1,2,4-trifluoro-6,7,10,11-tetraalkoxy-3-(perfluorophenyl)triphenylenes ( F They reacting above mentioned 2,2’-dilithiobiphenyl decafluorobiphenyl, C 6 5 –C . differ previously series, 1,2,4-trifluoro-6,7,10,11-tetraalkoxy-3-aryltriphenylenes PH ), solely terminal phenyl ring pentafluorophenyl ring. Thus, as expected, they Col hex mesophase over temperature ranges, only small differences transition temperatures. Furthermore, presence fluorophenyl group enables subsequent second annulation, yielding new extended polyaromatic mesomorphic compounds, i.e., 1,1',3,3',4,4'-hexafluoro-6,6',7,7',10,10',11,11'-octaalkoxy-2,2'-bitriphenylene G nm ) found rec mesophase. specific patterns antiparallel stacking mode into structures stabilized arene–perfluoroarene confirmed single-crystal structure alkoxy-free side chain analog, 1,2,4-trifluoro-3-(perfluorophenyl)triphenylene UV–vis absorption fluorescence emission spectroscopies reveal green photoluminescence quantum up 33% derivatives. J -aggregation inner fluorine-substituted dimers energetically stereoelectronically more favorable 66 exhibits thin-film red-shift peak.

Язык: Английский

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Synergistic σ/π-Hole Interactions Directing Supramolecular Assembly: Tellurium···Platinum Chalcogen Bonding Enhanced by π-Stacking

Crystal Growth & Design, Год журнала: 2024, Номер unknown

Опубликована: Ноя. 25, 2024

Язык: Английский

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