β-to-β Singly Linked Subphthalocyanine Dimers with Effective π-Conjugation

Organic Letters, Год журнала: 2024, Номер 26(44), С. 9471 - 9475

Опубликована: Окт. 31, 2024

In this work, a series of π-conjugated Subphthalocyanine dimers assembled by simple π-bridges were efficiently synthesized through metal-catalyzed reactions. Despite being singly linked, these readily accessible arrays exhibit excellent π-electron communication, significantly perturbing the orbital distribution conventional SubPcs and inducing notable alterations in their optical properties. The findings presented here demonstrate potential for constructing curved porphyrin with well-conjugated skeletons intriguing functionalities.

Язык: Английский

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Implementing magnetic properties on demand with a dynamic Lanthanoid-Organic Framework

Chemical Science, Год журнала: 2024, Номер unknown

Опубликована: Дек. 26, 2024

We present the synthesis of a lanthanoid-organic framework (LOF) featuring dynamic structure that exhibits tunable magnetic properties. The LOF undergoes breathing and gate-opening phenomena in response to changes DMF content N2 sorption, leading emergence new crystal phases with distinct characteristics. Notably, desolvated form excels as single-ion magnet, while fully activated demonstrates impressive qubit properties, exhibiting Rabi oscillations up 60 K. Our work enables precise control over LOF's geometry, allowing us selectively tailor its behavior achieve either these two intriguing functionalities.

Язык: Английский

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Synthesis and Self-Assembly of β-Octa[(4-Diethoxyphosphoryl)phenyl]porphyrins

Inorganic Chemistry, Год журнала: 2023, Номер 62(8), С. 3431 - 3444

Опубликована: Фев. 8, 2023

The β-substituted porphyrinoids commonly used to form functional assembled systems in nature yet are still scarcely material chemistry probably due the laborious synthesis of these compounds. In this work, β-octa[(4-diethoxyphosphoryl)phenyl]porphyrin (2HOPPP) and its metal (Zn(II), Cd(II), Cu(II), Ni(II)) complexes were prepared good yields. These highly soluble chromophores characterized solution using spectroscopic (NMR, UV–vis, fluorescence), electrochemical, spectroelectrochemical methods. Attachment electron-deficient residue (ArP(O)(OEt)2) porphyrin macrocycle leads easier reductions harder oxidations for all studied as compared corresponding meso-tetra[4-(diethoxyphosphoryl)phenyl]porphyrin derivatives reported previously. We demonstrated that strong character MOPPP porphyrins results principally from increase number electron-withdrawing groups at periphery tetrapyrrolic macrocycle. Electron-deficient required supramolecular part their ability assemblies via coordination axial ligands central atom. According single-crystal X-ray data, ZnOPPP forms crystalline phase dimers which each two macrocycles is connected through an unusual combination hydrogen bonding phosphoryl water molecules axially coordinated zinc atom partner molecule. involvement binding allows distance between mean N4 planes, up 4.478 Å. offset attached a 1,4-phenylene spacer withdraws whole one molecule spatial overlap with increases Zn–Zn 10.372 This unknown type get deeper insights into organization naturally occurring macrocycles. also labile dimeric complex 5.3 × 10–7–5.8 10–5 M chloroform solutions. contrast, other work exist monomeric species under experimental conditions. self-association constant has been determined by electronic absorption spectroscopy.

Язык: Английский

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Conjugated Porphyrin Tapes as Quantum Mediators for Vanadyl Qubits

Опубликована: Авг. 19, 2022

Vanadium(IV) magnetic centers are prime candidates as molecular quantum information units. One of the longstanding problems is to obtain an extendable scaffold that transmits interaction a degree usable for processing, and allows upscaling multiple centers, while preserving sufficiently long coherence time. Here, we show fused porphyrins allow tailored scaffolding vanadyl units, with almost flat conjugated π-system offers substantial advantages communication between ions, leading spin-lattice (T1 = 30 ms) (Tm 5.5 µs) times. The antiferromagnetic exchange coupling in these dimers (J 1 GHz) stronger than hyperfine interaction, resulting complex EPR spectra which both unpaired electrons couple equally I 7/2 51V nuclei. Isolation syn- anti-isomers, vanadyls on same or opposite sides con-jugated channel, showcases sensitivity units different configurational environments, way tune inter-action poly-porphyrin systems by controlling stereochemistry.

Язык: Английский

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Structures and magnetic relaxation properties of cyclopentadienyl/β-diketonate/trispyrazolylborate hybridized dysprosium single-molecule magnets

Chinese Chemical Letters, Год журнала: 2022, Номер 34(8), С. 108055 - 108055

Опубликована: Дек. 10, 2022

Язык: Английский

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Slow magnetic relaxation behavior of a {Dy2} complex based on a large π-conjugated bridging ligand

Polyhedron, Год журнала: 2022, Номер 232, С. 116271 - 116271

Опубликована: Дек. 22, 2022

Язык: Английский

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Interfacial nanoarchitectonics with porphyrins and related molecules: Langmuir-Blodgett method and layer-by-layer assembly

Journal of Porphyrins and Phthalocyanines, Год журнала: 2023, Номер 27(07n10), С. 924 - 945

Опубликована: Март 10, 2023

Nanoarchitectonics is the methodology for architecture of nano-units atoms, molecules, and nanomaterials to create functional material systems. This will integrate nanotechnology with other fields such as organic chemistry, supramolecular science, microfabrication technology, bio-related sciences. Through this review, it shown that nanoarchitectonics important development various materials. Porphyrins their analogues are exemplified players in strategies. The contents review can be briefly summarized follows. First, recent examples studies on porphyrins analogues, ranging from synthesis basic research biomedical applications advanced usages, presented. demonstrates broad utility nano-units, molecular nanoarchitectonics. In subsequent sections, organization function porphyrin assemblies by Langmuir-Blodgett (LB) method layer-by-layer (LbL) assembly described at interfaces. creation materials through rich possibilities. Conversely, wide range possibilities may make difficult easily design control. Confine system free three-dimensional space a two-dimensional field an interface, design, creation, evaluation become easier. structures plane also advantageous terms expression. use interfacial environments extremely powerful tool creating systems

Язык: Английский

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Enhanced Coherence by Coupling Spins through a Delocalized π-System: Vanadyl Porphyrin Dimers

Опубликована: Апрель 18, 2023

Vanadium(IV) magnetic centers are prime candidates as molecular quantum units. One longstanding question is how to obtain a scaffold that connects multiple and allows two communication modalities: electronic. We have synthesized studied selection of vanadyl porphyrin dimers, models the most synthetically accessible linear arrays. show strongly π-conjugated backbone places system in strong coupling regime protects coherence against electron pair flip-flop processes at low temperatures (<10 K). This result fundamental step towards design materials for single-molecule devices controlled by microwaves with electrical readout.

Язык: Английский

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LANTHANIDE-PORPHYRINS AND LANTHANIDE-PHTHALOCYANINES: DEVELOPMENT OF STABLE AND EFFECTIVE INFRARED 4F-EMITTIVE COMPOUNDS

Ukrainian Chemistry Journal, Год журнала: 2023, Номер 89(4), С. 73 - 89

Опубликована: Май 25, 2023

This review is devoted to different synthetic approaches for obtaining lanthanide complexes with porphyrins and phthalocyanines, studying their structure emission features. Lanthanide-tetrapyrroles can be core-coordinated or/and coordinated by additional binding sites in polytopic derivatives. It noteworthy that the tetrapyrroles allow poly­heteronuclear compounds, which quite interesting terms of particular 4f-sensitization mechanism. A general structural difference between lanthanide-porphyrins lanthanide-phthalocyanines ability latter easily form poly-decker leads changes photochemical processes including 4f-sensitization. The also shows main directions solution stability issue as well increasing 4f-luminescence effectiveness.

Язык: Английский

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Structural cutting and recombining in layered sodium dysprosium phosphonate: key roles of flexible pyrazinyl hydrazone molecular tools

CrystEngComm, Год журнала: 2022, Номер 24(43), С. 7554 - 7562

Опубликована: Янв. 1, 2022

A cutting [Na 5 Dy 6 ] phosphonate cluster and a recombinant 4 8 ∞ layer are isolated using the pyrazinyl hydrazone ligand. The latter presents first heterometal exhibiting triple N-bridges of groups.

Язык: Английский

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