Borylated Subphthalocyanines: Versatile Precursors for the Preparation of Functional Bowl‐Shaped Aromatics DOI Creative Commons
Marta Gómez‐Gómez, Jorge Labella, Tomás Torres⊗

et al.

Chemistry - A European Journal, Journal Year: 2023, Volume and Issue: 29(51)

Published: June 25, 2023

The peripheral borylation of porphyrinoids has become a key step to prepare advanced functional materials. This study reports the synthesis, electronic properties, and reactivity borylated subphthalocyanines. These compounds, which are prepared by Suzuki-Miyaura in excellent yields, easily purified, display great stability, serve as powerful starting materials for post-functionalization SubPcs via cross-coupling reactions. Remarkably, this novel approach is more efficient than methodologies already described enables preparation exotic systems, such SubPc dimeric species linked C-C bonds, not accessible so far present promising properties optoelectronic devices.

Language: Английский

Bulking Up the Bay-Position Substituents Enables Enhanced Selectivity of Cs-Symmetric Boron Subphthalocyanine–Subnaphthalocyanine Hybrids DOI Creative Commons
Nina F. Farac, Alan J. Lough, Timothy P. Bender

et al.

Precision Chemistry, Journal Year: 2024, Volume and Issue: 2(4), P. 161 - 181

Published: April 4, 2024

The precise synthesis of subporphyrinoid hybrids with π-expanded topologies and unique material properties plays a promising role in the design functional macrocycles. Easy, selective, controllable routes to boron subphthalocyanine–subnaphthalocyanine hybrids, Bsub(Pc3-p-Ncp)s, are desirable for this purpose yet synthetically challenging due random mixtures Cs-, C3v-, and, some cases, C1-symmetric compounds that form during traditional statistical mixed cyclotrimerizations. Herein, we addressed issue by developing sterically driven cyclotrimerization enhanced selectivity targeted Cs-symmetric hybrid complete suppression crowded macrocyclic byproducts. This process, coupled rationally designed precursor bearing bulky phenyl substituents, enabled characterization bay-position phenylated Ph2-(Rp)8Bsub(Pc2-Nc1) halogens (Rp = Cl or F) their peripheral isoindole rings. Reaction ranged between 59 72% remarkable yields, significantly higher than conventional These findings were augmented theoretical calculations on Lewis basicity as guiding principles into macrocycle formation. Additionally, incorporation unfused groups halogen atoms framework resulted fine-tuned optical, structural, electronic, electrochemical properties. straightforward approach achieved improved controlled narrowing product distribution, affording efficient structurally sophisticated Bsub(Pc2-Nc1) hybrids. then expands library 3-dimensional π-extended macrocycles use range applications, such optoelectronic devices precisely tailored optical

Language: Английский

Citations

4
Molecular Dynamics Simulation to Predict Assembly Structures of Bowl-Shaped π-Conjugated Molecules DOI Creative Commons
Shunsuke Sato, Barun Dhara, Dan He

et al.

Chemical Communications, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

We propose a novel computational method to predict the crystal structures of bowl-shaped π-conjugated molecules and reproduce their assembly structure from randomly dispersed using all-atom molecular dynamics (MD) simulation.

Language: Английский

Citations

0
Spin Filtering in Self-Assembled Bowl-Shaped Aromatics DOI Creative Commons
Jorge Labella, Anu Gupta, Anil Kumar

et al.

Chemical Science, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Magnetic-conductive AFM reveals that self-assembled bowl-shaped aromatics function as molecular spin filters.

Language: Английский

Citations

0
Isolating the ring-redox states of boron sub-phthalocyanines DOI Creative Commons

Wen Zhou,

Declan McKearney, Yusuke Okada

et al.

Chemical Communications, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

The first structurally characterized ring-reduced and oxidized boron subphthalocyanines include a doubly-reduced trinuclear cluster ring-oxidized [ sub PcBF] + . UV-vis absorption spectra TD-DFT calculations indicate the ring-oxidation state.

Language: Английский

Citations

0
Post-functionalization of tritopic subphthalocyanines with C3v symmetry DOI
Elisa López-Serrano, Jorge Labella, Tomás Torres⊗

et al.

Journal of Porphyrins and Phthalocyanines, Journal Year: 2025, Volume and Issue: 29(03n04), P. 488 - 492

Published: March 5, 2025

The successful applications of subphthalocyanines (SubPcs) in the field molecular materials largely stem from their unique post-functionalization versatility, where regioisomerism and substitution patterns play critical roles. In this context, chiral tritopic [Formula: see text]- or text]-symmetric SubPcs, as well more symmetric hexatopic C 3v have been extensively explored. However, derivatives with symmetry represent an appealing yet underexplored family, combining lower density former simplified latter. Herein, we explore triimide-SubPcs. Specifically, synthesize a versatile synthon based on triimide-SubPcs equipped iodoaryl groups. These SubPcs exhibit high sensitivity under typical reaction conditions employed for cross-coupling reactions, including Suzuki, Sonogashira, Buchwald-Hartwig protocols. Nonetheless, optimize Stille conditions, enabling selective installation ethenyl ethynyl substituents aryl groups attached to imide nitrogen atoms. UV-Vis absorption spectroscopy theoretical calculations reveal that do not significantly alter electronic structure SubPc macrocycle. Collectively, study establishes pathway toward synthesis unexplored highly promising family expanding toolbox advanced materials.

Language: Английский

Citations

0
Novel subporphyrazine-drug hybrid photosensitizers containing diclofenac and abiraterone: synthesis, photophysical properties and photodynamic activity in vitro DOI
Roman O. Eremeev, Tatiana V. Dubinina,

Ivan D. Burtsev

et al.

Dyes and Pigments, Journal Year: 2025, Volume and Issue: 241, P. 112868 - 112868

Published: May 6, 2025

Language: Английский

Citations

0
Acceleration of the Diels‐Alder Reaction between 9‐Functionalized Anthracenes and C60/C70 in the Cavity of a Water Soluble Subphthalocyanine Cage DOI Creative Commons
Ainhoa Salazar, Jorge Labella, Sunit Kumar

et al.

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: 366(4), P. 934 - 941

Published: Jan. 3, 2024

Abstract Herein we report on the acceleration of Diels‐Alder reaction between a series 9‐functionalized anthracenes and C 60 /C 70 encapsulated in water‐soluble metallo‐organic Pd(II)‐subphthalocyanine cage ( SubPc‐cage ), which performs as catalytic molecular reactor that provides beneficial hydrophobic environment. Negatively positively charged do not react either with or , due to favored solvation water medium and/or detrimental interactions positively‐charged Pd(II) corners . Experiments rendered parallel results, although proved more reactive, leading anthracene cycloadducts by α bonds. All results have been rationalized theoretical calculations at GFN2‐xTB level.

Language: Английский

Citations

3
Subphthalocyanines as fluorescence sensors for metal cations DOI Creative Commons
Mary Angelia Alfred, Kamil Lang, Kaplan Kirakci

et al.

Dalton Transactions, Journal Year: 2024, Volume and Issue: 53(6), P. 2635 - 2644

Published: Jan. 1, 2024

We have demonstrated that subphthalocyanines are a promising class of fluorescent sensors for metal cations suitable aqueous media. The ambient solvent molecules were found to play an important role in the coordination by aza-crowns.

Language: Английский

Citations

3
Columnar liquid crystals based on antiaromatic expanded porphyrins DOI Creative Commons

Duong D. Nguyen,

Jorge Labella,

Juan Laforga-Martín

et al.

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(25), P. 3401 - 3404

Published: Jan. 1, 2024

Antiaromatic expanded porphyrins designed to self-assemble into columnar liquid crystalline (LC) structures are synthesized and characterized by multiple techniques. The substituents were found play a crucial role in modulating the LC behaviour.

Language: Английский

Citations

3
The key role of chirality and peripheral substitution in the columnar organization of bowl-shaped subphthalocyanines DOI Creative Commons
Jorge Labella, Elisa López-Serrano, Daniel Aranda

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: 15(34), P. 13760 - 13767

Published: Jan. 1, 2024

This work describes the crucial effect that optical purity and substitution pattern exert on formation mechanism stability of columnar polymers formed from self-assembly bowl-shaped subphthalocyanines.

Language: Английский

Citations

2