A porphyrin-based molecular cage guided by designed local-electric field is highly selective and efficient

Siddiqui, Shakir Ali; Shaik, Sason; Kalita, Surajit; Dubey, Kshatresh Dutta

doi:10.1039/d3sc01720f

Cited by 3 publications

(6 citation statements)

References 66 publications

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“…Motivated by studies that have attributed encapsulation-mediated rate enhancements to the electrostatic environment provided by the cage, ,− we aimed to identify if encapsulation in the Ga 4 L 6 cage alters the electrostatic characteristics of TMCs. Specifically, we compared the ESP and partial charges at each TMC metal center in solvated and cage environments (see Section ).…”

Section: Resultsmentioning

confidence: 99%

Computational Screening of Putative Catalyst Transition Metal Complexes as Guests in a Ga₄L₆^12– Nanocage

Reinhardt,

Manetsch,

et al. 2024

Inorg. Chem.

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Metal−organic cages form well-defined microenvironments that can enhance the catalytic proficiency of encapsulated transition metal complexes (TMCs). We introduce a screening protocol to efficiently identify TMCs that are promising candidates for encapsulation in the Ga 4 L 6 12− nanocage. We obtain TMCs from the Cambridge Structural Database with geometric and electronic characteristics amenable to encapsulation and mine the text of associated manuscripts to curate TMCs with documented catalytic functionality. By docking candidate TMCs inside the nanocage cavity and carrying out electronic structure calculations, we identify a subset of successfully optimized candidates (TMC-34) and observe that encapsulated guests occupy an average of 60% of the cavity volume, in line with previous observations. Notably, some guests occupy as much as 72% of the cavity as a result of linker rotation. Encapsulation has a universal effect on the electrostatic potential (ESP), systematically decreasing the ESP at the metal center of each TMC in the TMC-34 data set, while minimally altering TMC metal partial charges. Collectively these observations support geometry-based screening of potential guests and suggest that encapsulation in Ga 4 L 6 12cages could electrostatically stabilize diverse cationic or electropositive intermediates. We highlight candidate guests with associated known reactivity and solubility most amenable for encapsulation in experimental follow-up studies.

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Section: Resultsmentioning

confidence: 99%

Computational Screening of Putative Catalyst Transition Metal Complexes as Guests in a Ga₄L₆^12– Nanocage

Reinhardt,

Manetsch,

et al. 2024

Inorg. Chem.

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“…Subsequently, to enhance the catalysis, we engineered the cage so as to orient the local electric field along the reaction axis (i.e., the Fe–O axis). It was found that the engineered cage possesses a significant dipole moment along y -axis which interact with the LEF along the y -direction and slightly lowers the barrier for R -selective reaction . Inspired by this finding, strong R / S switchable cages were computationally engineered as well, as shown in Figure .…”

Section: Designed-lef (D-lef) To Achieve the Desired Activity Through...mentioning

confidence: 99%

“…In a very recent study, we have extended the scope of tailored local electric fields to supramolecular cages, and we have shown that such D-LEFs enable precise and tunable control over the catalytic environment, providing a highly flexible and adjustable platform for enhancing reactivity and selectivity. 73 Here, a computational approach was used to engineer a porphyrin-based cage (PB-1) 74 and to encapsulate the active oxidant (HM1) 75 and substrate (tetralin, TLN) 76 inside it. Subsequently, to enhance the catalysis, we engineered the cage so as to orient the local electric field along the reaction axis (i.e., the Fe–O axis).…”

Section: Designed-lef (D-lef) To Achieve the Desired Activity Through...mentioning

confidence: 99%

“…It was found that the engineered cage possesses a significant dipole moment along y -axis which interact with the LEF along the y -direction and slightly lowers the barrier for R -selective reaction. 73 Inspired by this finding, strong R / S switchable cages were computationally engineered as well, as shown in Figure 9 . When a charged substituent (two COO – groups) was placed in the negative y -direction, the reaction resulted in R -enantioselectivity, while placing the same charged substitution on the positive y -direction resulted in S -enantioselectivity.…”

Section: Designed-lef (D-lef) To Achieve the Desired Activity Through...mentioning

confidence: 99%

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Designed Local Electric Fields─Promising Tools for Enzyme Engineering

Siddiqui,

Stuyver,

Shaik

et al. 2023

JACS Au

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Designing efficient catalysts is one of the ultimate goals of chemists. In this Perspective, we discuss how local electric fields (LEFs) can be exploited to improve the catalytic performance of supramolecular catalysts, such as enzymes. More specifically, this Perspective starts by laying out the fundamentals of how local electric fields affect chemical reactivity and review the computational tools available to study electric fields in various settings. Subsequently, the advances made so far in optimizing enzymatic electric fields through targeted mutations are discussed critically and concisely. The Perspective ends with an outlook on some anticipated evolutions of the field in the near future. Among others, we offer some pointers on how the recent data science/machine learning revolution, engulfing all science disciplines, could potentially provide robust and principled tools to facilitate rapid inference of electric field effects, as well as the translation between optimal electrostatic environments and corresponding chemical modifications.

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“…As a light-absorbing molecule with the ability to activate oxygen, cobalt porphyrin has found wide applications in the field of photocatalysis. , For example, by inserting a single cobalt atom into the porphyrin skeleton, Li and coworkers significantly reduced the charge transfer resistance, inhibited electron/hole recombination, and broadened the light absorption, thereby significantly improving the photocatalytic performance . Introducing porphyrins into metal–organic cages as efficient photocatalysts is also considered as a highly effective strategy. , …”

Section: Introductionmentioning

confidence: 99%

A Porphyrin-Faced Zn₈L₆ Cage for Selective Oxidation of C(sp³)–H Bonds and Sulfides

Zhai,

Wei,

Jing

et al. 2024

Inorg. Chem.

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Catalytic oxidation of benzyl C−H bonds and sulfides from fuel oils stands as an attractive proposition in the quest for clean energy, yet their simultaneous oxidation with a singular, economically friendly catalyst is not well established. In this work, the combination of a cobalt(II) porphyrin ligand with 2-pyridinecarboxaldehyde and Zn II yielded a Zn 8 L 6 cage (Co cube). The three-dimensional conjugated structure effectively enhances energy transfer efficiency, enabling the Co cube to show a good ability to activate oxygen under light conditions for photooxidation. Moreover, this catalytic system demonstrates high selectivity for the photocatalytic oxidation of C(sp 3 )−H bonds and sulfides, employing the Co cube as a single component catalyst, molecular oxygen as the oxidant, and activating oxygen into 1 O 2 under mild reaction conditions. This provides significant insights for organic synthesis and future design of photocatalysts with complex molecular components.

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A porphyrin-based molecular cage guided by designed local-electric field is highly selective and efficient

Abstract: The present work outlines a general methodology for designing efficient catalytic machineries that can easily be tweaked to meet the demands of the target reactions.

Cited by 3 publications

References 66 publications

Computational Screening of Putative Catalyst Transition Metal Complexes as Guests in a Ga₄L₆^12– Nanocage

Computational Screening of Putative Catalyst Transition Metal Complexes as Guests in a Ga₄L₆^12– Nanocage

Designed Local Electric Fields─Promising Tools for Enzyme Engineering

A Porphyrin-Faced Zn₈L₆ Cage for Selective Oxidation of C(sp³)–H Bonds and Sulfides

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A porphyrin-based molecular cage guided by designed local-electric field is highly selective and efficient

Abstract: The present work outlines a general methodology for designing efficient catalytic machineries that can easily be tweaked to meet the demands of the target reactions.

Cited by 3 publications

References 66 publications

Computational Screening of Putative Catalyst Transition Metal Complexes as Guests in a Ga4L612– Nanocage

Computational Screening of Putative Catalyst Transition Metal Complexes as Guests in a Ga4L612– Nanocage

Designed Local Electric Fields─Promising Tools for Enzyme Engineering

A Porphyrin-Faced Zn8L6 Cage for Selective Oxidation of C(sp3)–H Bonds and Sulfides

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Product

Resources

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Computational Screening of Putative Catalyst Transition Metal Complexes as Guests in a Ga₄L₆^12– Nanocage

Computational Screening of Putative Catalyst Transition Metal Complexes as Guests in a Ga₄L₆^12– Nanocage

A Porphyrin-Faced Zn₈L₆ Cage for Selective Oxidation of C(sp³)–H Bonds and Sulfides