The introduction of a base component to porous organic salts and their CO<sub>2</sub> storage capability

Ami, Takahiro; Oka, Kouki; Tuchiya, Keiho; Kosaka, Wataru; Miyasaka, Hitoshi; Tohnai, Norimitsu

doi:10.1039/d3ce00086a

“…[110] The efficient and robust supramolecular structure of [4 + 4] ion-pair clusters consisting of four ion pairs can be used as materials for gas adsorption and sensing. [111][112][113][114][115][116] Organic amidines are more basic than amines and have similar directionality to carboxylic acids. Supramolecular structures based on organic carboxylic acids and amidines are constructed by White.…”

Section: Introductionmentioning

confidence: 99%

“…In 2006, Tohnai reported that Porous organic salts (POSs) were prepared by organosulfonic acid and triphenylmethylamine [110] . The efficient and robust supramolecular structure of [4+4] ion‐pair clusters consisting of four ion pairs can be used as materials for gas adsorption and sensing [111–116] . Organic amidines are more basic than amines and have similar directionality to carboxylic acids.…”

Section: Introductionmentioning

confidence: 99%

Charge‐Assisted Ionic Hydrogen‐Bonded Organic Frameworks: Designable and Stabilized Multifunctional Materials

Chen,

Cao,

Bai

et al. 2024

Chemistry A European J

9

0

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Hydrogen‐bonded organic frameworks (HOFs) are a class of crystalline framework materials assembled by hydrogen bonds. HOFs have the advantages of high crystallinity, mild reaction conditions, good solution processability, and reproducibility. Coupled with the reversibility and flexibility of hydrogen bonds, HOFs can be assembled into a wide diversity of crystalline structures. Since the bonding energy of hydrogen bonds is lower than that of ligand and covalent bonds, the framework of HOFs is prone to collapse after desolventisation and the stability is not high, which limits the development and application of HOFs. In recent years, numerous stable and functional HOFs have been developed by π‐π stacking, highly interpenetrated networks, charge‐assisted, ligand‐bond‐assisted, molecular weaving, and covalent cross‐linking. Charge‐assisted ionic HOFs introduce electrostatic attraction into HOFs to improve stability while enriching structural diversity and functionality. In this paper, we review the development, the principles of rational design and assembly of charge‐assisted ionic HOFs, introduces the different building block construction modes of charge‐assisted ionic HOFs. Highlight the applications of charge‐assisted ionic HOFs in gas adsorption and separation, proton conduction, biological applications, etc., and prospects for the diverse design of charge‐assisted ionic HOFs structures and multifunctional applications.

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Highly Fluorinated Nanospace in Porous Organic Salts with High Water Stability/Capability and Proton Conductivity

Ami,

Oka,

Kitajima

et al. 2024

Angewandte Chemie

0

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Water in hydrophobic nanospaces shows specific dynamic properties different from bulk water. The investigation of these properties is important in various research fields, including materials science, chemistry, and biology. The elucidation of the correlation between properties of water and hydrophobic nanospaces requires nanospaces covered only with simple hydrophobic group (e.g., fluorine) without impurities such as metals. This work successfully fabricated all‐organic diamondoid porous organic salts (d‐POSs) with highly fluorinated nanospaces, wherein hydrophobic fluorine atoms are densely exposed on the void surfaces, by combining fluorine substituted triphenylmethylamine (TPMA) derivatives with tetrahedral tetrasulfonic acid. This d‐POSs with a highly fluorinated nanospace significantly improved their water stability, retaining their crystal structure even when immersed in water over one week. Moreover, this highly hydrophobic and fluorinated nanospace adsorbs 160 mL(STP)/g of water vapor at Pe/P0 = 0.90; this is the first hydrophobic nanospace, which water molecules can enter, in an all‐organic porous material. Furthermore, this highly fluorinated nanospace exhibits very high proton conductivity (1.34 × 10−2 S/cm) at 90°C and 95%RH. POSs with tailorable nanospaces may significantly advance the elucidation of the properties of specific “water” in pure hydrophobic environments.

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Highly Fluorinated Nanospace in Porous Organic Salts with High Water Stability/Capability and Proton Conductivity

Ami,

Oka,

Kitajima

et al. 2024

Angew Chem Int Ed

2

0

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Water in hydrophobic nanospaces shows specific dynamic properties different from bulk water. The investigation of these properties is important in various research fields, including materials science, chemistry, and biology. The elucidation of the correlation between properties of water and hydrophobic nanospaces requires nanospaces covered only with simple hydrophobic group (e.g., fluorine) without impurities such as metals. This work successfully fabricated all‐organic diamondoid porous organic salts (d‐POSs) with highly fluorinated nanospaces, wherein hydrophobic fluorine atoms are densely exposed on the void surfaces, by combining fluorine substituted triphenylmethylamine (TPMA) derivatives with tetrahedral tetrasulfonic acid. This d‐POSs with a highly fluorinated nanospace significantly improved their water stability, retaining their crystal structure even when immersed in water over one week. Moreover, this highly hydrophobic and fluorinated nanospace adsorbs 160 mL(STP)/g of water vapor at Pe/P0 = 0.90; this is the first hydrophobic nanospace, which water molecules can enter, in an all‐organic porous material. Furthermore, this highly fluorinated nanospace exhibits very high proton conductivity (1.34 × 10−2 S/cm) at 90°C and 95%RH. POSs with tailorable nanospaces may significantly advance the elucidation of the properties of specific “water” in pure hydrophobic environments.

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The introduction of a base component to porous organic salts and their CO₂ storage capability

Abstract: Porous organic salts (POSs) are constructed by charge-assisted hydrogen bonding between amino and sulfonic groups, and can design a variety of porous structures based on the molecular design. In particular,...

Cited by 5 publications

References 40 publications

Charge‐Assisted Ionic Hydrogen‐Bonded Organic Frameworks: Designable and Stabilized Multifunctional Materials

Charge‐Assisted Ionic Hydrogen‐Bonded Organic Frameworks: Designable and Stabilized Multifunctional Materials

Highly Fluorinated Nanospace in Porous Organic Salts with High Water Stability/Capability and Proton Conductivity

Highly Fluorinated Nanospace in Porous Organic Salts with High Water Stability/Capability and Proton Conductivity

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The introduction of a base component to porous organic salts and their CO2 storage capability

Abstract: Porous organic salts (POSs) are constructed by charge-assisted hydrogen bonding between amino and sulfonic groups, and can design a variety of porous structures based on the molecular design. In particular,...

Cited by 5 publications

References 40 publications

Charge‐Assisted Ionic Hydrogen‐Bonded Organic Frameworks: Designable and Stabilized Multifunctional Materials

Charge‐Assisted Ionic Hydrogen‐Bonded Organic Frameworks: Designable and Stabilized Multifunctional Materials

Highly Fluorinated Nanospace in Porous Organic Salts with High Water Stability/Capability and Proton Conductivity

Highly Fluorinated Nanospace in Porous Organic Salts with High Water Stability/Capability and Proton Conductivity

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The introduction of a base component to porous organic salts and their CO₂ storage capability