Pillar-Assisted Construction of a Three-Dimensional Framework from a Two-Dimensional Bilayer Based on a Zn/Cd Heterometal Cluster: Pore Tuning and Gas Adsorption

Song, Danhua; Hou, Haiyang; Gao, Yanhua; Jiang, Feilong; Yuan, Daqiang; Chen, Qihui; Liang, Linfeng; Wu, Dong; Hong, Maochun

doi:10.1021/acs.cgd.7b01694

“…Pyridine Driven Generation of Chirality aa chiral 2D coordination polymer,{ [Zn 2 Cd(BTB) 2 (H 2 O) 2 ] n } (FJI-H16); [21] while adding extra pyridine into such selfassembly system led to ac hiral 3D MOF,{ [Zn 2 Cd(BTB) 2 -(H 2 O) 2 ] n }( FJI-H27)( Scheme 1a,b). FJI-H16 crystallizes in the achiral space group P-31c.…”

Section: Resultsmentioning

confidence: 99%

Induction of Chirality in a Metal–Organic Framework Built from Achiral Precursors

Wu

¹

,

Zhou

²

,

Tian

³

et al. 2020

Self Cite

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Induction of chirality from an achiral assembly system remains a huge challenge related to the origin of life. Here, induction of chirality in a metal–organic framework (MOF) built from achiral precursors has been realized. Assembling achiral H3BTB ligands and ZnII/CdII clusters leads to a 2D coordination polymer (FJI‐H16), while introduction of achiral pyridine into such assembly system leads to a 3D chiral MOF (FJI‐H27 (M) or (P)). The driven force for chiral generation has been proved to be a pyridine participated kinetic‐control assembly process, which can be controlled by changing the amount of pyridine and temperature, from no induction to partial induction to complete induction. The chiral generation process has been identified in detail through a pyridine‐involved key intermediate (FJI‐H28). The targeted modification of pyridine can selectively lead to FJI‐H27 (M) or FJI‐H27 (P), making the chiral orientation and distribution of bulk FJI‐H27 samples can be controlled. Our work not only represents a new chiral induction process that may relate to the chiral origin in nature, but also firstly reveals how achiral external stimuli generate chirality from achiral precursors, and offers a guide for rational preparation of chiral MOFs.

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“…Solvothermal reaction of Zn(NO 3 ) 2 , Cd(NO 3 ) 2 , and H 3 BTB in DEF/EtOH solution at 85 °C for 3 days led to a achiral 2D coordination polymer, {[Zn 2 Cd(BTB) 2 (H 2 O) 2 ] n } ( FJI‐H16 ); [21] while adding extra pyridine into such self‐assembly system led to a chiral 3D MOF, {[Zn 2 Cd(BTB) 2 (H 2 O) 2 ] n } ( FJI‐H27 ) (Scheme 1 a,b). FJI‐H16 crystallizes in the achiral space group P ‐31 c .…”

Section: Resultsmentioning

confidence: 99%

Induction of Chirality in a Metal–Organic Framework Built from Achiral Precursors

Wu

¹

,

Zhou

²

,

Tian

³

et al. 2020

Self Cite

View full text Add to dashboard Cite

Induction of chirality from an achiral assembly system remains a huge challenge related to the origin of life. Here, induction of chirality in a metal–organic framework (MOF) built from achiral precursors has been realized. Assembling achiral H3BTB ligands and ZnII/CdII clusters leads to a 2D coordination polymer (FJI‐H16), while introduction of achiral pyridine into such assembly system leads to a 3D chiral MOF (FJI‐H27 (M) or (P)). The driven force for chiral generation has been proved to be a pyridine participated kinetic‐control assembly process, which can be controlled by changing the amount of pyridine and temperature, from no induction to partial induction to complete induction. The chiral generation process has been identified in detail through a pyridine‐involved key intermediate (FJI‐H28). The targeted modification of pyridine can selectively lead to FJI‐H27 (M) or FJI‐H27 (P), making the chiral orientation and distribution of bulk FJI‐H27 samples can be controlled. Our work not only represents a new chiral induction process that may relate to the chiral origin in nature, but also firstly reveals how achiral external stimuli generate chirality from achiral precursors, and offers a guide for rational preparation of chiral MOFs.

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“…Porous coordination polymers (PCPs), or metal−organic frameworks (MOFs), have attracted great interest because of their designable frameworks and pore structures as well as interesting structural transformations. , PCPs have many classic structure types, most of which can be simplified as topological nets . As a special type of PCP prototypes, pillared-layer structures consist of stable or dense metal–ligand layers and variable pillar ligands. − Because the pores in the metal–ligand layers are very small, pillared-layer structures can prevent interpenetration. Therefore, changing the pillar ligand can rationally control the pore environment.…”

Section: Introductionmentioning

confidence: 99%

A Metal–Ligand Layer Compatible with Various Types of Pillars for New Porous Coordination Polymers

Li

¹

,

Mo

²

,

Zhang

³

et al. 2020

Crystal Growth & Design

1

0

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Pillared-layer structures are classic for porous coordination polymers (PCPs), but suitable metal−ligand layers for such structures are rare. Here, we report a cationic {Zn 2 (pzdc)} + (H 3 pzdc = 3,5-pyrazoledicarboxylic acid) layer compatible with various types of pillar ligands. Solvothermal reactions of Zn(NO 3 ) 2 •6H 2 O and H 3 pzdc with 4-(pyridin-4-yl)-1H-pyrazole (Hpypz), 1,4-benzenedicarboxylic acid (H 2 bdc), or 2amino-1,4-benzenedicarboxylic acid (H 2 abdc) in a mixed solvent of H 2 O and N,N-dimethylformamide (DMF) produced three pillared-layer PCPs, namely [Zn 4 (pzdc) 2 (pypz) 2 ]•guest (1), [Zn 4 (pzdc) 2 (bdc)(H 2 O) 1. 5 3 (DMF) 0. 4 7 ]•guest (2), and [Zn 4 (pzdc) 2 (abdc)(H 2 O) 1.52 (DMF) 0.48 ]•guest (3), respectively. Single-crystal X-ray analyses revealed that the {Zn 2 (pzdc)} + layers are fully pillared by pypz − in 1 and half pillared by bdc 2− and abdc 2− in 2 and 3, because the anionic pillars possess different charges.Consequently, 1 shows one-dimensional (1D) channels with a small porosity and 2 and 3 show 2D channels with large porosities, both of which were verified by N 2 and CO 2 adsorption isotherms. While 1 has no coordinated solvent molecules and exhibits a high water stability, 2 and 3 possess coordinated solvent molecules and quickly transform to crystals of 2D coordination networks in water, [Zn 4 (pzdc) 2 (OH) 2 (H 2 O) 6 ]•H 2 bdc•4H 2 O (4) and [Zn 4 (pzdc) 2 (H 2 abdc)(OH) 2 (H 2 O) 5 ]•2H 2 O (5), respectively, which can be further exfoliated into ultrathin nanosheets in an ammonia solution.

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Pillar-Assisted Construction of a Three-Dimensional Framework from a Two-Dimensional Bilayer Based on a Zn/Cd Heterometal Cluster: Pore Tuning and Gas Adsorption

Cited by 6 publications

References 42 publications

Induction of Chirality in a Metal–Organic Framework Built from Achiral Precursors

Induction of Chirality in a Metal–Organic Framework Built from Achiral Precursors

Induction of Chirality in a Metal–Organic Framework Built from Achiral Precursors

A Metal–Ligand Layer Compatible with Various Types of Pillars for New Porous Coordination Polymers

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