Synthesis and structural characterization of adaptable shape-persistent building blocks

Degenhardt, Charles F.; Shortell, David Brian; Adams, Richard D.; Shimizu, Ken D.

doi:10.1039/b002085k

Cited by 26 publications

(24 citation statements)

References 4 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Ligand synthesis: The synthesis of N,N'-bis(3,5-dicarboxyphenyl)pyromellitic diimide (H 4 BDCPPI) was achieved by using a modified version of a previously reported procedure: [26] 1,2,4,5-benzene tetracarboxylate dianhydride (2.18 g, 10 mmol) and 5-aminoisophthalic acid (3.62 g, 20 mmol) were dissolved in DMF (40 mL). The solution was heated at reflux for 8 h, and then allowed to cool to room temperature.…”

Section: Methodsmentioning

confidence: 99%

High Gas Sorption and Metal‐Ion Exchange of Microporous Metal–Organic Frameworks with Incorporated Imide Groups

Prasad

Hong

Suh

2010

Chemistry A European J

251

117

View full text Add to dashboard Cite

Metal-organic frameworks (MOFs), {[Cu(2)(bdcppi)(dmf)(2)]·10DMF·2H(2)O}(n) (SNU-50) and {[Zn(2)(bdcppi)(dmf)(3)]·6DMF·4H(2)O}(n) (SNU-51), have been prepared by the solvothermal reactions of N,N'-bis(3,5-dicarboxyphenyl)pyromellitic diimide (H(4)BDCPPI) with Cu(NO(3))(2) and Zn(NO(3))(2), respectively. Framework SNU-50 has an NbO-type net structure, whereas SNU-51 has a PtS-type net structure. Desolvated solid [Cu(2)(bdcppi)](n) (SNU-50'), which was prepared by guest exchange of SNU-50 with acetone followed by evacuation at 170 °C, adsorbs high amounts of N(2), H(2), O(2), CO(2), and CH(4) gases due to the presence of a vacant coordination site at every metal ion, and to the presence of imide groups in the ligand. The Langmuir surface area is 2450 m(2) g(-1). It adsorbs H(2) gas up to 2.10 wt% at 1 atm and 77 K, with zero coverage isosteric heat of 7.1 kJ mol(-1), up to a total of 7.85 wt% at 77 K and 60 bar. Its CO(2) and CH(4) adsorption capacities at 298 K are 77 wt% at 55 bar and 17 wt% at 60 bar, respectively. Of particular note is the O(2) adsorption capacity of SNU-50' (118 wt% at 77 K and 0.2 atm), which is the highest reported so far for any MOF. By metal-ion exchange of SNU-51 with Cu(II), {[Cu(2)(bdcppi)(dmf)(3)]·7DMF·5H(2)O}(n) (SNU-51-Cu(DMF)) with a PtS-type net was prepared, which could not be synthesized by a direct solvothermal reaction.

show abstract

Section: Methodsmentioning

confidence: 99%

High Gas Sorption and Metal‐Ion Exchange of Microporous Metal–Organic Frameworks with Incorporated Imide Groups

Prasad

Hong

Suh

2010

Chemistry A European J

251

117

View full text Add to dashboard Cite

show abstract

“…The twist α1 and α2 angles (defined here as α1 = C2-C1-C1 A-C2 A, α2 = C4-C5-C1 B-C2 B) define the relative orientation of biphenyl moieties A and B to the central terephthalaldehyde unit C. The computational study clearly indicates that the low-energy conformers are characterized by the values of the α angles ranging from ±60 • to ±120 • . As it was in the case described previously, the low-energy conformers of 2c, by analogy to the B-A-B-type triads, can be considered of C or S-type [45][46][47]. Conformers characterized by the opposite signs of the α1 and α2 angles (S-type conformers) were of higher energy than C-type structures characterized by the same signs (not necessarily the values) of the α angles.…”

Section: Compoundmentioning

confidence: 77%

“Double-Twist”-Based Dynamic Induction of Optical Activity in Multichromophoric System

2021

View full text Add to dashboard Cite

The electronic circular dichroism (CD)-silent 2,5-bis(biphen-2-yl)terephthalaldehyde has been used as a sensor (reporter) of chirality for primary amines. The through-space inductor–reporter interactions force a change in the chromophore conformation toward one of the diastereomeric forms. The structure of the reporter, with the terminal flipping biphenyl groups, led to generating Cotton effects in both lower- and higher-energy regions of the ECD spectrum. The induction of an optical activity in the chromophore was due to the cascade point-to-axial chirality transmission mechanism. The reporter system turned out to be sensitive to the subtle differences in the inductor structure. Despite the size of the chiral substituent, the molecular structure of the inductor–reporter systems in the solid-state showed many similarities. The most important one was the tendency of the core part of the molecules to adapt pseudocentrosymmetric conformation. Supported by a weak dispersion and Van der Waals interactions, the face-to-face and edge-to-face interactions between the π-electron systems present in the molecule were found to be responsible for the molecular arrangement in the crystal.

show abstract

“…Our goal has been to design and study molecules and polymers that combine the advantages of conformationally flexible and shapepersistent systems to better control conformation on the molecular level. [8][9][10][11] At higher temperatures, the molecules are conformationally flexible and thus, can be shaped and molded into specific conformations. On cooling to ambient temperature, the new conformations can then be 'saved' as the molecules becomes rigid and shape-persistent.…”

mentioning

confidence: 99%

“…These isomeric forms have been shown to display very different dipole, solubility, shape, and recognition properties. [8][9][10][11] These systems are complementary to the azobenzene based polymers and macrocycles 12,13 that contain building blocks that can adopt similar convergent cis and divergent trans conformations that can be switched via UV irradiation. [14][15][16]…”

mentioning

confidence: 99%

Shape-Persistent and Shape-Adaptable Macrocycles Based on Restricted Rotation: Studies Building Toward ‘Macromolecular Playdough’

Chong¹,

Shimizu²

2002

Synthesis

View full text Add to dashboard Cite

A rigid 48-membered macrocycle 1 was synthesized and studied that comprises two atropisomeric N,N¢-diarylnaphthalenediimide building blocks that adopt stable syn and anti conformations due to restricted rotation about two C aryl -N imide bonds. The resulting macrocycle maintains three distinct conformations: anti/ anti, syn/anti and syn/syn conformers that are stable and separable at room temperatures, and each with distinct shapes and sizes as measured by GPC. At elevated temperatures, macrocycle 1 was conformationally flexible and showed interconversion of the respective isomers. Conformational preferences established at higher temperatures were preserved on cooling to room temperature as the restricted rotation was reestablished and the macrocycle becomes conformationally rigid.

show abstract

Synthesis and structural characterization of adaptable shape-persistent building blocks

Cited by 26 publications

References 4 publications

High Gas Sorption and Metal‐Ion Exchange of Microporous Metal–Organic Frameworks with Incorporated Imide Groups

High Gas Sorption and Metal‐Ion Exchange of Microporous Metal–Organic Frameworks with Incorporated Imide Groups

“Double-Twist”-Based Dynamic Induction of Optical Activity in Multichromophoric System

Shape-Persistent and Shape-Adaptable Macrocycles Based on Restricted Rotation: Studies Building Toward ‘Macromolecular Playdough’

Contact Info

Product

Resources

About