An Amphiphilic Folding Molecule That Undergoes an Irreversible Conformational Change

Nguyen, Jessica; Iverson, Brent L.

doi:10.1021/ja9838920

Cited by 140 publications

(91 citation statements)

References 9 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…The distinct S-shaped folded conformation arose from double-sided association of the NDI unit [12,13] with two PI termini. The average distance between NDI and PI planes was 3.322 .…”

Section: Resultsmentioning

confidence: 99%

“…Nevertheless, there have been no studies on the vapochromism of organic crystals, probably owing to their imagined low adsorption ability in comparison to metal-organic framework systems, [4k, 6a, 7] and the absence of d orbital interactions needed for versatile color change. As part of our program aimed at the creation of new organic functional materials, we have been investigating the development of functional organic crystals utilizing 1,4,5,8-naphthalenetetracarboxylic diimide (NDI), which provides molecules with specific assembling, [10,11] folding [12,13] and chromic [11] behaviors, owing to its planar structure and strong p-electron accepting properties. [14] In this paper, we describe the first vapochromic organic crystals in which flexible open-close motions of Sshaped, donor-linked NDI unit results in strong adsorption properties and molecular shape-dependent color changes upon exposure to a variety of organic vapors.…”

Section: Introductionmentioning

confidence: 99%

“…In this compound, the potentially chromic NDI [11,13] moiety was doubly connected to pyrrole imine (PI) units through trimethylene spacers. This compound readily gave orange crystals 2 from MeOH solution, in which each unit of 1 a had an S-shaped, folded conformation [12,13] by intramolecular donor-acceptor interactions between NDI and PI units. Two MeOH molecules were included tightly in the cavity of this S-shaped template with strong H-bonding to nitrogen atoms of the pyrrole and imine moieties.…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Dynamic Vapochromic Behaviors of Organic Crystals Based on the Open–Close Motions of S‐Shaped Donor–Acceptor Folding Units

Takahashi

Takaya

Naota

2010

Chemistry A European J

View full text Add to dashboard Cite

The first vapochromic organic crystals are described with respect to their preparation, color change, adsorption/desorption properties, crystal structures, and color-change mechanism. Non-solvatochromic, 1,4,5,8-naphthalene-tetracarboxylic diimide (NDI) derivatives 1 a bearing two pyrrole imine (PI) tethers have been used as a motif for the crystal packing template. Red-purple vapochromic solid 3 was prepared by evacuation of orange crystals 2 (equivalent to 1 a2 MeOH), obtained by recrystallization of 1 a from MeOH. Solid 3 showed high-adsorption ability and unprecedented vapor-dependent color changes upon exposure to a variety of organic vapors, whereas light brown amorphous solid 1 a, did not show vapo- or solvatochromic behavior toward any organic solvent. The strong adsorption capability of 3 was confirmed by TGA experiments and adsorption/desorption isotherms. Analysis of the solid-state UV/Vis analysis revealed that the vapor-dependent color changes of 3 were owed to the specific interference of solvent vapors with its broad CT absorbance at lambda=450-650 nm. Packing structures of 1 a in orange crystals 2, red-purple solid 3, and regenerated orange solid 2 were unequivocally established by single crystal and synchrotron powder X-ray diffraction, respectively. Molecular structures and arrays of 1 a in these materials indicated that 1) unit 1 a had an S-shaped folded conformation in 2 and 3 by intramolecular donor-acceptor interactions between NDI and two PI units; 2) inclusion of the guest vapor into the S-shaped template decreased the intramolecular PI-NDI interactions, accompanied by increasing intermolecular NDI-NDI and PI-PI interactions; and 3) such flexible, open-close motions of the S-shaped template could be repeated during reversible adsorption/desorption processes without degradation of crystal packing. The adsorption properties and mechanism of molecular shape-dependent vapochromic behavior of 3 are discussed with reference to experimental results, crystallographic data, and theoretical calculations.

show abstract

“…The distinct S-shaped folded conformation arose from double-sided association of the NDI unit [12,13] with two PI termini. The average distance between NDI and PI planes was 3.322 .…”

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Dynamic Vapochromic Behaviors of Organic Crystals Based on the Open–Close Motions of S‐Shaped Donor–Acceptor Folding Units

Takahashi

Takaya

Naota

2010

Chemistry A European J

View full text Add to dashboard Cite

show abstract

“…Although the molecular stacks of tetrathiafulvalene-7,7,8,8,-tetracyanoquinodimethane and tetramethyltetraselenafulvaene-PF 6 complexes were achieved in crystal, a p-stacked structure has also been constructed using polymer chains. Stable and regulated p-stacked structures in polymers have been realized for DNAs, 3 oligo(m-phenyleneethynylene)s, 4 oligomers consisting of alternating donor and acceptor monomeric units, 5,6 oligomers consisting of acceptor monomeric units in the main chain that interact with a low-molecular-weight donor molecule, 7 oligomers having perylene moieties in the main chain, 8,9 polymers consisting of cyclophane units, [10][11][12] a polymer of bezofulvene derivative, 13,14 and polymers of dibenzofulvene (DBF) and its derivatives (Chart 1).…”

mentioning

confidence: 99%

“…Stable and regulated p-stacked structures in polymers have been realized for DNAs, 3 oligo(m-phenyleneethynylene)s, 4 oligomers consisting of alternating donor and acceptor monomeric units, 5,6 oligomers consisting of acceptor monomeric units in the main chain that interact with a low-molecular-weight donor molecule, 7 oligomers having perylene moieties in the main chain, 8,9 polymers consisting of cyclophane units, [10][11][12] a polymer of bezofulvene derivative, 13,14 and polymers of dibenzofulvene (DBF) and its derivatives (Chart 1). [15][16][17][18][19][20][21][22] In a DNA duplex, paired bases are regularly stacked inside the helical strand.…”

mentioning

confidence: 99%

Synthesis, structure and function of π-stacked polymers

Nakano

2010

Polym J

128

101

View full text Add to dashboard Cite

Macromolecular conformation often has a significant effect on the properties of polymeric materials, and hence, conformational control in synthesizing a polymer is an important goal in polymer science. As a new conformational motif of vinyl polymers having side-chain p-electronic groups, we have introduced a 'p-stacked structure' in which side-chain chromophores are regularly stacked on top of each other and main-chain C-C bonds have a nearly all-trans, zigzag conformation. p-Stacked polymers can be prepared by vinyl polymerization of dibenzofulvene (DBF) and its derivatives. On the basis of the controlled structure, poly(DBF) and its derivatives exhibit unique photophysical and electronic properties as vinyl polymers. In addition, introduction of chirality to p-stacked polymers was also achieved. In this review, the synthesis of poly(DBF) and its derivatives and their structural analyses and properties are described. Polymer Journal (2010) 42, 103-123; doi:10.1038/pj.2009 Keywords: charge transport; chirality; dibenzofulvene; helix; photophysical properties; p-stacked structureIn designing functional organic materials with desired properties, spatial arrangement control of constituent molecules is an important factor because molecules in a regulated assembly often indicate properties different from those in solution or in gas phase because of specific intermolecular interactions. Effective molecular assembly control can be achieved by arrangement of functional molecules as a part of a polymer chain with a regulated conformation and configuration in which the polymer backbone functions as a structural template or scaffold. This is possible either by polymerizing functional molecules as monomers or by attaching functional molecules through a chemical reaction to a polymer chain. In the former case, the functional molecules to be aligned need to have a polymerizable moiety such as a vinyl group; they are a part of monomers and become constituents of a polymer chain as a part of monomeric units, typically as side-chain groups. The monomer structure itself may significantly contribute to the formation of a regulated polymer chain structure through intermolecular repulsion or attraction. An advantage of these polymer-based methods over other methodologies developed mainly for low-molecular-weight compounds based on the accumulation of relatively weak forces is that molecular orders formed along a polymer chain are generally stable due to covalent bonds. Moreover, using a polymer chain, a very tight or close packing of molecules (monomeric units), which is not plausible for the method based on weak intermolecular attractions, is possible when the enthalpy gain in covalent bond formation by polymerization or by polymer reaction outweighs the loss in free energy in packing molecules tightly into a small space around the polymer chain.Although these polymer-based methods generally require more synthetic efforts than intermolecular-force-based methods, a wider variety of molecular orders may be possible on the basis of re...

show abstract

Improved treatment of cyclic ?-amino acids and successful prediction of ?-peptide secondary structure using a modified force field: AMBER*C

et al. 2000

View full text Add to dashboard Cite

We added parameters to the AMBER* force field to model cyclic β‐amino acid derivatives more accurately within the commonly used MacroModel program. In an effort to generate an improved treatment of cyclohexane and cyclopentane conformational preferences, carbon–carbon torsional parameters were modified and incorporated into a force field we call AMBER*C. Simulation of trans‐2‐aminocyclohexanecarboxylic acid (trans‐ACHC) and trans‐2‐aminocyclopentanecarboxylic acid (trans‐ACPC) derivatives using AMBER*C produces more realistic energy differences between (pseudo)diaxial and (pseudo)diequatorial conformations than does simulation using AMBER*. AMBER*C molecular dynamics simulations more accurately reproduce the experimental hydrogen‐bonding tendencies of simple diamide derivatives of trans‐ACHC and trans‐ACPC than do simulations using the AMBER* force field. More importantly, this modified force field allows accurate qualitative prediction of the helical secondary structures adopted by β‐amino acid homo‐oligomers. © 2000 John Wiley & Sons, Inc. J Comput Chem 21: 763–773, 2000

show abstract

An Amphiphilic Folding Molecule That Undergoes an Irreversible Conformational Change

Cited by 140 publications

References 9 publications

Dynamic Vapochromic Behaviors of Organic Crystals Based on the Open–Close Motions of S‐Shaped Donor–Acceptor Folding Units

Dynamic Vapochromic Behaviors of Organic Crystals Based on the Open–Close Motions of S‐Shaped Donor–Acceptor Folding Units

Synthesis, structure and function of π-stacked polymers

Improved treatment of cyclic ?-amino acids and successful prediction of ?-peptide secondary structure using a modified force field: AMBER*C

Contact Info

Product

Resources

About