‘Lock and key’ control of optical properties in a push–pull system

Jordan, Brian J.; Pollier, Michael A.; Ofir, Yuval; Joubanian, Steven; Mehtala, Jonathan G.; Sinkel, Carsten; Caldwell, Stuart T.; Kennedy, Andrew; Rabani, Gouher; Cooke, Graeme; Rotello, Vincent M.

doi:10.1039/b718015b

Cited by 10 publications

(12 citation statements)

References 39 publications

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“…ABFL is a D,A molecule with hydrogen‐bonding capabilities 10. Methylation at the N(3) position of ABFL (MABFL) eliminates the hydrogen‐bonding capabilities (Figure 1a) but maintains a similar total dipole moment (Supporting Information).…”

Section: Resultsmentioning

confidence: 99%

“…The larger bathochromic shift observed for ABFL was not surprising when comparing the relative solubility and hydrogen‐bonding ability of the two chemical structures. Initial stabilization of the CT for ABFL and MABFL was presumably due to a combination of solute/solvent hydrogen‐bonding interactions,10 as well as strong dipole–dipole interactions that initiate aggregation.…”

Section: Resultsmentioning

confidence: 99%

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Controlled Self‐Assembly of Organic Nanowires and Platelets Using Dipolar and Hydrogen‐Bonding Interactions

Jordan

Ofir

Patra

et al. 2008

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Synergistic dipole-dipole and hydrogen-bonding interactions are used to assemble nanostructured materials. Precipitation of a hydrogen-bonding donor-acceptor molecule 8-[[p-[bis(ethyl)amino]phenyl]azo]-isobutylflavin (ABFL) yields nanowires approximately 50-150 nm in diameter and lengths of several millimeters. Precipitation of the non-hydrogen-bonding analog, methylated ABFL (MABFL), generates micrometer-sized hexagonal platelets that are 5-10 microm in length, 1-5 microm in width, and 0.1-0.5 microm thick. The structural similarity of the two molecules allows intermediate morphologies to be formed via co-precipitation. Doping experiments demonstrate efficient control over nanowire length and diameter due to the disruption of the hydrogen bonding within the nanowires.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Controlled Self‐Assembly of Organic Nanowires and Platelets Using Dipolar and Hydrogen‐Bonding Interactions

Jordan

Ofir

Patra

et al. 2008

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“…A recent example is that of a CT dyad consisting of an azobenzyl donor group flavin tethered to the C8 position of N10-isobutylflavin. 18 The largest optical absorption band had a |Δμ| of over 23 D, with an accompanying large difference isotropic polarizability (TrΔα) of over 1200 Å 3 . 19 For purposes of comparison, the flavin by itself has |Δμ| ≈ 2 D and a very small TrΔα for its lowest π−π* transition.…”

Section: ■ Introductionmentioning

confidence: 99%

“…Thus, CT transitions that are usually broad or difficult to distinguish from non-CT transitions are well-resolved and easily identified. A recent example is that of a CT dyad consisting of an azobenzyl donor group flavin tethered to the C8 position of N10-isobutylflavin . The largest optical absorption band had a |Δμ| of over 23 D, with an accompanying large difference isotropic polarizability (TrΔα) of over 1200 Å 3 .…”

Section: Introductionmentioning

confidence: 99%

Dipole Moment and Polarizability of Tunable Intramolecular Charge Transfer States in Heterocyclic π-Conjugated Molecular Dyads Determined by Computational and Stark Spectroscopic Study

et al. 2018

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The annulation of two redox-active molecules into a compact and planar structure paves the way toward a new class of electronically versatile materials whose physical properties can be tuned via a substitution of one of the constituting moieties. Specifically, we present tetrathiafulvalene− benzothiadiazole donor−acceptor molecules. The critical role played by the dielectric properties of these molecules is evident by the large spectral shifts of the ground-state absorption spectra in a range of solvents. Stark spectroscopy is performed to determine experimentally dipole and polarizability change over transitions in the visible range with particular attention to the transition from the highest-occupied molecular orbital (HOMO) to the lowest-unoccupied molecular orbital (LUMO). The experimental results are compared to the results of time-dependent density functional theory calculations, and we reciprocally validate results from calculation and experiment. This allows us to filter out effective models and reveal important insights. The calculations are initially performed in the gas phase and subsequently a polarizable continuum model is adopted to probe the influence of the solvent on the molecular dielectric properties. The results show a large charge displacement from the HOMO to the LUMO and confirm the intramolecular charge transfer nature of the lowest-energy transition. Substitution of the acceptor moiety with electronwithdrawing groups results in changes to the experimentally determined molecular properties consistent with the effects predicted by computational results. The dominant contribution to the electroabsorption signal is due to the change in dipole moment, which is measured to be roughly 20 D for all samples and forms a small angle with the transition dipole moment in a toluene solvent environment.

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“…1–5 Molecular recognition, 6, 7 self-assembly, 8 lock-key modality 9 and reversibility 10 are among the most important features that enable supramolecular chemistry to be employed in many applications including catalysis, 11, 12 delivery, 13, 14 sensing, 15–17 and imaging. 18 These applications use building blocks assembled together by intermolecular interactions including electrostatic interactions, 19 hydrogen bonding, 20 π–π interactions, 21 ion-dipole interactions, 22, 23 hydrophobic or solvophobic effects.…”

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confidence: 99%

Binding studies of cucurbit[7]uril with gold nanoparticles bearing different surface functionalities

Tonga

Mizuhara

Saha

et al. 2015

Tetrahedron Letters

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Host-guest interactions between a synthetic receptor, cucurbit[7]uril (CB[7]), and gold nanoparticles (AuNPs) have been quantified using isothermal titration calorimetry. AuNPs were functionalized with ligands containing tertiary or quaternary benzylamine derivatives, with electron donating or withdrawing groups at the para position of the benzene ring. Analysis of binding interactions reveals that functional groups at the para position have no significant effect on binding constant. However, headgroups bearing a permanent positive charge increased the binding of AuNPs to CB[7] ten-fold compared to monomethyl counterparts.

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‘Lock and key’ control of optical properties in a push–pull system

Cited by 10 publications

References 39 publications

Controlled Self‐Assembly of Organic Nanowires and Platelets Using Dipolar and Hydrogen‐Bonding Interactions

Controlled Self‐Assembly of Organic Nanowires and Platelets Using Dipolar and Hydrogen‐Bonding Interactions

Dipole Moment and Polarizability of Tunable Intramolecular Charge Transfer States in Heterocyclic π-Conjugated Molecular Dyads Determined by Computational and Stark Spectroscopic Study

Binding studies of cucurbit[7]uril with gold nanoparticles bearing different surface functionalities

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