Effective tuning of the electronic and photophysical properties of tetrathiafulvalene pyrroles via aromatic heterocycle annulation

Park, Jung Su; Kim, Ji-Hae; Kim, Yong Hoon; Sessler, Jonathan L.

doi:10.1039/c5ra14811a

Cited by 4 publications

(4 citation statements)

References 24 publications

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“…120 They designed and synthesized various TTF-C4Ps and other oligopyrrolic macrocycles. 55,[121][122][123][124][125][126] They utilized TTF-based C4P 31 (Scheme 4) and carried out anion binding studies with diverse anions such Table 1 Binding constants (using UV-Vis titrations) of 1, 56 and 57 for various anions…”

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New dimensions in calix[4]pyrrole: the land of opportunity in supramolecular chemistry

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New dimensions in calix[4]pyrrole: the land of opportunity in supramolecular chemistry

et al. 2019

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“…Recently, we reported the synthesis of three aromatic heterocycles (furan, pyrazine, and 1,2,5‐thiadiazole)‐annulated TTF‐pyrrole derivatives and systematic comparisons of these materials with three other reported aromatic‐annulated ones (pyrrolo‐, thiopheno‐, and benzo‐TTF‐pyrroles) in terms of electronic, chemical, and photophysical properties . It shows that degrees of electron‐donating ability and magnitude of dipole moments of TTF‐pyrrole can be readily tuned in a wide range by the heterocycle‐annulation strategy.…”

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Synthesis and Properties Study of Novel Unsymmetrical Pyrrolo‐annulated Benzo‐diselenadithiafulvalene

Pak

Ali

Park

2016

Bulletin Korean Chem Soc

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Since the discovery of the tetrathiafulvalene (TTF)-based organic conductors, composed of TTF and tetracyanoquinodimethane in 1973, 1 investigations on the chemical, physical, and functional properties of the TTFs and its higher chalcogen analogues such as tetraselenafulvalene (TSF) and diselenadithiafulvalene (DSDTF) derivatives, have attracted much interest and been widely studied. 2 These intensified and extensive research efforts on chemistry of TTFs provide an expansion of the research scopes beyond electrically conducting materials to various fields of functional material chemistry, such as nonlinear optics, photovoltaics, molecular electronics, molecular receptors, molecular switches, logic gates, molecular machines, etc. [2][3][4][5][6][7] Among various types of TTFs and its congeners, we are particularly interested in design, synthesis, and property studies of pyrrole-containing systems. This is because these derivatives can be used as versatile building blocks to construct a wide range of functional supramolecular materials. 8 In fact, several pyrrole-annulated TTF derivatives have been synthesized, some of which were successfully applied to construct porphyrins, expand porphyrins, calix[n]pyrroles, and rotaxanes, so on. [8][9][10][11][12][13][14][15][16][17][18][19] In the particular case of TTF-calix[4]pyrrole (TTF-C4P) receptors for the colorimetric detection of nitro-aromatic explosives, it has been demonstrated that their performance such as binding affinities and colorimetric responsiveness can be dramatically enhanced through electronic modulation of the parent TTF-pyrrole building blocks used to construct the C4P frameworks. 18 This improvement was accomplished by benzene-or thiophene-annulation on TTF-pyrrole core. It is thus appreciated that appropriate electronic modulation on the fundamental building blocks is one of the key importances in determining the overall performance of the resulting supramolecular frameworks.Recently, we reported the synthesis of three aromatic heterocycles (furan, pyrazine, and 1,2,5-thiadiazole)-annulated TTF-pyrrole derivatives and systematic comparisons of these materials with three other reported aromatic-annulated ones (pyrrolo-, thiopheno-, and benzo-TTF-pyrroles) in terms of electronic, chemical, and photophysical properties. 20 It shows that degrees of electron-donating ability and magnitude of dipole moments of TTF-pyrrole can be readily tuned in a wide range by the heterocycle-annulation strategy. To the best of our knowledge, to date, there are no reports on pyrrole-containing DSDTF and very few reports are available on TSF derivatives, although the importance of the selenium containing TTF-type electron donors is well recognized in TTF chemistry. As pointed out in the literature, the replacement of sulfur atoms in the TTF core with selenium atoms is an efficient way to increase intermolecular interactions, dimensionality, and polarizability. 2 With this consideration in mind, the first novel unsymmetrical benzene-annulated DSDTF-pyrrole 5 was targeted, ...

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“…We and others have pursued the development of C4P derivatives with multiple recognition features along two generalized lines. − The first involves functionalization at the meso positions and the second replacement of the β-pyrrolic protons with synthetically more elaborate substituents. − While the first approach has proved highly effective for the preparation of second- and third-generation ion receptors, we felt that the second option would prove more useful in the context of creating systems that display allosteric recognition features. With such a view in mind and in conjunction with collaborators from Odense, we created a series of TTF-bearing pyrrolic building blocks. , These were then used to prepare a number of TTF-annulated calix[ n ]pyrroles − and other oligopyrrolic macrocyles. , The smallest members of this family, the TTF-C4Ps, have proved capable of binding a variety of guest molecules in organic media. Often allosteric binding is observed.…”

Section: Conformational Properties and Allosteric Nature Of Ttf-calix...mentioning

confidence: 99%

“…With such a view in mind and in conjunction with collaborators from Odense, we created a series of TTF-bearing pyrrolic building blocks. 17,18 These were then used to prepare a number of TTF-annulated calix[n]pyrroles 19−21 and other oligopyrrolic macrocyles. 22,23 The smallest members of this family, the TTF-C4Ps, have proved capable of binding a variety of guest molecules in organic media.…”

Section: ■ Conformational Properties and Allosteric Nature Of Ttf-cal...mentioning

confidence: 99%

Tetrathiafulvalene (TTF)-Annulated Calix[4]pyrroles: Chemically Switchable Systems with Encodable Allosteric Recognition and Logic Gate Functions

Park

Sessler

2018

Acc. Chem. Res.

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Molecular and supramolecular systems capable of switching between two or more states as the result of an applied chemical stimulus are attracting ever-increasing attention. They have seen wide application in the development of functional materials including, but not limited to, molecular and supramolecular switches, chemosensors, electronics, optoelectronics, and logic gates. A wide range of chemical stimuli have been used to control the switching within bi- and multiple state systems made up from either singular molecular entities or supramolecular ensembles. In general, chemically triggered switching systems contain at least two major functional components that provide for molecular recognition and signal transduction, respectively. These components can be connected to one another via either covalent or noncovalent linkages. Of particular interest are switchable systems displaying cooperative or allosteric features. Such advanced control over function is ubiquitous in nature and, in the case of synthetic systems, may allow the capture and release of a targeted chemical entity or permit the transduction of binding information from one recognition site to another. Allosterically controlled complexation and decomplexation could also permit the amplification or deamplification of analyte-specific binding affinity, lead to nonlinear binding characteristics, or permit a magnification of output signals. Our own efforts to develop chemically driven supramolecular switches, advanced logic gates, and multifunction cascade systems have focused on the use of tetrathiafulvalene (TTF) annulated calix[4]pyrroles (C4Ps). These systems, TTF-C4Ps, combine several orthogonal binding motifs within what are conformationally switchable receptor frameworks. Their basic structure and host-guest recognition functions can be controlled via application of an appropriate chemical stimulus. Homotropic or heterotropic allosteric molecular recognition behavior is often seen. This has allowed us to (1) produce self-assembled structures, (2) control switching between bi- and multistate constructs, (3) generate chemical logic gates performing chemical-based Boolean logic operations, (4) create ionically controlled three-state logic systems that release different chemical messengers and activate disparate downstream reactions, and (5) encode a variety advanced functional operations into what are relatively simple molecular-scale devices. Looking to the future, we believe that exploiting allosteric control will expand opportunities for supramolecular chemists and allow some of the complexity seen in biology to be reproduced in simple constructs. Of particular appeal would be a capacity to release chemical messengers at will, perhaps after a prior capture and chemical modification step, that then encode for further downstream functions as seen in the case of the small molecules, such as neurotransmitters and pheromones, used by nature for the purpose of intraentity communication. Molecular scale logic devices with allosteric functions are thus the...

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Effective tuning of the electronic and photophysical properties of tetrathiafulvalene pyrroles via aromatic heterocycle annulation

Cited by 4 publications

References 24 publications

New dimensions in calix[4]pyrrole: the land of opportunity in supramolecular chemistry

New dimensions in calix[4]pyrrole: the land of opportunity in supramolecular chemistry

Synthesis and Properties Study of Novel Unsymmetrical Pyrrolo‐annulated Benzo‐diselenadithiafulvalene

Tetrathiafulvalene (TTF)-Annulated Calix[4]pyrroles: Chemically Switchable Systems with Encodable Allosteric Recognition and Logic Gate Functions

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