Binding studies of tetrathiafulvalene-calix[4]pyrroles with electron-deficient guests

Nielsen, Kent A.; Martín‐Gomis, Luis; Sarova, Ginka H.; Sanguinet, Lionel; Gross, Dustin E.; Fernández‐Lázaro, Fernando; Stein, Paul C.; Levillain, Eric; Sessler, Jonathan L.; Guldi, Dirk M.; Sastre‐Santos, Ángela; Jeppesen, Jan O.

doi:10.1016/j.tet.2008.05.141

Cited by 62 publications

(41 citation statements)

References 49 publications

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“…These complexes, as well as somewhat analogous 3 2 ⊂ 1 complexes, have been previously characterized in dichloromethane. The TNB 2 ⊂ 1 complexes display similar absorption profiles, ascribed to CT interactions between TTF units and electron‐acceptor nitroaromatic substrates, as does 3 2 ⊂ 1 , although they are characterized by a maximum absorption band that is hypsochromically shifted compared to this latter species …”

Section: Resultsmentioning

confidence: 91%

Design and Sensing Properties of a Self‐Assembled Supramolecular Oligomer

Bähring

Martín‐Gomis

Olsen

et al. 2015

Chemistry A European J

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Supramolecular polymers are a class of macromolecules stabilized by weak non-covalent interactions. These self-assembled aggregates typically undergo stimuli-induced reversible assembly and disassembly. They thus hold great promise as so-called functional materials. In this work, we present the design, synthesis, and responsive behavior of a short supramolecular oligomeric system based on two hetero-complementary subunits. These "monomers" consist of a tetrathiafulvalene-functionalized calix[4]pyrrole (TTF-C[4]P) and a glycol diester-linked bis-2,5,7-trinitrodicyanomethylenefluorene-4-carboxylate (TNDCF), respectively. We show that when mixed in organic solvents, such as CHCl , CH ClCH Cl, and methylcyclohexane, supramolecular aggregation takes place to produce short oligomers stabilized by hydrogen bonding and donor-acceptor charge-transfer (CT) interactions. The self-associated materials were characterized by H NMR and UV/Vis/NIR absorption spectroscopy, as well as by concentration- and temperature-dependent absorption spectroscopy and dynamic light scattering (DLS) analyses of both the monomeric and oligomerized species. The self-associated system produced from TTF-C[4]P and TNDCF exhibits a concentration-dependent aggregation behavior typical of supramolecular polymers. Further support for the proposed self-assembly came from theoretical calculations. The fluorescence emitting properties of TNDCF are quenched under conditions that promote the formation of supramolecular aggregates containing TTF-C[4]P and TNDCF. This quenching effect has been utilized as a probe for the detection of substrates in the form of anions (i.e., chloride) and nitroaromatic explosives (i.e., 1,3,5-trinitrobenzene). Specifically, the addition of these substrates to mixtures of TTF-C[4]P and TNDCF produced a fluorescence "turn-on" response.

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Section: Resultsmentioning

confidence: 91%

Design and Sensing Properties of a Self‐Assembled Supramolecular Oligomer

Bähring

Martín‐Gomis

Olsen

et al. 2015

Chemistry A European J

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“…The transannular distance between the centroids of the biphenyl disulfonyl and pyromellitimide units is 7.46 , a very significant reduction from the value of 7.91 found for uncomplexed macrocycle 4. The binding constant, K a , for 1:1 complexation of 7 with macrocyle 4 in CHCl 3 /6F-iPA (6:1) at 20 8C (determined from the charge-transfer band at l = 540 nm by the UV/Vis dilution method) [24] was found to be (33 AE 5) Complexation of 4 and 5 with anthracene: Anthracene (9) has a greater p-surface area than naphthalene and is known to be a good p-electron donor, forming a wide range of pstacked complexes with electron-deficient aromatic molecules, such as 1,3,5-trinitrobenzene, 1,4,5,8-naphthalenetetracarboxylic dianhydride and dichloropyromellitic dianhydride. [25] Herein it was found that co-dissolving 5 and anthracene in CDCl 3 /6F-iPA (6:1) gave a purple solution, clearly indicative of a charge-transfer absorption, and a 1:1 mixture of 5 (8 mm) and anthracene gave a Dd = 0.125 ppm upfield complexation shift of the singlet naphthalene diimide resonance.…”

Section: Resultsmentioning

confidence: 99%

“…X-ray data for macrocycles 4 and 5 and for complexes 4·7, 5·11, 4·12, 5·14, 5 2 ·15 and 5 2 ·17 were determined at Imperial College by using a Siemens P4/ RA diffractometer with graphite-monochromated Cu Ka radiation. Binding constants were determined by using the UV/Vis dilution method [24] and have an uncertainty of around AE 15 %.…”

Section: Methodsmentioning

confidence: 99%

Induced‐Fit Binding of π‐Electron‐Donor Substrates to Macrocyclic Aromatic Ether Imide Sulfones: A Versatile Approach to Molecular Assembly

Colquhoun

Zhu

Williams

et al. 2010

Chemistry A European J

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Novel macrocyclic receptors that bind electron-donor aromatic substrates through pi-stacking donor-acceptor interactions are obtained by cycloimidisation of an amine-functionalised aryl ether sulfone with pyromellitic and 1,4,5,8-naphthalenetetracarboxylic dianhydrides. These macrocycles can form complexes with a wide variety of pi-donor substrates, including tetrathiafulvalene, naphthalene, anthracene, pyrene, perylene and functional derivatives of these polycyclic hydrocarbons. The resulting supramolecular assemblies range from simple 1:1 complexes to [2]- and [3]pseudorotaxanes and even (as a result of crystallographic disorder) an apparent polyrotaxane. Direct five-component self-assembly of a metal-centred [3]pseudorotaxane is also observed on complexation of a macrocyclic ether imide with 8-hydroxyquinoline in the presence of palladium(II) ions. Binding studies in solution were carried out by using (1)H NMR and UV/Vis spectroscopy, and the stoichiometries of binding were confirmed by Job plots based on the charge-transfer absorption bands. The highest association constants were found for strong pi-donor guests with large surface areas, notably perylene and 1-hydroxypyrene, for which K(a) values of 1.4x10(3) and 2.3x10(3) M(-1), respectively, were found. Single-crystal X-ray analyses of the receptors and their derived complexes reveal large induced-fit distortions of the macrocyclic frameworks as a result of complexation. These structures provide compelling evidence for the existence of strong attractive forces between the electronically complementary aromatic pi systems of host and guest.

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“…Each dye is chosen as to react selectively towards various analytes or analyte mixtures. This change of color is based on non-covalent host-guest interaction and redox interaction between the dye (host) and analyte (guest) [17,18]. A change in a color signature indicates the presence of explosives (Fig.…”

Section: Colorimetric Arraymentioning

confidence: 99%

The Xsense project: The application of an intelligent sensor array for high sensitivity handheld explosives detectors

Kostesha

Schmidt

Bosco

et al. 2011

2011 IEEE Sensors Applications Symposium

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Abstract-Multiple independent sensors are used in security and military applications in order to increase sensitivity, selectivity and data reliability. The Xsense project has been initiated at the Technical University of Denmark in collaboration with a number of partners in an effort to produce a handheld sensor for trace detection of explosives. We are using micro-and nano technological approaches for integrating four sensing principles into a single device. At the end of the project, the consortium aims at having delivered a sensor platform consisting of four independent detector principles capable of identifying concentrations of TNT, DNT, HMX and RDX at sub parts-per-billion (ppb) levels and with a false positive rate less than 1 parts-perthousand. The specificity, sensitivity, reliability and the speed of responses are ensured by the use of advanced data processing, surface functionalization and nanostructured sensors and sensor design.

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Binding studies of tetrathiafulvalene-calix[4]pyrroles with electron-deficient guests

Cited by 62 publications

References 49 publications

Design and Sensing Properties of a Self‐Assembled Supramolecular Oligomer

Design and Sensing Properties of a Self‐Assembled Supramolecular Oligomer

Induced‐Fit Binding of π‐Electron‐Donor Substrates to Macrocyclic Aromatic Ether Imide Sulfones: A Versatile Approach to Molecular Assembly

The Xsense project: The application of an intelligent sensor array for high sensitivity handheld explosives detectors

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