Synthesis and Self‐Assembly of a Rigid Exotopic Bisphenanthroline Macrocycle: Surface Patterning and a Supramolecular Nanobasket

Kalsani, Venkateshwarlu; Ammon, Horst; Jäckel, Frank; Rabe, Jürgen P.; Schmittel, Michael

doi:10.1002/chem.200305770

Cited by 59 publications

(35 citation statements)

References 74 publications

(28 reference statements)

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“…Following the work of Schmittel and colleagues (52,53), we reasoned that the bulky ligands of 1a might favor exchange with those of a less hindered copper(I) complex to give a mixed-ligand species as the thermodynamic product. Indeed, this substitution occurred; the aqueous reaction of the two homoleptic complexes 1a and 3 (43) resulted in ligand exchange, giving heteroleptic complex 4 (Eq.…”

Section: Resultsmentioning

confidence: 99%

Dynamic covalent and supramolecular direction of the synthesis and reassembly of copper(I) complexes

Schultz

Nitschke

2005

Proc. Natl. Acad. Sci. U.S.A.

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The technique of subcomponent self-assembly has been applied to the preparation of a set of copper(I) complexes from diamines and aldehydes in aqueous solution. These complexes may be synthesized alongside one another in solution despite the chemical nonorthogonality of their respective starting materials; thermodynamic equilibration eliminates all mixed products. The reactivity of these complexes has been studied, revealing that in certain cases, the substitution of both ligands and ligand subcomponents could be independently carried out. In one particular case, a complex was shown to be inert to ligand substitution but readily underwent ligand subcomponent substitution, creating the possibility of a previously undocumented kind of cascade reaction: Once ligand subcomponent substitution had occurred, ligand exchange could then happen, allowing both reactions to be triggered by a single chemical event.self-assembly ͉ coordination chemistry ͉ cascade reactions T he generation of complex metal-containing architectures from simple building blocks through self-assembly (1-8) is a compelling means by which to build up functional molecular machines (9-11). Such molecular devices are beginning to give substance to the promises of nanotechnology; recent examples include Mirkin and coworkers' (12) signal-amplifying allosteric catalyst, Nolte and colleagues' (13) ''chain-walking'' epoxidation catalyst, Leigh and coworkers' (14) reversible molecular motor, and the molecular elevator of Stoddart and colleagues (15).A powerful technique in metallo-organic self-assembly consists of the simultaneous formation of covalent (carbonheteroatom) and dative (heteroatom-metal) bonds, bringing both ligand and complex into being at the same time. This ''subcomponent self-assembly'' has its roots in the template synthesis of Busch and coworkers (16) and has recently been used in the synthesis of a wealth of structures, including rotaxanes (17), catenanes (18), helicates (19-22), grids (23-25), and a Borromean link (26). These structures belong to the domains of both dynamic covalent (27) and supramolecular (28) Because subcomponent self-assembly reactions operate on two distinct levels simultaneously, one might expect that these reactions would give rise to mixtures of diverse products or large dynamic combinatorial libraries (30-35), as the multiple components combine in different ways. Although many structures might in theory be possible at both covalent and supramolecular levels, the metal and the subcomponents of the ligand may be chosen such that the thermodynamic preferences of both converge to give rise to a single product or a limited number of products (22)(23)(24)(36)(37)(38). It is important to note that it is the reversible formation of intraligand imine bonds (in addition to the metal-ligand bonds) that allows for this dynamic sorting͞ selection effect to occur.Along similar lines, although the addition of further ligand components might be expected to increase the number of species present in the product mixture, it is non...

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Section: Resultsmentioning

confidence: 99%

Dynamic covalent and supramolecular direction of the synthesis and reassembly of copper(I) complexes

Schultz

Nitschke

2005

Proc. Natl. Acad. Sci. U.S.A.

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“…Tetrahedral metal ions have been combined with substituted bis-and tris-phenantholine-based ligands to produce oligonuclear grids [62], boxes [63], and baskets [64] as shown in an example of a box-like structure (Fig. 14) [63].…”

Section: Assembly By Tetrahedral Metal Ionsmentioning

confidence: 99%

Self-assembly of discrete metallosupramolecular luminophores

Cooke

Chartrand

Hanan

2008

Coordination Chemistry Reviews

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“…Porous molecular monolayers are used as two-dimensional hosts for molecular guests, which may be employed for molecular selection or the isolation of single molecules. They have been obtained from macrocycles at the interface between an organic solution and the basal plane of graphite, providing pores in the range of 1.2 to 2.7 nm [19][20][21][22][23]. Alternatively, supramolecular two-dimensional structures have been self-assembled at such solid-liquid interfaces, which are stabilized van der Waals interactions between pending alkyl chains [11,[24][25][26][27][28].…”

Section: Honeycomb Lattices From Polycyclic Aromatic Hydrocarbon Derimentioning

confidence: 99%

Optical switching studies of an azobenzene rigidly linked to a hexa-peri-hexabenzocoronene derivative in solution and at a solid–liquid interface

Groeper

Zhuang

et al. 2008

Appl. Phys. A

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An azobenzene moiety rigidly linked to a hexa-peri-hexabenzocoronene (HBC) derivative has been switched optically between its trans-and cis-conformations in solution. Crystalline monolayers of the flat lying transconformer have been obtained at the interface between the basal plane of graphite and an organic solution. However, from the illuminated solution no cis-conformer was observed adsorbed to the interface, indicating that the resulting cis-conformer is not thermodynamically stable at this interface, possibly due to the competition with the coexisting trans-conformers. Therefore, two-dimensional honeycombs self-assembled from derivatives of three-fold symmetric polycyclic aromatic hydrocarbons were investigated, which may be employed as templates, providing the necessary space for conformational switching of an azobenzene moiety, and tune the current-voltage characteristics through the aromatic cores. As a first step towards this goal, the capability of the template to host single molecular guests was studied by filling the voids with individual coronene molecules.

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Synthesis and Self‐Assembly of a Rigid Exotopic Bisphenanthroline Macrocycle: Surface Patterning and a Supramolecular Nanobasket

Cited by 59 publications

References 74 publications

Dynamic covalent and supramolecular direction of the synthesis and reassembly of copper(I) complexes

Dynamic covalent and supramolecular direction of the synthesis and reassembly of copper(I) complexes

Self-assembly of discrete metallosupramolecular luminophores

Optical switching studies of an azobenzene rigidly linked to a hexa-peri-hexabenzocoronene derivative in solution and at a solid–liquid interface

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