Stable mixed phenanthroline copper(i) complexes. Key building blocks for supramolecular coordination chemistry

Schmittel, Michael; Ganz, Andrea

doi:10.1039/a701509g

Cited by 204 publications

(146 citation 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%

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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%

“…Contrary to expectation, complexes 1b and 1c provided no evidence of reacting with 3 by NMR or ESI-MS. In the absence of steric programming, copper(I) bis-imine complexes generally give statistical mixtures of homoleptic and heteroleptic complexes (52); the rationale behind this lack of reactivity is currently unknown.…”

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 organic layer was separated and the residue twice extracted with 50 ml of chloroform. The combined organic layers were washed with 100 ml of concentrated KOH solution and then dried over MgSO 4 (10): To a solution of 6e (1.00 g, 1.95 mmol), phenylacetylene (0.67 ml, 6.12 mmol), and 10 ml of dry triethylamine in benzene (20 ml) a mixture of PdCl 2 (PPh 3 ) 2 (0.15 g) and CuI (0.30 g) was added. After refluxing the mixture for three days under nitrogen the solvent was evaporated.…”

Section: General Procedures For the Preparation Of 12-bis(β-ethoxycarmentioning

confidence: 99%

“…Herefore, rigid and planar oligophenanthrolines would be most interesting. [10] [11] Our first approach to the macrocyclic oligophenanthrolines A [11] commenced from 4,7-dichloro-and 4,7-dibromophenanthroline.…”

Section: Introductionmentioning

confidence: 99%

A Short Synthetic Route to 4,7‐Dihalogenated 1,10‐Phenanthrolines with Additional Groups in 3,8‐Position: Soluble Precursors for Macrocyclic Oligophenanthrolines

Schmittel

Ammon

1998

European J Organic Chem

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A short and efficient preparation of 3,8‐dialkylated or 3,8‐diarylated 1,10‐phenanthrolines‐4,7‐diones is described. Their chlorination or bromination furnishes the corresponding, highly soluble 4,7‐dichloro‐ or 4,7‐dibromo phenanthrolines that constitute versatile precursors to macrocyclic oligophenanthrolines with exo‐coordination sites. They can be further reacted by nucleophilic aromatic substitution or Heck‐coupling reactions.

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“…However, the lability is one of the serious drawbacks for the Cu(I)-based complexes [14,21]. To overcome this problem, Schmittle and colleagues employed the "HETPHEN" design strategy (where HETPHEN stands for HETeroleptic PHENanthroline Cu(I) complexes) by grafting bulky substituents at the 2 and 9 positions of the phenanthroline skeleton [22,23]. According to this conception, a great many original and versatile molecular structures of the heteroleptic Cu(I) complexes [24] were developed, in which one diimine ligand served as electron acceptor and the other as electron donor to provide sustainable photo-induced electron transfer [14,23e25].…”

Section: Introductionmentioning

confidence: 99%

Heteroleptic Cu(I) complexes integrating functionalized chromophores for dye-sensitized solar cells: An in-depth analysis of electronic structure, spectrum, excitation, and intramolecular electron transfer

Wei

Shao

Shi

et al. 2016

Organic Electronics

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Stable mixed phenanthroline copper(i) complexes. Key building blocks for supramolecular coordination chemistry

Cited by 204 publications

References 19 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

A Short Synthetic Route to 4,7‐Dihalogenated 1,10‐Phenanthrolines with Additional Groups in 3,8‐Position: Soluble Precursors for Macrocyclic Oligophenanthrolines

Heteroleptic Cu(I) complexes integrating functionalized chromophores for dye-sensitized solar cells: An in-depth analysis of electronic structure, spectrum, excitation, and intramolecular electron transfer

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