Messages in Molecules: Ligand/Cation Coding and Self‐Recognition in a Constitutionally Dynamic System of Heterometallic Double Helicates

Marquis, Annie; Smith, Virginia C. M.; Harrowfield, Jack; Lehn, Jean‐Maríe; Herschbach, Haiko; Sanvito, Rossella; Leize‐Wagner, Emmanuelle; Dorsselaer, Alain Van

doi:10.1002/chem.200600143

Cited by 76 publications

(44 citation statements)

References 57 publications

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“…[13,14] Metals are in many respects the carriers of functions particularly desired in the nanoworld. [1,15] Nanoscopic metal wires may allow conducting electrons through self-assembled networks. Magnetic coupling of the metal ions may create nanomagnets with defined orientation and strength of the magnetic fields.…”

Section: Introductionmentioning

confidence: 99%

DNA–Metal Base Pairs

2007

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Recent developments show encouraging results for the use of DNA as a construction material for nanometer-sized objects. Today, however, DNA-based molecular nanoarchitectures are constructed with mainly unmodified or at best end-modified oligonucleotides, thus shifting the development of functionalized DNA structures into the limelight. One of most recent developments in this direction is the substitution of the canonical Watson-Crick base pairs by metal complexes. In this way "metal-base pairs" are created, which could potentially impart magnetic or conductive properties to DNA-based nanostructures. This review summarizes research which started almost 45 years ago with the investigation of how metal ions interact with unmodified DNA and which recently culminated in the development of artificial ligand-like nucleobases so far able to coordinate up to ten metal ions inside a single DNA duplex in a programmable fashion.

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Section: Introductionmentioning

confidence: 99%

DNA–Metal Base Pairs

2007

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“…The selective insertion of tpy and dpp at the 5' and 3' termini of complementary DNA strands a and b, followed by hybridization, resulted in the formation of three DNA-templated coordination spheres: tpy 2 :ab, tpy:dpp:ab, and dpp 2 :ab (Figure 1 a). In contrast to metal-driven supramolecular coordination, [9,10] the programmed self-assembly of duplex DNA can template the formation of any combination of ligands, whether homoleptic or mixed, in close proximity.We studied the thermal stability of DNA duplexes tpy 2 :ab and their metal complexes (Figure 2 a). For these duplexes, even without the addition of a metal, the melting temperature increased from 43 8C for the unmodified DNA to 66 8C for tpy 2 :ab.…”

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confidence: 99%

Templated Ligand Environments for the Selective Incorporation of Different Metals into DNA

et al. 2009

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DNA has emerged as a unique template for the construction and organization of nanostructures and arrays with precisely controlled features.[1] The incorporation of transition metals into DNA has enabled the transfer of functionality, in the form of enhanced stability, redox activity, photoactivity, and magnetic and catalytic properties, to this otherwise passive biomolecular template. [2][3][4][5] A particularly attractive goal would be the selective incorporation of different transition metals into DNA. This allows the use of the programmable character of DNA to organize transition metals into arbitrarily designed symmetric or asymmetric structures, resulting in a number of applications in artificial photosynthesis, multimetallic catalysis, nanooptics, nanoelectronics, and data storage.[3] It would also result in the expansion of the DNA "alphabet" to new metal "letters" that would increase the information content of this biomolecule and reduce errors in its assembly into nanostructures.For this goal to reached, different DNA-ligand environments must be designed in a manner that maximizes metalbinding selectivity, promotes close interaction between the metal complex and the DNA duplex, and offers coordination programmability. The incorporation of metals into DNA constructs has been demonstrated through replacement of the hydrogen-bonded DNA base pairs with metal complexes within the interior of the DNA duplex. [2, 3] The extension of this strategy to different ligand environments is, however, limited by the steric and spatial requirements of the DNA duplex, and has been successful for planar metal centers that fit in the DNA interior. Metal complexes have been appended as nucleobase and (deoxy)ribose modifications; however, this method is generally limited to a small subset of kinetically inert and unreactive metal complexes that resist the harsh conditions of automated DNA synthesis. [4] A third approach developed by our research group is to insert ligands into the phosphodiester backbone, such that the hybridization of DNA with its complementary strand templates the assembly of a metal-coordination environment in close contact with the DNA base stack.[5] We report herein the site-specific incorporation of terpyridine (tpy) and diphenylphenanthroline (dpp) ligands into DNA strands.[6] The DNAtemplated creation of three ligand environments resulted: tpy 2 :DNA, tpy:dpp:DNA, and dpp 2 :DNA. These ligand environments are highly selective for six-, five-, and fourcoordinate metal ions, respectively (Figure 1 a) II when placed in the tpy:dpp:DNA structure. Finally, the addition of Fe II to the tpy:dpp:DNA structure resulted in reorganization of the ligand environment, such that two of these constructs were brought together with Fe II binding to their terpyridine units. In a similar manner to the ligand pockets of metalloenzymes, [7] this new class of DNAtemplated coordination environments defines a toolbox for the selective positioning of different transition metals at exact locations within DNA nanostructures.Det...

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“…[11] One of the important attributes of artificial helical systems is the enormous variety of chemical structures that can be incorporated within the ligands and the subtlety of the interplay between metal-ion coordination preferences and the donor-atom array of the ligand. [4][5][6][7]12] In general, the use of homotopic N-donor ligands and metal ions in self-assembly processes has attracted much attention for the design and synthesis of novel functional materials; [13][14][15] one report of particular promise is that of the development of transistors incorporating complexes containing Co II bonded to polypyridine ligands. [16] There is, of course, very esterification, gives ligand L2, which also forms a dinuclear Cu I helicate and a mononuclear Co II complex; one of the ester groups appears to be involved in complexation in the latter.…”

Section: Introductionmentioning

confidence: 99%

Quaterpyridine Ligands Forming Helical Complexes of Mono‐ and Dinuclear (Helicate) Forms

et al. 2008

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The dimethylquaterpyridine ligand L1 reacts with Cu I and Ag I to give dinuclear complexes of "helicate" form, in which the metals are in an approximate tetrahedral coordination, whereas reactions with Co II and Zn II provide mononuclear complexes, in which the metals are apparently six-coordinate with markedly distorted octahedral coordination, and the ligand retains a helical conformation. Oxidation of the methyl substituents of L1 into carboxylic acid groups, followed by

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Messages in Molecules: Ligand/Cation Coding and Self‐Recognition in a Constitutionally Dynamic System of Heterometallic Double Helicates

Cited by 76 publications

References 57 publications

DNA–Metal Base Pairs

DNA–Metal Base Pairs

Templated Ligand Environments for the Selective Incorporation of Different Metals into DNA

Quaterpyridine Ligands Forming Helical Complexes of Mono‐ and Dinuclear (Helicate) Forms

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