Figure 1. Structures of some metallodrugs which interact with DNA via coordination, groove binding, intercalation, insertion, or dual function binding (coordination and intercalation).
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Figure 2. X‐ray structure showing threading intercalation of 9‐amino‐6‐bromo‐DACA (space‐filling model) into the DNA duplex 5′‐d(C|G(5‐BrU)AC|G) 2‐3′ (wireframe), where | indicates intercalation [ 17].
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Figure 3. Schematic representation adducts known to form on DNA upon treatment with cisplatin.
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Figure 4. (a) Average solution structure of the dodecamer DNA duplex d(CCTCAGGCCTCC)·d(GGAGTCCGGAGG) platinated by cisplatin (kinked by 60°) and (b) the native DNA duplex with AGGC sequence. The platinum atom in the cisplatin–DNA adduct is shown as a sphere [ 31]. (c–d) Chemical shift differences for  NMR resonances of platinated and unplatinated DNA duplexes (d(ATACATG*G*TACATA)·(TATGTACCATGTAT), III* or III, respectively). Chemical shift differences, Δδ, measured as (δ III * − δ III) for (c) aromatic and (d) H1′ resonances. Shift changes are indicated for the platinated GG strand (▪) and for the complementary CC strand (▿) [ 28].
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Figure 5. Schematic drawings of the L1 and R2 rotamers of [Pt(R‐tmen){d(GpG)}] + and [Pt(S‐tmen){d(GpG)}] + [ 30].
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Figure 6. (a) Molecular structure of [Ru(bpy) 2(pqx)] 3+. (b) A molecular model showing the binding of Λ‐[Ru(bpy) 2(pqx)] 2+ to d(CGCGAATTCGCG) 2 in the major groove [ 44]. (c) Selected NOEs between [{Pt(dien)} 2µ‐H 2N‐(CH 2) 6‐NH 2] 4+ and a single strand of the dodecanucleotide d(CGCGAATTCGCG) 2 (dotted lines), indicative of minor groove binding [ 46].
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Figure 7. (a) Molecular structure of [Pt(terpy)(HET)] +. (b) Molecular structure of [Rh(bpy) 2chrysi] 3+. (c) Crystal structure of [Pt(terpy)(HET)] + d(CpG) 2 showing the intercalation of HET between two GC base pairs [ 47]. (d) Structural model for insertion binding of the Rh complex at the mismatched site in the 9mer duplex (5′‐CGGACTCCG‐3′) 2 based upon an NMR study, viewed from the major groove [ 50]. (e) Molecular structure of Δ‐α‐[Rh(R, R‐Me 2trien)Phi] 3+. (f) Crystal structure of Δ‐α‐[Rh(R, R‐Me 2trien)Phi] 3+ bound to 5′‐d(GTTGCAAC) 2‐3′ duplex DNA [ 49].
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Figure 8. (a) Structures of ACRAMTU, (b) Pt‐ACRAMTU, and (c) adduct of DNA duplex 5′‐CCTCG*TCC‐3′/3′‐GGAGCAGG‐5′, with Pt‐ACRAMTU (right, the acridine chromophore is depicted in space‐filling form) [ 16].
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Figure 9. Molecular models of two conformers of duplex d(ATACATGGTACATA)·(TATGTACCATGTAT) ruthenated at N7 of G18 with {(η 6‐bip)Ru(en)} 2+. In (a) the biphenyl arene is intercalated and in (b) stacked on T17 as a flipped‐out base. The bip is in green [ 14].
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Figure 10. Molecular models of the DNA hexamer duplex d(CGGCCG) 2 ruthenated at N7 of G3 (a–c) or N7 of G6 (d–f) with {(η 6‐tha)Ru(en)} 2+, showing a novel penetrative intercalation [ 64]. The tetrahydroanthracene ligand tha is in green.
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Figure 11. Two‐dimensional  – HSQC NMR spectra of the duplex d(CGGCCG) 2 (II) (bottom), and a 1 : 1 equilibrium mixture of duplex II and Ru‐tha (top) in 90% H 2O/10% D 2O, showing the  (−1.2 to −0.70 ppm) to sugar ring H3′ and H4′ (5.2–4.1 ppm) connectivities. Significant changes are observed for  , H3′, and H4′ resonances of bases G3, C4, C5, and G6, minor changes are observed for the corresponding resonances of bases C1/C7 and G2/G8 [ 64].
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