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A new cyclometalated Ir(III) complex [Ir(ppy)2(hdppz)]PF6 (Hppy = 2‐phenylpyridine and hdppz = 6‐hydroxydipyrido[3,2‐a:2′,3′‐c]phenazine) was synthesized and characterized. The pH effects on the UV–vis absorption spectra were studied and ground‐state acid ionization constant pKa values of the complex were derived. The calf thymus DNA (ct‐DNA) binding properties of the complex were investigated with UV‐vis absorption spectrophotometric titrations, DNA competitive binding with ethidium bromide, DNA melting experiments, viscosity measurements and density functional theory (DFT) calculations. The complex was demonstrated to act as a ct‐DNA intercalator with a large DNA binding constant value of (6.06 ± 0.32) × 106M−1 in 50 mM NaCl. The avid DNA binding affinity observed was rationalized by the DFT calculations. Copyright © 2011 John Wiley & Sons, Ltd.
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