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Amide Coupling Reaction for the Synthesis of Bispyridine-based Ligands and Their Complexation to Platinum as Dinuclear Anticancer Agents
Published on: May 28, 2014
Synthesis and spectroscopic properties of platinum(II) terpyridine complexes having an arylborane charge transfer
Eri Sakuda1, Akiko Funahashi, Noboru Kitamura
1Division of Chemistry, Graduate School of Science, Hokkaido University, Sapporo 060-0810, Japan.
Abstract:
Synthesis, redox, spectroscopic, and photophysical properties of a new class of Pt(II) complexes of the type [PtLnCl]+ are reported, where Ln is 4'-phenyl(dimesitylboryl)-2,2':6',2"-terpyridine (L1) or 4'-duryl(dimesitylboryl)-2,2':6',2"-terpyridine (L2). The free L1 or L2 ligand in CH3CN shows the absorption band responsible for intramolecular charge transfer (CT) from the pi-orbital of the aryl group in L1 or L2 (pi(aryl)) to the vacant p-orbital on the boron atom (p(B)), in addition to pipi* absorption in the 2,2':6',2"-terpyridine (tpy) unit. In particular, the L1 ligand shows an intense CT absorption band as compared with L2. Such intramolecular pi(aryl)-p(B) CT interactions in L1 give rise to large influences on the redox, spectroscopic, and photophysical properties of [PtL1Cl]+. In practice, [PtL1Cl]+ shows strong room-temperature emission in CHCl3 with the quantum yield and lifetime of 0.011 and 0.6 micros, respectively, which has been explained by synergetic effects of Pt(II)-to-L1 MLCT and pi(aryl)-p(B) CT interactions on the electronic structures of the complex. In the case of [PtL2Cl]+, the dihedral angle between the planes produced by the tpy and duryl(dimesitylborane) groups is very large (84 degrees ) as compared with that between the tpy and phenyl(dimesitylborane) units in [PtL1Cl]+ (26-39 degrees ), which disturbs electron communication between the Pt(II)-tpy and arylborane units in [PtL2Cl]+. Thus, [PtL2Cl]+ is nonemissive at room temperature. The important roles of the synergetic CT interactions in the excited-state properties of the [PtL1Cl]+ complex are shown clearly by emission quenching of the complex by a fluoride ion. The X-ray crystal structure of [PtL1Cl]+ is also reported.
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