Abstract
To understand how the PtII ion perturbs the electronic structures of tetracene, 10 dinuclear [X(Et3P)2PtII]2-5,12-diethynyltetracene complexes with different auxiliary ligands were synthesized. Interactions between the PtII ion and 5,12-diethynyltetracene were probed spectroscopically and computationally. The dinuclear [X(Et3P)2PtII]2-5,12-diethynyltetracene complexes exhibit red-shifted absorption and fluorescence in comparison with those of 5,12-bis(triisopropylsilylethynyl)tetracene, with the neutral complexes with π-donating auxiliary ligands showing a larger red shift than the cationic complexes with π-accepting ligands. Electronic structures of the complexes and effects of the metal ions and the ligands on the electronic transitions of the complexes were investigated by TD-DFT calculations, the results of which showed that the electronic structure of the 5,12-diethynyltetracene core is perturbed by π interactions with the Pt fragments, the extent of which depends on the energies of the dπ orbitals of the Pt fragments.
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