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Issue 14, 2017
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Phosphorescent platinum(II) alkynyls end-capped with benzothiazole units

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Abstract

Symmetric trans-bis(alkynyl)bis(phosphine) PtII complexes based on the 2-phenylbenzothiazole (pbt) unit [trans-Pt(C[triple bond, length as m-dash]C-pbt)2L2] [L = PPh31, PEt32, 1,3,5-triaza-7-phosphaadamantane (PTA) 3] and the mixed alkynyl–cyanide anionic complex (NBu4)2[trans-Pt(C[triple bond, length as m-dash]C-pbt)2(CN)2] (4) were synthesized. The complexes have been fully characterized including X-ray crystallography for 2 and 4. All complexes display long-lived emission with moderate quantum yields (ϕ 6.8–22.6%) in doped PMMA films at 298 K and complex 4 is also emissive in DMSO fluid and in rigid media (solid, glass at 77 K). Complex 4 displays a negative solvatochromic behavior. Absorption and emission energies have been analyzed by means of linear solvation energy based on Kamlet–Taft solvatochromism parameters and the Gutmann's acceptor numbers. The study indicates that solvatochromism is due to the contribution of solvent-to-cyanide hydrogen bonding and increased solvent dipolarity–polarizability. TD and TD-DFT calculations were performed on the ground and excited states of two different conformers of 2 and 4 to provide insight into the structural, electronic and optical properties of these systems.

Graphical abstract: Phosphorescent platinum(ii) alkynyls end-capped with benzothiazole units

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Publication details

The article was received on 04 Jan 2017, accepted on 13 Mar 2017 and first published on 13 Mar 2017


Article type: Paper
DOI: 10.1039/C7DT00029D
Citation: Dalton Trans., 2017,46, 4628-4641
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    Phosphorescent platinum(II) alkynyls end-capped with benzothiazole units

    R. Lara, E. Lalinde and M. T. Moreno, Dalton Trans., 2017, 46, 4628
    DOI: 10.1039/C7DT00029D

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