Pentacene- and BODIPY-Containing trans-Bis(ethynyl)bis(phosphine)platinum(II) Organometallic Polymers: A DFT Point of View
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The effect of the polymer dimension and the nature of the end-group of oligomer models containing pentacence ([pen]) and BODIPY ([BOD]) alternating with the organometallic fragment trans-bis(trialkylphosphine)platinum(II) ([Pt]), i.e. ([Ar] n–[Pt] m)x with [Ar] = C≡C–[pen]–C≡C, C≡C–[BOD]–C≡C, and 1 < x < 4, on their structures and optical properties were investigated by means of DFT and TDDFT (B3LYP) calculations. For sake of reduction of computation size for the oligomers, the trialkylphosphine was set to PMe3 instead of the commonly encountered PBu3 in the experimental articles. Two specific aspects were addressed. Firstly, a series of computations were performed in a systematic manner in order to find the best conditions for these calculations (namely the choice of basis sets and solvent fields), due to the large size of the oligomer models. Secondly, the effect of the oligomer size and nature of the terminal unit of ([Ar] n–[Pt] m)x, namely C≡C–[pen]–C≡CH or C≡C–[BOD]–C≡CH and [Pt]–Cl, on the structure and electronic properties have also been examined. These calculations indicate that the nature of end-groups has a little impact on the properties mentioned above for the alternating ((C≡C–[BOD]–C≡C) n–[Pt] m)x oligomers, but some minor effects are noted for the (C≡C–[pen]–C≡C)-containing species. Noteworthy, the evolution of the properties, notably the position of the lowest energy electronic transition, shows no significant evolution above 3 units. This computational result indicates the limitation of the electronic communication across the polymer chains. The lowest energy electronic states are all mainly ππ* located in the [Ar] fragment. Consequently, this work was limited to 4 units only.
KeywordsOrganometallic polymer Mono-dispersed oligomer Platinum BODIPY Pentacene DFT computations
This research was supported by the Natural Sciences and Engineering Research Council of Canada (NSERC), le Fonds Québécois de la Recherche sur la Nature et les Technologies (FQRNT), the Centre d’Études des Matériaux Optiques et Photoniques de l’Université de Sherbrooke (CEMOPUS), and the Agence National de la Recherche (ANR) for a grant of a Research Chair of Excellence.
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