Highly efficient deep-blue emitters based on cis and trans N-heterocyclic carbene Pt-II acetylide complexes

Synthesis, photophysical properties, and mechanistic studies

Yuzhen Zhang, Olivier Blacque, Koushik Venkatesan*

*Corresponding author for this work

Research output: Contribution to journalArticle

26 Citations (Scopus)

Abstract

We have synthesized cis and trans N-heterocyclic carbene (NHC) platinum(II) complexes bearing σ-alkynyl ancillary ligands, namely [Pt(dbim) 2(Cï£CR)2] [DBIM=N,N′- didodecylbenzimidazoline-2-ylidene; R=C6H4F (4), C 6H5 (5), C6H2(OMe)3 (6), C4H3S (7), and C6H4Cï£ CC6H5 (8)] and [Pt(ibim)2(Cï£CC 6H5)2] (9) (ibim=N,N′- diisopropylbenzimidazoline-2-ylidene), starting from [Pt(cod)(Cï£CR) 2] (COD=cyclooctadiene) and 2equivalents of [dbimH]Br ([ibimH]Br for complexes 9) in the presence of tBuOK and THF. Mechanistic investigations aimed at uncovering the cis to trans isomerization reaction have been performed on the representative cis complex 5 a [Pt(dbim)2(Cï£CC 6H5)2] and revealed the isomerization to progress smoothly in good yield when 5 a was treated with catalytic amounts of [Pt(cod)(Cï£CR)2] at 75 °C in THF or when 5 a was heated at 200 °C in the solid state under an inert atmosphere. Detailed examination of the reactions points to the possible involvement, in a catalytic fashion, of a solvent-stabilized PtII dialkyne complex in the former case and a Pt0 NHC complex in the latter case, for the transformation of the cis isomer to the corresponding trans complex. Thermal stability and the isomerization process in the solid state have been further investigated on the basis of TGA and DSC measurements. X-ray diffraction studies have been carried out to confirm the solid-state structures of 4 b, 5 a, 5 b, and 9 b. All of the synthesized dialkyne complexes 4-9 exhibit phosphorescence in solution, in the solid state at room temperature (RT), and also in frozen solvent glasses at 77K. The emission wavelengths and quantum yields have been found to be highly tunable as a function of the alkynyl ligand. In particular, the trans isomer of complex 9 in a spin-coated film (10wt % in poly(methyl methacrylate), PMMA) exhibits a high phosphorescence quantum yield of 80 %, which is the highest reported for PtII-based deep-blue emitters. Experimental observations and time-dependent density functional theory (TD-DFT) calculations are strongly indicative of the emission being mainly governed by metal-perturbed interligand (3IL) charge transfer. Deep-blue emitters: Triplet emitters based on cis and trans N-heterocyclic carbene platinum(II) complexes have been synthesized and characterized (see scheme). The structural features of the complexes offer highly tunable emission properties. A deep-blue emitter with a quantum yield of 80 % has been achieved.

Original languageEnglish
Pages (from-to)15689-15701
Number of pages13
JournalChemistry - A European Journal
Volume19
Issue number46
DOIs
Publication statusPublished - 11 Nov 2013
Externally publishedYes

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Keywords

  • acetylides
  • isomerization
  • N-heterocyclic carbenes
  • OLEDs
  • phosphorescence
  • platinum

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