TY - JOUR
T1 - Highly efficient deep-blue emitters based on cis and trans N-heterocyclic carbene Pt-II acetylide complexes
T2 - Synthesis, photophysical properties, and mechanistic studies
AU - Zhang, Yuzhen
AU - Blacque, Olivier
AU - Venkatesan, Koushik
PY - 2013/11/11
Y1 - 2013/11/11
N2 - 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.
AB - 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.
KW - acetylides
KW - isomerization
KW - N-heterocyclic carbenes
KW - OLEDs
KW - phosphorescence
KW - platinum
UR - http://www.scopus.com/inward/record.url?scp=84887025557&partnerID=8YFLogxK
U2 - 10.1002/chem.201302196
DO - 10.1002/chem.201302196
M3 - Article
C2 - 24108420
AN - SCOPUS:84887025557
SN - 0947-6539
VL - 19
SP - 15689
EP - 15701
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
IS - 46
ER -