Highly Efficient Deep‐Blue Emitters Based on cis and trans N‐Heterocyclic Carbene Pt^II Acetylide Complexes: Synthesis, Photophysical Properties, and Mechanistic Studies

Abstract

We have synthesized cis and trans N-heterocyclic carbene (NHC) platinum(II) complexes bearing σ-alkynyl ancillary ligands, namely [Pt(dbim)2 (CCR)2 ] [DBIM=N,N'-didodecylbenzimidazoline-2-ylidene; R=C6 H4 F (4), C6 H5 (5), C6 H2 (OMe)3 (6), C4 H3 S (7), and C6 H4 CCC6 H5 (8)] and [Pt(ibim)2 (CCC6 H5 )2 ] (9) (ibim=N,N'-diisopropylbenzimidazoline-2-ylidene), starting from [Pt(cod)(CCR)2 ] (COD=cyclooctadiene) and 2 equivalents 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 (CCC6 H5 )2 ] and revealed the isomerization to progress smoothly in good yield when 5 a was treated with catalytic amounts of [Pt(cod)(C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 Pt(II) dialkyne complex in the former case and a Pt(0) 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 77 K. 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 (10 wt % in poly(methyl methacrylate), PMMA) exhibits a high phosphorescence quantum yield of 80 %, which is the highest reported for Pt(II) -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 ((3) IL) charge transfer.

Influence of a Naphthaldiimide Substituent at the Diimine Ligand on the Photophysics and Reverse Saturable Absorption of PtII Diimine Complexes and Cationic IrIII Complexes

“…promising candidates for applications in organic light-emitting devices (OLEDs), [3][4][5][6] low-power upconversion, [7][8][9] luminescent bioimaging, [10][11][12][13] nonlinear optical devices, [14][15][16][17][18][19][20][21][22][23][24][25][26][27][28][29] etc. In addition, the chemical structures of Pt II and Ir III complexes are readily modified to tune the photophysical properties in order to tailor the specific requirements for each application.…”

Photophysical Enhancement of Triplet Emitters by Coordination‐Driven Self‐Assembly

“…[25] As shown in Figure 2, the square planar Pt II centers enable idealized 1808 and 908 angularity,d efined by the terminal pyridyl groups of D1' and the PtÀNb onds in 2.T he angle defined by C(1)-Pt(1)-C(1)' in D1 deviates slightly from linearity at 179.2(1)8.The N(1)-Pt(1)-N(2)a ngle in 2 is 91.1(4)8. The crystallographic detailsa re summarized in Ta ble S4 in the Supporting Information.…”

“…Compound D1-Me exhibits one low-energy absorptionb and centered at 372 nm. [25] Compound D1-Me exhibits phosphores-cence at 515 nm assigned as 3 ILCT(p * CC-py-Me !p CC-py-Me ). This collection of absorption bands is assigned to 1 ILCT(p CC-py-Me !p * CC-py-Me )a nd 1 LLCT(p carb !p * CC-py-Me )a nd 1 MLCT(Pt 5d !p * CC-py-Me )( Figure S26).…”

“…The Pt-carbene distances span from 2.020(3) to 2.029(2) in 1 and D1',w hich are similart oa nalogous compounds. [25] As shown in Figure 2, the square planar Pt II centers enable idealized 1808 and 908 angularity,d efined by the terminal pyridyl groups of D1' and the PtÀNb onds in 2.T he angle defined by C(1)-Pt(1)-C(1)' in D1 deviates slightly from linearity at 179.2(1)8.The N(1)-Pt(1)-N(2)a ngle in 2 is 91.1(4)8.…”

“…Thise mission can be assigned to am ixture of 3 ILCT(p * CC-py !p CC-py )a nd MLCT,s imilar to that of Pt phenylacetylides. [25] Compound D1-Me exhibits phosphores-cence at 515 nm assigned as 3 ILCT(p * CC-py-Me !p CC-py-Me ). M1 exhibited as imilar emission spectrum to D1-Me at 510 nm.…”