Tuning the color and phosphorescent properties of iridium(III) complexes with phosphine-silanolate ancillary ligand: A theoretical investigation

Zhang, Qing; Wang, Li; Wang, Xin; Li, Yonghong; Zhang, Jinglai

doi:10.1016/j.orgel.2015.10.021

Cited by 12 publications

(4 citation statements)

References 38 publications

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“…[53] In these P^SiO complexes, their photophysical properties and emission color seem mainly determined by the cyclometalated ligand, while the P^SiO chelates only played a secondary role in controlling the electronic properties. [54] These observations are consistent with recent theoretical analysis that both the cyclometalated and non-chromophoric ancillary chelates of the studied Ir(III) complexes have exerted profound influence on their fundamental photophysical properties. [55] Finally, tris-bidentate, heteroleptic Ir(III) complexes [Ir(C^N) 2 (CBP)] supported by the C^N chelates such as ppy, dfppy, and ocarboranyl-phosphine ligand (CBP) have been synthesized, for which CBP ancillary constituted a strong-field ligand that leads to a large blue shift of emission bands.…”

Section: Emitters Bearing Single Anionic P-based Ancillarysupporting

confidence: 91%

Emissive Iridium(III) Complexes with Phosphorous‐Containing Ancillary

Chi

Wang

Ganesan

2018

The Chemical Record

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Ir(III) metal complexes and related emitters bearing all kind of cyclometalated chromophoric chelates and non-chromophoric ancillary are extensively studied during the past three decades. Many of them have been found to display bright room temperature phosphorescence from triplet excited states in both solution and solid states, offering a possible application in contemporary optoelectronic technologies, including organic light emitting diodes, electrochemiluminescence, biological imaging and chemical sensing. Among reported materials, there are Ir(III) complexes with at least one phosphorus (P)-containing ligand and/or ancillary chelate, together with cyclometalates or equivalents that are in control of the actual emission energy. Particularly, possession of P-based donor can lead to divergent structural and photophysical properties compared to the traditional designs. This review aims to provide a literature overview as well as the authors' personal account to the development of relevant Ir(III) based phosphors bearing these P-donors. To the readers' convenience, the contents are subdivided into six sessions, according to whether or not they are charge natural, or with mono-or dianionic electronic character, and in accordance to their divergent bonding modes, i. e. monodentate, bidentate and tripodal coordination. In many cases, the P-based ancillaries offer an easy accessible route to the formation of efficient sky-blue and true-blue emitters due to their p-accepting property, together with enlarged emission energy gap and destabilized upper lying quenching state. . Emitters Bearing Monodentate P Donor Neutral Ir(III) metal complex [Ir(ppy) 2 (PBu n 3 )Cl] (5) depicted in Scheme 3, had been synthesized from treatment of dimer [Ir(ppy) 2 (m-Cl)] 2 with stoichiometric amount of P(n-Bu) 3 in CH 2 Cl 2 at RT. [8] It showed mixed 3 MLCT and pp* based emission profile with peak max. at 492 nm. Its emission is blue-shifted with respect to that of parent [Ir(ppy) 3 ], indicating the higher ligand field strength of phosphine and increased HOMO-LUMO energy gap. . His current research interests involve the design and evaluation of transition-metal based true-blue and NIR phosphors and thermally activated delay fluorescence materials for organic light emitting diodes (OLEDs). He has coauthored over 340 scientific articles with overall H-index > 61 and held over 50 patents worldwide. Scheme 1. Structural drawings of Os(II) complexes 1 and 2. Scheme 2. Structural drawings of Pt(II) complexes 3 and 4.

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Section: Emitters Bearing Single Anionic P-based Ancillarysupporting

confidence: 91%

Emissive Iridium(III) Complexes with Phosphorous‐Containing Ancillary

Chi

Wang

Ganesan

2018

The Chemical Record

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“…53−55 Despite this fact, investigations on phosphorescence at the level of modern quantum mechanics are quite limited and a detailed description of phosphorescence mechanisms has therefore remained elusive. 11…”

Section: Short Historical Backgroundmentioning

confidence: 99%

“…In great contrast, the absorption or emission involving singlet and triplet states (T n ) are strongly spin-prohibited since they proceed as second-order, or nonlinear, processes involving both spin–orbit and dipole couplings. A large body of phosphorescence measurements has been accumulated over the years, covering simple diatomic molecules and more complicated compounds like polyacenes, − porphyrins, ,, circulenes, , heavy metal complexes, − , and others. − Despite this fact, investigations on phosphorescence at the level of modern quantum mechanics are quite limited and a detailed description of phosphorescence mechanisms has therefore remained elusive …”

Section: Principles Of Computational Phosphorescencementioning

confidence: 99%

Theory and Calculation of the Phosphorescence Phenomenon

2017

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Phosphorescence is a phenomenon of delayed luminescence that corresponds to the radiative decay of the molecular triplet state. As a general property of molecules, phosphorescence represents a cornerstone problem of chemical physics due to the spin prohibition of the underlying triplet-singlet emission and because its analysis embraces a deep knowledge of electronic molecular structure. Phosphorescence is the simplest physical process which provides an example of spin-forbidden transformation with a characteristic spin selectivity and magnetic field dependence, being the model also for more complicated chemical reactions and for spin catalysis applications. The bridging of the spin prohibition in phosphorescence is commonly analyzed by perturbation theory, which considers the intensity borrowing from spin-allowed electronic transitions. In this review, we highlight the basic theoretical principles and computational aspects for the estimation of various phosphorescence parameters, like intensity, radiative rate constant, lifetime, polarization, zero-field splitting, and spin sublevel population. Qualitative aspects of the phosphorescence phenomenon are discussed in terms of concepts like structure-activity relationships, donor-acceptor interactions, vibronic activity, and the role of spin-orbit coupling under charge-transfer perturbations. We illustrate the theory and principles of computational phosphorescence by highlighting studies of classical examples like molecular nitrogen and oxygen, benzene, naphthalene and their azaderivatives, porphyrins, as well as by reviewing current research on systems like electrophosphorescent transition metal complexes, nucleobases, and amino acids. We furthermore discuss modern studies of phosphorescence that cover topics of applied relevance, like the design of novel photofunctional materials for organic light-emitting diodes (OLEDs), photovoltaic cells, chemical sensors, and bioimaging.

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“…From the viewpoint of the structure of the bis-cyclometalated iridium( iii ) complex, the emission color and efficiency of a given material strongly depend on the choice of both the cyclometalated ligand and ancillary ligand. 30–33 The rigid π-conjugation structure not only extends the emission wavelength but also efficiently reduces the rotation and vibration decay pathways. Therefore, a simple, efficient, and low-cost orange-red iridium( iii ) complex can be ingeniously constructed by the exquisite combination of an ancillary ligand with a rigid and planar structure and a commonly used cyclometalated ligand (1-phenylisoquinoline).…”

Section: Introductionmentioning

confidence: 99%