Amlan K. Pal

Discrete Covalent Organic–Inorganic Hybrids: Terpyridine Functionalized Polyoxometalates Obtained by a Modular Strategy and Their Metal Complexation

The rational design and synthesis of organic-inorganic hybrids as functional molecular materials relies on both the careful conception of building-blocks and the strategy for their assembly. Three families of trialkoxo polyoxometalates (Lindqvist 2, Anderson 3, Dawson 4) grafted with remote terpyridine coordination sites have been synthesized to extend the available building-blocks. These new units can be combined with metal complexes that play a role as (i) chromophores toward charge-separated systems in light-harvesting devices and (ii) coordination motifs for metal-directed self-assembly toward multifunctional molecular hybrid materials. The X-ray crystal structures of polyoxometalate-terpyridine hybrids indicate distances of 21 Å and 19 Å between the two terpyridyl coordination sites in 2 and 3, respectively, with angles between the coordination vectors of 180° and 177.4°, respectively. Lindqvist 2 displays a reduction at -0.52 V vs SCE while Anderson 3 exhibits one reversible oxidation attributed to Mn(III)/Mn(IV) (+0.75 V vs SCE) and a broad wave at -1.28 V vs SCE assigned to the Mn(III)/Mn(II) reduction. Dawson 4 displays several processes on a wide range of potentials (+0.5 to -2.0 V vs SCE) centered on V(V), W(VI) and the organic ligand in order of decreasing potentials. The grafted terpyridine ligands in Anderson 3 and Dawson 4 were successfully coordinated to {PdCl}(+) and {RuCl(3)} moieties, respectively. The polyoxometalates and transition metal complexes retain their intrinsic properties in the final assemblies.

Synthesis, Properties, and Light-Emitting Electrochemical Cell (LEEC) Device Fabrication of Cationic Ir(III) Complexes Bearing Electron-Withdrawing Groups on the Cyclometallating Ligands

The structure–property relationship study of a series of cationic Ir(III) complexes in the form of [Ir(C^N)2(dtBubpy)]PF6 [where dtBubpy = 4,4′-di-tert-butyl-2,2′-bipyridine and C^N = cyclometallating ligand bearing an electron-withdrawing group (EWG) at C4 of the phenyl substituent, i.e., −CF3 (1), −OCF3 (2), −SCF3 (3), −SO2CF3 (4)] has been investigated. The physical and optoelectronic properties of the four complexes were comprehensively characterized, including by X-ray diffraction analysis. All the complexes exhibit quasireversible dtBubpy-based reductions from −1.29 to −1.34 V (vs SCE). The oxidation processes are likewise quasireversible (metal + C^N ligand) and are between 1.54 and 1.72 V (vs SCE). The relative oxidation potentials follow a general trend associated with the Hammett parameter (σ) of the EWGs. Surprisingly, complex 4 bearing the strongest EWG does not adhere to the expected Hammett behavior and was found to exhibit red-shifted absorption and emission maxima. Nevertheless, the concept of introducing EWGs was found to be generally useful in blue-shifting the emission maxima of the complexes (λem = 484–545 nm) compared to that of the prototype complex [Ir(ppy)2(dtBubpy)]PF6 (where ppy = 2-phenylpyridinato) (λem = 591 nm). The complexes were found to be bright emitters in solution at room temperature (ΦPL = 45–66%) with microsecond excited-state lifetimes (τe = 1.14–4.28 μs). The photophysical properties along with density functional theory (DFT) calculations suggest that the emission of these complexes originates from mixed contributions from ligand-centered (LC) transitions and mixed metal-to-ligand and ligand-to-ligand charge transfer (LLCT/MLCT) transitions, depending on the EWG. In complexes 1, 3, and 4 the 3LC character is prominent over the mixed 3CT character, while in complex 2, the mixed 3CT character is much more pronounced, as demonstrated by DFT calculations and the observed positive solvatochromism effect. Due to the quasireversible nature of the oxidation and reduction waves, fabrication of light-emitting electrochemical cells (LEECs) using these complexes as emitters was possible with the LEECs showing moderate efficiencies.

Controlling the emission efficiency of blue-green iridium(III) phosphorescent emitters and applications in solution-processed organic light-emitting diodes

We show that the emission efficiency of blue-green phosphorescent emitters can be controlled through coupling of the excited state to vibrational modes. We controlled this vibrational coupling through choice of different ligands and as a result, complexes with CF3-groups on the ancillary ligand were essentially non-emissive (ΦPL 50%). Emission of the complexes can be drastically improved (30 times higher ΦPL compared to degassed solution for the CF3-containing complexes) by blending them with an inert solid host such as PMMA, which mitigates metal-ligand vibrations. Solution-processed organic light-emitting diodes made from these materials showed efficiency as high as 6.3%.

Blue-to-Green Emitting Neutral Ir(III) Complexes Bearing Pentafluorosulfanyl Groups: A Combined Experimental and Theoretical Study

A structure–property relationship study of neutral heteroleptic (1 and 2, [Ir(C∧N)2(L∧X)]) and homoleptic (3 and 4, fac-[Ir(C∧N)3]) Ir(III) complexes (where L∧X = anionic 2,2,6,6-tetramethylheptane-3,5-dionato-κO3,κO6 (thd) and C∧N = a cyclometalating ligand bearing a pentafluorosulfanyl (−SF5) electron-withdrawing group (EWG) at the C4 (HL1) and C3 (HL2) positions of the phenyl moiety) is presented. These complexes have been fully structurally characterized, including by single-crystal X-ray diffraction, and their electrochemical and optical properties have also been extensively studied. While complexes 1 ([Ir(L1)2(thd)]), 3 (Ir(L1)3), and 4 (Ir(L2)3) exhibit irreversible first reduction waves based on the pentafluorosulfanyl substituent in the range of −1.71 to −1.88 V (vs SCE), complex 2 ([Ir(L2)2(thd)]) exhibits a quasi-reversible pyridineC∧N-based first reduction wave that is anodically shifted at −1.38 V. The metal + C∧N ligand oxidation waves are all quasi-reversible in the range of 1.08–1.54 V (vs SCE). The optical gap, determined from the lowest energy absorption maxima, decreases from 4 to 2 to 3 to 1, and this trend is consistent with the Hammett behavior (σm/σp with respect to the metal–carbon bond) of the −SF5 EWG. In degassed acetonitrile, for complexes 2–4, introduction of the −SF5 group produced a blue-shifted emission (λem 484–506 nm) in comparison to reference complexes [Ir(ppy)2(acac)] (R1, where acac = acetylacetonato) (λem 528 nm in MeCN), [Ir(CF3-ppy) (acac)] (R3, where CF3-ppyH = 2-(4-(trifluoromethyl)phenyl)pyridine) (λem 522 nm in DCM), and [Ir(CF3-ppy)3] (R8) (λem 507 nm in MeCN). The emission of complex 1, in contrast, was modestly red shifted (λem 534 nm). Complexes 2 and 4, where the −SF5 EWG is substituted para to the Ir–CC∧N bond, are efficient phosphorescent emitters, with high photoluminescence quantum yields (ΦPL = 58–79% in degassed MeCN solution) and microsecond emission lifetimes (τε = 1.35–3.02 μs). Theoretical and experimental observations point toward excited states that are principally ligand centered (3LC) in nature, but with a minor metal-to-ligand charge-transfer (3MLCT) transition component, as a function of the regiochemistry of the pentafluorosulfanyl group. The 3LC character is predominant over the mixed 3CT character for complexes 1, 2, and 4, while in complex 3, there is exclusive 3LC character as demonstrated by unrestricted density functional theory (DFT) calculations. The short emission lifetimes and reasonable ΦPL values in doped thin film (5 wt % in PMMA), particularly for 4, suggest that these neutral complexes would be attractive candidate emitters in organic light-emitting diodes.

Simple design to achieve red-to-near-infrared emissive cationic Ir(III) emitters and their use in light emitting electrochemical cells

Two cationic Ir(III) complexes bearing 2-phenylpyridinato cyclometalating ligands and bithiazole-type ancillary ligands have been synthesized and optoelectronically characterised. These emitters exhibit unusually deep red-to-near-infrared emission at room temperature, thereby rendering them as attractive emitters in solution-processed light emitting electrochemical cell (LEEC) electroluminescent devices.

Synthesis and characterization of green-to-yellow emissive Ir(III) complexes of pyridylbenzothiadiazine ligand

Abstract Reaction of tetrakis(2-phenylpyridinato-C2,N′)(μ-dichloro)di-iridium with 3-(pyridin-2-yl)-4H-benzo[e][1,2,4]thiadiazine (L1) under neutral and basic media afforded the charged and neutral Ir-complexes, 1 and 2, respectively, in good yields (63–79%). Single-crystal XRD analysis confirms that the ancillary ligands in both 1 and 2 bind to the iridium via coordination of N2 of the benzo[e][1,2,4]thiadiazine. Upon isolation of the neutral complex, the sulfur rapidly oxidizes to form 2. The UV–vis absorption spectra of the complexes exhibit both ligand-centered and mixed metal-to-ligand and ligand-to-ligand charge transfer transitions that are typical of many heteroleptic iridium complexes. Complexes 1 and 2 were emissive at room temperature in the green and yellow region of the electromagnetic spectrum, respectively, albeit with poor photoluminescence quantum yield (ΦPL = 1.1–2.5%).

Palladium(II)-directed self-assembly of a neutral molecular triangle as a heteroditopic receptor for ion pairs.

A molecular triangle, based on the self-assembly of 4,7-phenanthroline by a neutral palladium complex, has been synthesized and characterized by a combination of techniques: (1)H NMR and UV-vis absorption spectroscopies, mass spectrometry, elemental analysis, and gel permeation chromatography. This new neutral metallocavitand has demonstrated the capacity to host both anionic and cationic guests, thus acting as an open-shaped heteroditopic receptor. Density functional theory calculations have shown that (i) there is no overtension in the assembly of the discrete triangle, which is more stable than open-chain oligomers, (ii) the adducts formed between the triangle and some salts (modeled in the gas phase) are thermodynamically stable, and (iii) two types of cavities coexist in the triangle, which host ions and ion pairs. This easily accessible triangular unit extends further the rational design of model nanoarchitectures in host-guest chemistry with applications in analytical chemistry and multifunctional molecular materials.

Blue-emitting cationic iridium(III) complexes featuring pyridylpyrimidine ligands and their use in sky-blue electroluminescent devices

EZ-C acknowledges the University of St Andrews for financial support. EZ-C and AKP thank EPSRC (EP/M02105X/1) for funding. The authors would like to thank the Engineering and Physical Sciences Research Council for financial support for Adam Henwood: EPSRC DTG Grants: EP/J500549/1; EP/K503162/1; EP/L505097/1 and the European Research Council (HetIridium, CIG-322280). The Valencian team acknowledges the financial support from the Spanish Ministry of Economy and Competitiveness (MINECO) via the Unidad de Excelencia Mara de Maeztu MDM-2015-0538 and MAT2014-55200, PCIN-2015-255 and the Generalitat Valenciana (Prome-teo/2016/135). C. M. thanks MINECO for her predoctoral contract.

Synthesis, Characterization, and Optoelectronic Properties of Iridium Complexes Bearing Nonconjugated Six-Membered Chelating Ligands

We report the synthesis, characterization, and optoelectronic properties of a series of four new luminescent iridium(III) complexes, 1-4, of the form [Ir(C∧N)2(N∧N)]PF6 (where C∧N is the nonconjugated benzylpyridinato (bnpy) and N∧N is a neutral diimine ancillary ligand) with the goal of investigating the effect of the methylene spacer between the coordination moieties of the C∧N ligand on the optoelectronic properties of the complexes. The crystal structures of 1-3 illustrate two possible orientations of the methylene unit of the bnpy ligand. The formation of these two separate conformers is a result of the conformational flexibility of the bnpy ligand. In complexes 3 and 4, mixtures of the two conformers were observed by 1H NMR spectroscopy in CDCl3 at room temperature, whereas only a single conformer is detected for 1 and 2. Detailed DFT calculations corroborate NMR experiments, accounting for the presence and relative populations of the two conformers. The optoelectronic properties of all four complexes, rationalized by the theoretical study, demonstrate that the interruption of conjugation in the C∧N ligands results in a reduced electrochemical gap but similar triplet state energies and lower photoluminescence quantum yields in comparison to the reference complexes R1-R4. Depending on the nature of the N∧N ligand, we observe (1) marked variations of the ratio of the conformers at ambient temperature and (2) phosphorescence ranging from yellow to red.

Blue‐Emissive Cobalt(III) Complexes and Their Use in the Photocatalytic Trifluoromethylation of Polycyclic Aromatic Hydrocarbons

Room-temperature luminescent CoIII complexes (1 and 2) are presented that exhibit intense ligand-to-metal and ligand-to-ligand charge transfer absorption in the low-energy UV region (λabs ≈360-400 nm) and low-negative quasi-reversible reduction events (E1/2(red) =-0.58 V and -0.39 V vs. SCE for 1 and 2, respectively). The blue emission of 1 and 2 at RT is due to the large bite angles and strong σ-donation of the ligands, the combined effect of which helps to separate the emissive 3 LMCT (triplet ligand-to-metal charge transfer) and the non-emissive 3 MC (triplet metal-centered) states. 1 and 2 were found to be powerful photo-oxidants (ECoIII*/CoII =2.26 V and 2.75 V vs. SCE of 1 and 2, respectively) and were used as inexpensive photoredox catalysts for the regioselective mono(trifluoromethylation) of polycyclic aromatic hydrocarbons (PAHs) in good yields (ca. 40-58 %).