Structural Diversity in 2-(2-Aminoethyl)pyridine-Based Lead Iodide Hybrids.

While 2D metal-organic hybrids have emerged as promising solar absorbers due to their improved moisture stability, their inferior transport properties limit their potential translation into devices. We report a new hybrid containing 2-(2-ammonioethyl)pyridine [(2-AEP)+], forming a 2D hybrid with the composition (2-AEP)2PbI4. The organic bilayer comprises of (2-AEP)+, which is arranged in a face-to-face stacking that promotes π-π interactions between neighboring pyridyl rings. We also demonstrate the structural diversity of 2-(2-aminoethyl)pyridine-based lead iodide hybrids in solution-processed films. This report highlights the importance of solution-processing conditions in trying to obtain single-phase films of hybrids containing dibasic organic species.

Two-Coordinate Thermally Activated Delayed Fluorescence Coinage Metal Complexes: Molecular Design, Photophysical Characters, and Device Application.

Since the emergence of the first green light emission from a fluorescent thin-film organic light emitting diode (OLED) in the mid-1980s, a global consumer market for OLED displays has flourished over the past few decades. This growth can primarily be attributed to the development of noble metal phosphorescent emitters that facilitated remarkable gains in electrical conversion efficiency, a broadened color gamut, and vibrant image quality for OLED displays. Despite these achievements, the limited abundance of noble metals in the Earth's crust has spurred ongoing efforts to discover cost-effective electroluminescent materials. One particularly promising avenue is the exploration of thermally activated delayed fluorescence (TADF), a mechanism with the potential to fully harness excitons in OLEDs. Recently, investigations have unveiled TADF in a series of two-coordinate coinage metal (Cu, Ag, and Au) complexes. These organometallic TADF materials exhibit distinctive behavior in comparison to their organic counterparts. They offer benefits such as tunable emissive colors, short TADF emission lifetimes, high luminescent quantum yields, and reasonable stability. Impressively, both vacuum-deposited and solution-processed OLEDs incorporating these materials have achieved outstanding performance. This review encompasses various facets on two-coordinate TADF coinage metal complexes, including molecular design, photophysical characterizations, elucidation of structure-property relationships, and OLED applications.

Bis-oxazoline derivatives as ancillary ligands for bis-cyclometalated iridium complexes.

Organometallic iridium complexes with two cyclometalated ligands (CN) and one bis-oxazoline derived ancillary ligand (L^X), i.e. (CN)2Ir(L^X), are reported. The CN ligands are 1-phenylpyrazoline (ppz), 2-(4,6-difluorophenyl)pyridine (F2ppy), 2-phenylpyridine (ppy), 1-phenylisoquinoline (piq). The box ligand is (4S)-(+)-phenyl-α-[(4S)-phenyloxazolidin-2-ylidene]-2-oxazoline-2-acetonitrile. The emission of these complexes span across the visible and into the near-ultraviolet region of the electromagnetic spectrum with moderate to high photoluminescence quantum yields (ΦPL = 0.45-1.0). These complexes were found to emit from a metal-ligand to ligand charge transfer (ML'LCT) state and have lifetimes (1.3-2.1 µs), radiative rates (105 s-1), and nonradiative rates (104-105 s-1) comparable to state-of-the-art iridium emitters. The (ppy)2Ir(BOX-CN) complexes were resolved into the Δ- and Λ- diastereomers using differences in their solubility and additionally characterized by x-ray crystallography, stability, and chiroptic studies. The high ΦPL of these isomers results in the best to date brightness for circularly polarized luminescence (CPL) from iridium complexes (7.0 M-1 cm-1), with dissymmetry factors of -0.57 × 10-3 and +1.9 × 10-3 for 3Δ and 3Λ, respectively. The significant difference in CPL magnitude between 3Δ and 3Λ likely arises from interligand interactions (edge-to-face arrangement versus strong π-π interaction) for the pendant phenyl ring of the BOX-CN ligand which differ for the two isomers.

Temperature dependence of radiative and non-radiative decay in the luminescence of one-dimensional pyridinium lead halide hybrids.

The photoluminescence properties of organic-inorganic pyridinium lead bromide [(pyH)PbBr3] and iodide [(pyH)PbI3] compounds were investigated as a function of temperature. The inorganic substructure consists of face-sharing chains of PbX6 octahedra. Diffuse reflectance spectra of the compounds show low energy absorption features consistent with charge transfer transitions from the PbX3 chains to the pyridinium cations. Both compounds display extremely weak luminescence at room temperature that becomes strongly enhanced upon cooling to 77 K. Broad, featureless low energy emission (λem > 600 nm) in both compounds have large Stokes shifts [1.1 eV for (pyH)PbBr3 and 0.46 eV for (pyH)PbI3] and are assigned to transitions from self-trapped excitons on the inorganic chains whereas emission at higher energy in (pyH)PbBr3 (λem = 450 nm) is assigned to luminescence from a free exciton state. Analysis of data from temperature-dependent luminescence intensity measurements gives activation energies (Ea) for non-radiative decay of the self-trapped excitons in (pyH)PbBr3 and (pyH)PbI3, (Ea = 0.077 eV and 0.103 eV, respectively) and for the free exciton in (pyH)PbBr3 (Ea = 0.010 eV). Analysis of temperature dependent luminescence lifetime data indicates another non-radiative decay process in (pyH)PbI3 at higher temperatures (Ea = 0.17 eV). A large increase in the luminescence lifetime of (pyH)PbI3 below 80 K is consistent with thermalization between triplet sublevels. Analysis of the luminescence power dependence for (pyH)PbI3 shows superlinear response suggestive of quenching by static traps.

Luminescent Bimetallic Two-Coordinate Gold(I) Complexes Utilizing Janus Carbenes.

A series of bimetallic carbene-metal-amide (cMa) complexes have been prepared with bridging biscarbene ligands to serve as a model for the design of luminescent materials with large oscillator strengths and small energy differences between the singlet and triplet states (ΔEST). The complexes have a general structure (R2N)Au(:carbene─carbene:)Au(NR2). The bimetallic complexes show solvation-dependent absorption and emission that is analyzed in detail. It is found that the molar absorptivity of the bimetallic complexes is correlated with the energy barrier to rotation of the metal-ligand bond. The bimetallic cMa complexes also exhibit short emission lifetimes (τ = 200-300 ns) with high photoluminescence efficiencies (ΦPL > 95%). The radiative rates of bimetallic cMa complexes are 3-4 times faster than that of the corresponding monometallic complexes. Analysis of temperature-dependent luminescence data indicates that the lifetime for the singlet state (τS1) of bimetallic cMa complexes is near 12 ns with a ΔEST of 40-50 meV. The presented compounds provide a general design for cMa complexes to achieve small values for ΔEST while retaining high radiative rates. Solution-processed organic light-emitting devices (OLEDs) made using two of the complexes as luminescent dopants show high efficiency and low roll-off at high luminance.

A Comparison between Triphenylmethyl and Triphenylsilyl Spirobifluorenyl Hosts: Synthesis, Photophysics and Performance in Phosphorescent Organic Light-Emitting Diodes.

This study presents the synthesis and characterization of two spirobifluorenyl derivatives substituted with either triphenylmethyl (SB-C) or triphenylsilyl (SB-Si) moieties for use as host materials in phosphorescent organic light-emitting diodes (PHOLED). Both molecules have similar high triplet energies and large energy gaps. Blue Ir(tpz)3 and green Ir(ppy)3 phosphorescent devices were fabricated using these materials as hosts. Surprisingly, SB-Si demonstrated superior charge-transporting ability compared to SB-C, despite having similar energies for their valence orbitals. In particular, SB-Si proved to be a highly effective host for both blue and green devices, resulting in maximum efficiencies of 12.6% for the Ir(tpz)3 device and 9.6% for the Ir(ppy)3 device. These results highlight the benefits of appending the triphenylsilyl moiety onto host materials and underscore the importance of considering the morphology of hosts in the design of efficient PHOLEDs.

Two-Coordinate Coinage Metal Complexes as Solar Photosensitizers.

Generating sustainable fuel from sunlight plays an important role in meeting the energy demands of the modern age. Herein, we report two-coordinate carbene-metal-amide (cMa, M = Cu(I) and Au(I)) complexes that can be used as sensitizers to promote the light-driven reduction of water to hydrogen. The cMa complexes studied here absorb visible photons (εvis > 103 M-1 cm-1), maintain long excited-state lifetimes (τ ∼ 0.2-1 µs), and perform stable photoinduced charge transfer to a target substrate with high photoreducing potential (E+/* up to -2.33 V vs Fc+/0 based on a Rehm-Weller analysis). We pair these coinage metal complexes with a cobalt-glyoxime electrocatalyst to photocatalytically generate hydrogen and compare the performance of the copper- and gold-based cMa complexes. We also find that the two-coordinate complexes herein can perform photodriven hydrogen production from water without the addition of the cobalt-glyoxime electrocatalyst. In this "catalyst-free" system, the cMa sensitizer partially decomposes to give metal nanoparticles that catalyze water reduction. This work identifies two-coordinate coinage metal complexes as promising abundant metal, solar fuel photosensitizers that offer exceptional tunability and photoredox properties.

Polarizable Anionic Sublattices Can Screen Molecular Dipoles in Noncentrosymmetric Inorganic-Organic Hybrids.

We report the growth and photophysical characterization of two polar hybrid lead halide phases, methylenedianiline lead iodide and bromide, (MDA)Pb2I6 and (MDA)Pb2Br6, respectively. The phases crystallize in noncentrosymmetric space group Fdd2, which produces a highly oriented molecular dipole moment that gives rise to second harmonic generation (SHG) upon excitation at 1064 nm. While both compositions are isostructural, the size dependence of the SHG signal suggests that the bromide exhibits a stronger phase-matching response whereas the iodide exhibits a significantly weaker non-phase-matching signal. Similarly, fluorescence from (MDA)Pb2Br6 is observed around 630 nm below 75 K whereas only very weak luminescence from (MDA)Pb2I6 can be seen. We attribute the contrasting optical properties to differences in the character of the halide sublattice and postulate that the increased polarizability of the iodide ions acts to screen the local dipole moment, effectively reducing the local electric field in the crystals.

Metal-Catalyzed and Metal-Free Nucleophilic Substitution of 7-I-B18H21.

In this work, two pathways of reactivity are investigated to generate site-specific substitutions at the B7 vertex of the luminescent boron cluster, anti-B18H22. First, a palladium-catalyzed cross-coupling reaction utilizing the precursor 7-I-B18H21 and a series of model nucleophiles was developed, ultimately producing several B-N- and B-O-substituted species. Interestingly, the B-I bond in this cluster can also be substituted in an uncatalyzed fashion, leading to the formation of various B-N, B-O, and B-S products. This work highlights intricate differences corresponding to these two reaction pathways and analyzes the role of solvents and additives on product distributions. As a result of our synthetic studies, seven new B18-based clusters were synthesized, isolated, and characterized by mass spectrometry and nuclear magnetic resonance (NMR) spectroscopy. The photoluminescence properties of two structurally similar ether and thioether products were further investigated, with both exhibiting blue fluorescence in solution at 298 K and long-lived green or yellow phosphorescence at 77 K. Overall, this work shows, for the first time, the ability to perform substitution of a boron-halogen bond with nucleophiles in a B18-based cluster, resulting in the formation of photoluminescent molecules.

π-Extended Ligands in Two-Coordinate Coinage Metal Complexes.

Two-coordinate carbene-MI-amide (cMa, MI = Cu, Ag, Au) complexes have emerged as highly efficient luminescent materials for use in a variety of photonic applications due to their extremely fast radiative rates through thermally activated delayed fluorescence (TADF) from an interligand charge transfer (ICT) process. A series of cMa derivatives was prepared to examine the variables that affect the radiative rate, with the goal of understanding the parameters that control the radiative TADF process in these materials. We find that blue-emissive complexes with high photoluminescence efficiencies (ΦPL > 0.95) and fast radiative rates (kr = 4 × 106 s-1) can be achieved by selectively extending the π-system of the carbene and amide ligands. Of note is the role played by the increased separation between the hole and electron in the ICT excited state. Analysis of temperature-dependent luminescence data and theoretical calculations indicate that the hole-electron separation exerts a primary effect on the energy gap between the lowest-energy singlet and triplet states (ΔEST) while keeping the radiative rate for the singlet state relatively unchanged. This interpretation provides guidelines for the design of new cMa derivatives with even faster radiative rates in addition to those with slower radiative rates and thus extended excited state lifetimes.

Benchmarking the dynamic luminescence properties and UV stability of B18H22-based materials.

The dynamic photoluminescence properties, and potential quenching mechanisms, of anti-B18H22, 4,4'-Br2-anti-B18H20, and 4,4'-I2-anti-B18H20 are investigated in solution and polymer films. UV stability studies of the neat powders show no decomposition occurring after intense 7 day light soaking. In contrast, clusters incorporated into polymer films are found to degrade into smaller borane fragments under the same irradiation conditions. To highlight the utility of these compounds, we leverage their favorable optical properties in a prototype UV imaging setup.

π-Extension of heterocycles via a Pd-catalyzed heterocyclic aryne annulation: π-extended donors for TADF emitters.

We report the annulation of heterocyclic building blocks to access π-extended polycyclic aromatic hydrocarbons (PAHs). The method involves the trapping of short-lived hetarynes with catalytically-generated biaryl palladium intermediates and allows for the concise appendage of three or more fused aromatic rings about a central heterocyclic building block. Our studies focus on annulating the indole and carbazole heterocycles through the use of indolyne and carbazolyne chemistry, respectively, the latter of which required the synthesis of a new carbazolyne precursor. Notably, these represent rare examples of transition metal-catalyzed reactions of N-containing hetarynes. We demonstrate the utility of our methodology in the synthesis of heterocyclic π-extended PAHs, which were then applied as ligands in two-coordinate metal complexes. As a result of these studies, we identified a new thermally-activated delayed fluorescence (TADF) emitter that displays up to 81% photoluminescence efficiency, along with insight into structure-property relationships. These studies underscore the utility of heterocyclic strained intermediates in the synthesis and study of organic materials.

Molecular Alignment of Homoleptic Iridium Phosphors in Organic Light-Emitting Diodes.

The orientation of facial (fac) tris-cyclometalated iridium complexes in doped films prepared by vacuum deposition is investigated by altering the physical shape and electronic asymmetry in the molecular structure. Angle-dependent photoluminescence spectroscopy and Fourier-plane imaging microscopy show that the orientation of roughly spherical fac-tris(2-phenylpyridyl)iridium (Ir(ppy)3 ) is isotropic, whereas complexes that are oblate spheroids, fac-tris(mesityl-2-phenyl-1H-imidazole)iridium (Ir(mi)3 ) and fac-tris((3,5-dimethyl-[1,1'-biphenyl]-4-yl)-2-phenyl-1H-imidazole)iridium (Ir(mip)3 ), have a net horizontal alignment of their transition dipole moments. Optical anisotropy factors of 0.26 and 0.15, respectively, are obtained from the latter complexes when doped into tris(4-(9H-carbazol-9-yl)phenyl)amine host thin films. The horizontal alignment is attributed to the favorable van der Waals interaction between the oblate Ir complexes and host material. Trifluoromethyl groups substituted on one polar face of the Ir(ppy)3 and Ir(mi)3 complexes introduce chemical asymmetries in the molecules at the expense of their oblate shapes. The anisotropy factors of films doped with these substituted derivatives are lower relative to the parent complexes, indicating that the fluorinated patches reinforce horizontal alignment during deposition. High efficiencies obtained from organic light emitting diodes prepared using the Ir dopants is attributed, in part, to improved outcoupling of electroluminescence brought about by molecular alignment.

A Luminescent Two-Coordinate AuI Bimetallic Complex with a Tandem-Carbene Structure: A Molecular Design for the Enhancement of TADF Radiative Decay Rate.

A luminescent bimetallic AuI complex comprised of N-heterocyclic carbene (NHC) and carbazole (Cz) ligands, that is, (NHC')Au(NHC)AuCz has been synthesized and studied. Both carbene ligands in the bimetallic complex act as electron acceptors in tandem to increase the energy separation between the ground and excited state, which is higher than those found in either monometallic analogue, (NHC)AuCz and (NHC')AuCz. A coplanar geometry designed into the tandem complex ensures sufficient electronic coupling between the π-orbitals of the ligands to impart a strong oscillator strength to the singlet intra-ligand charge-transfer (1 ICT) transition. Theoretical modelling indicates that the emissive ICT excited state involves both NHC ligands. The tandem complex gives blue luminescence (λmax =480 nm) with a high photoluminescent quantum yield (ΦPL =0.80) with a short decay lifetime (τ=0.52 µs). Temperature-dependent photophysical studies indicate that emission is via thermally assisted delayed fluorescence (TADF) and give a small singlet-triplet energy difference (ΔEST =50 meV, 400 cm-1 ) consistent with the short TADF lifetime.

Synthesis and Characterization of Zinc(II) Complexes Bearing 4-Acridinol and 1-Phenazinol Ligands.

The synthesis and characterization of zinc(II) chelates bearing acridin-4-ol (A), phenazin-1-ol (P), and benzo[b]phenazin-1-ol (bP) are presented. The formation of homoleptic (ZnX2) or heteroleptic (ZnX1) products can be controlled by stochiometric or excess amounts of zinc(II) acetylacetonate monohydrate, Zn(acac)2, respectively. Electrochemical and photophysical studies show that the homoleptic complexes (ZnA2, ZnP2, and ZnbP2) have ligand-centered properties inherited from the corresponding free ligands. Calculations using density functional theory (DFT) agree with the observed experimental ligand-centered photophysical and electrochemical behavior.

Influence of Dimethyl Sulfoxide on the Structural Topology during Crystallization of PbI2.

Hybrid metal-organic halides are an exciting class of materials that offer the opportunity to examine how fundamental aspects of chemical bonding can influence the structural topology. In this work, we describe how solvent adducts of lead halides can influence the crystallization and subsequent annealing of these hybrid phases. While the size and shape of organic molecules are known to govern the final topology of the hybrid, we show that the affinity of solvent molecules for Pb ions may also play a previously underappreciated role.

A molecular boron cluster-based chromophore with dual emission.

Bromination of the luminescent borane, anti-B18H22, via electrophilic substitution using AlCl3 and Br2, yields the monosubstituted derivative 4-Br-anti-B18H21 as an air-stable crystalline solid. In contrast to the unsubstituted parent compound, 4-Br-anti-B18H21 possesses dual emission upon excitation with UV light and exhibits fluorescence at 410 nm and phosphorescence at 503 nm, with Φtotal = 0.07 in oxygen-free cyclohexane. Increased oxygen content in cyclohexane solution quenches the phosphorescence signal. The fluorescent signal intensity remains unaffected by oxygen, suggesting that this molecule could be used as a ratiometric oxygen probe.

Highly Efficient Deep Blue Luminescence of 2-Coordinate Coinage Metal Complexes Bearing Bulky NHC Benzimidazolyl Carbene.

The structural, photophysical and electrochemical properties of three luminescent 2-coordinate coinage metal (i.e., M = Cu, Ag, Au) complexes bearing a sterically bulky benzimidazolyl carbene, 1,3-bis(2,6-diisopropylphenyl)-1-H-benzo[d]imidazol-2-ylidene (BZI), and carbazolide (Cz) as the anionic ligand were investigated. All the complexes emit in the deep blue region (~430 nm) with relatively narrow spectra (full width at half maximum = 44 nm, 2,300 cm-1) characterized by vibronic fine structure in nonpolar media (methylcyclohexane at room temperature), and with high photoluminescence quantum yields (ΦPL > 80%) and radiative rate constants (k r ~ 7.8 × 105 s-1). The luminescence is solvatochromic, undergoing a red-shift in a polar solvent (CH2Cl2) at room temperature that are accompanied by a decrease in quantum yields (ΦPL < 23%) and radiative rate constants (k r < 4.0 × 104 s-1), whereas the non-radiative rate constants remain nearly constant (k nr ~ 1.0 × 105 s-1). The radiative rate is controlled via thermally assisted delayed fluorescence (TADF) and temperature-dependent luminescence studies of the gold complex (Au BZI) in methylcyclohexane solution reveal an energy difference between the lowest singlet and triplet excited states of 920 cm-1. An organic light-emitting diode (OLED) fabricated using Au BZI as a luminescent dopant has an external quantum efficiency of 12% and narrow, deep-blue emission (CIE = 0.16, 0.06).