Probing the Electron Accepting Ability of Phosphaphenalenes.

Phosphaphenalenes, extended π conjugates with the incorporation of phosphorus, are attractive avenues towards molecular materials for the applications in organic electronics, but their electron accepting ability have not been investigated. In this study, we present systematic studies on the reductive behavior of a representative phosphaphenalene and its oxide by chemical and electrochemical methods. The chemical reduction of the phosphaphenalene by alkali metals reveals the facile P‒C bond cleavage to form phosphaphenalenide anion, which functions as a transfer block for structure modification on the phosphorus atom. In contrast, the pentavalent P-oxide reacts with one or two equivalents of elemental sodium to form stable radical anion and dianion salts, respectively.

Manipulating Chiroptical Activities in 0D Chiral Hybrid Manganese Bromides by Solvent Molecular Engineering.

0D hybrid metal halides (0D HMHs) with fully isolated inorganic units provide an ideal platform for studying the correlations between chiroptical activities and crystal structures at atomic levels. Here, through the incorporation of different solvent molecules, a series of 0D chiral manganese bromides (RR/SS-C20H28N2)3MnBr8·2X (X = C2H5OH, CH3OH, or H2O) are synthesized to elucidate their chiroptical properties. They show negligible circular dichroism signals of Mn absorptions due to C2v-symmetric [MnBr4]2- tetrahedra. However, they display distinct circularly polarized luminescence (CPL) signals with continuously increased luminescence asymmetry factors (glum) from 10-4 (X = C2H5OH) to 10-3 (X = H2O). The increased glum value is structurally revealed to originate from the enhancement of [MnBr4]2- tetrahedral bond-angle distortions, due to the presence of different solvent molecules. Furthermore, (RR/SS-C20H28N2)MnBr4·H2O enantiomers with larger bond-angle distortions of [MnBr4]2- tetrahedra are synthesized based on hydrobromic acid-induced structural transformation of (RR/SS-C20H28N2)3MnBr8·2H2O enantiomers. Therefore, such (RR/SS-C20H28N2)MnBr4·H2O enantiomers exhibit enhanced CPL signals with |glum| up to 1.23 × 10-2. This work provides unique insight into enhancing chiroptical activities in 0D HMH systems.

Polarizability matters in enantio-selection.

The prevalence of chirality, or, handedness in biological world is a fundamental phenomenon and a characteristic hallmark of life. Thus, understanding the origin of enantio-selection, i.e., the sense and magnitude of asymmetric induction, has been a long-pursued goal in asymmetric catalysis. Herein, we demonstrated a polarizability-derived electronic effect that was shown to be capable of rationalizing a broad range of stereochemical observations made in the field of asymmetric catalysis. This effect provided a consistent enantio-control model for the prediction of major enantiomers formed in a ruthenium-catalyzed asymmetric transfer hydrogenations of ketones. Direct and quantitative linear free energy relationships between substrates' local polarizabilities and observed enantio-selectivity were also revealed in three widely known asymmetric catalytic systems covering both reductions and oxidations. This broadly applicable polarizability-based electronic effect, in conjunction with conventional wisdom mainly leveraging on steric effect considerations, should aid rational design of enantio-selective processes for better production of chiral substances.

Phosphorescent fac-Bis(triarylisocyanide) W(0) and Mo(0) Complexes.

Homoleptic W(0) and Mo(0) complexes containing bis(triarylisocyanide) ligands with bulky substituents were synthesized and spectroscopically characterized. Crystallographically determined structures revealed that these complexes are hourglass-like in shape with the tridentate ligands adopting a facial coordination mode to the metal center. These complexes luminesce in fluid solutions and in the solid state. Typically in toluene at 298 K, the two W(0) complexes display the emission maximum (lifetime and quantum yield) at 591 nm (0.83 µs and 0.35) and 628 nm (1.04 µs and 0.39), and similarly, the two Mo(0) complexes display it at 575 nm (0.54 µs and 0.15) and 617 nm (0.56 µs and 0.23). DFT and TDDFT calculations indicated that the low-energy absorption bands of the W(0) and Mo(0) complexes could be metal-to-ligand charge transfer (MLCT) transitions in nature. These complexes exhibited a reversible M+/0 redox couple at -0.70 and -0.63 V vs Fc+/0 for the W(0) complexes and -0.86 and -0.67 V for the Mo(0) complexes. The excited-state reduction potentials were hence estimated to be -2.91 and -2.74 V vs Fc+/0 for the W(0) complexes and -3.10 and -2.81 V vs Fc+/0 for the Mo(0) complexes, indicating that they are potentially strong photoreductants.

Thermally Activated Delayed Fluorescent Binuclear Copper(I) Alkynyl Complexes with Cuprophilic Interactions.

Copper(I)-based thermally activated delayed fluorescence (TADF) emitters have been conceived to be promising candidates for display and lighting applications because of their multifarious structures and strong photoluminescence. Herein a string of binuclear Cu(I) complexes bearing pronounced cuprophilic interactions have been designed and synthesized. [Cu2(dppb)2(µ2-η1-C≡C-Ph)2] (1 a) and [Cu2(dppb)2(µ2-η1-C≡C-PPXZ)2] (1 b) display photoluminescence quantum yields of up to 67 % in doped films and solid states via TADF and exhibit reversible bicolor luminescence switching upon mechanical stimuli. Computational studies manifest that the metal-to-ligand charge transfer predominant transitions ensure a small energy splitting (ΔEST) between the lowest singlet (S1) and triplet (T1) excited states and cuprophilic interactions promote the spin-orbit coupling (SOC), favoring the reverse intersystem crossing (RISC) process. This study provides a new strategy for the construction of stimuli-responsive metal-based TADF materials.

A stable rhodium-coordinated carbene with a σ0π2 electronic configuration.

Isolable singlet carbenes have universally adopted a σ2π0 electronic state, making them σ-donors and π-acceptors. We present a rhodium-coordinated, cationic cyclic diphosphinocarbene with a σ0π2 ground state configuration. Nuclear magnetic resonance spectroscopy studies show a carbene carbon chemical shift below -30.0 parts per million. X-ray crystallography reveals a planar RhP2C configuration. Quantum chemical calculations rationalize how σ-electron delocalization/donation and π-electron negative hyperconjugation together stabilize the formally vacant σ orbital and the filled π orbital at the carbene center. In contrast to traditional carbene counterparts this carbene can undergo synthetic transformations with both a Lewis base and a silver salt, producing a Lewis acid/base adduct and a silver π-complex, respectively. Exhibiting ambiphilic reactivity, it can also form a ketenimine through reaction with an isocyanide.

An Isolable Radical Anion Featuring a 2-Center-3-Electron π-Bond without a Clearly Defined σ-Bond.

Featuring an extra electron in the π* antibonding orbital, species with a 2-center-3-electron (2c3e) π bond without an underlying σ bond are scarcely known. Herein, we report the synthesis, isolation and characterization of a radical anion salt [K(18-C-6)]+ {[(HCNDipp)2 Si]2 P2 }⋅- (i.e. [K(18-C-6)]+ 3⋅- ) (18-C-6=18-crown-6, Dipp=2,6-diisopropylphenyl), in which 3⋅- features a perfectly planar Si2 P2 four-membered ring. This species represents the first example of a Si- and P-containing analog of a bicyclo[1.1.0]butane radical anion. The unusual bonding motif of 3⋅- was thoroughly investigated via X-ray diffraction crystallography, electron paramagnetic resonance spectroscopy (EPR), and calculations by density functional theory (DFT), which collectively unveiled the existence of a 2c3e π bond between the bridgehead P atoms and no clearly defined supporting P-P σ bond.

Tunable Yellow to Near-Infrared Fluorescent Boron-Amino-Chelating Complexes with Stokes Shifts >100 nm.

A series of diphenylboron-chelating N-substituent 8-aminoquinoline, 5-aminoquinoxaline, and 1-aminophenazine were prepared. They exhibit lowest energy absorption peaks of 444-766 nm, emission peaks of 563-820 nm, and quantum yields of up to 46.5%. Electrochemical and theoretical studies indicate that the N-substituent mainly determines the HOMO and the framework determines the LUMO, thus allowing for a wide-tuning of absorptions/emissions. Intramolecular charge transfer transition leads to large Stokes shifts of up to 166 nm. One selected compound showed satisfactory cytocompatibility and cytoplasm-targeting cell imaging ability.

Cyanide-Bridged Rope-like Chains Based on Trigonal-Bipyramidal [Fe2Cu3] Subunits.

Extending a selected cyanometalate block into a higher dimensional framework continues to present intriguing challenges in the fields of chemistry and material science. Here, we prepared two rope-like chain compounds of {[(Tp*Me)Fe(CN)3]2Cu2X2(L)}·sol (1, X = Cl, L = (MeCN)0.5(H2O/MeOH)0.5, sol = 2MeCN·1.5H2O; 2, X = Br, L = MeOH, sol = 2MeCN·0.75H2O; Tp*Me = tris(3, 4, 5-trimethylpyrazole)borate) in which the cyanide-bridged trigonal-bipyramidal [Fe2Cu3] subunits were linked with the adjacent ones via two vertex Cu(II) centers, providing a new cyanometallate chain archetype. Direct current magnetic study revealed the presence of ferromagnetic couplings between Fe(III) and Cu(II) ions and uniaxial anisotropy due to a favorable alignment of the anisotropic tricyanoiron(III) units. Moreover, compound 1 exhibits single-chain magnet behavior with an appreciable energy barrier of 72 K, while 2 behaves as a metamagnet, likely caused by the subtle changes in the interchain interactions.

Circularly polarized chemiluminescence from planar chiral bis(adamantylidene-1,2-dioxetane)s.

Bis(adamantylidene-1,2-dioxetane), upon conjugation to a planar chiral scaffold of [2.2]paracyclophane, gave chemical-triggerable circularly polarized chemiluminescence with a dissymmetry factor of 1.1 × 10-3 scale, to which exciton chirality upon chemiexcitation was assigned as the origin.

Organophotocatalysed synthesis of 2-piperidinones in one step via [1 + 2 + 3] strategy.

Six-membered N-containing heterocycles, such as 2-piperidinone derivatives, with diverse substitution patterns are widespread in natural products, drug molecules and serve as key precursors for piperidines. Thus, the development of stereoselective synthesis of multi-substituted 2-piperidinones are attractive. However, existing methods heavily rely on modification of pre-synthesized backbones which require tedious multi-step procedure and suffer from limited substitution patterns. Herein, an organophotocatalysed [1 + 2 + 3] strategy was developed to enable the one-step access to diverse substituted 2-piperidinones from easily available inorganic ammonium salts, alkenes, and unsaturated carbonyl compounds. This mild protocol exhibits exclusive chemoselectivity over two alkenes, tolerating both terminal and internal alkenes with a wide range of functional groups.

Long-Persistent Circularly Polarized Luminescence from a Host-Guest System Regulated by the Multiple Roles of a Gold(I)-Carbene Motif.

The promotion of intersystem crossing (ISC) is critical for achieving a high-efficiency long-persistent luminescence (LPL) from organic materials. However, the use of a transition-metal complex for LPL materials has not been explored because it can also shorten the emission lifetime by accelerating the phosphorescence decay. Here, we report a new class of LPL materials by doping a monovalent Au-carbene complex into a boron-embedded molecular host. The donor-acceptor systems exhibit photoluminescence with both high efficiencies (>57 %) and long lifetimes (ca. 40 ms) at room temperature. It is revealed that the Au atom promotes the population of low-lying triplet excited states of the host aggregate (T1 *) which can be converted into the charge-transfer (CT) state, thereby resulting in afterglow luminescence. Moreover, the use of a chirality unit on the guest molecule results in the LPL being circularly polarized. This work illustrates that transition-metal complexes can be used for developing organic afterglow systems by exquisite control over the excited state mechanism.

Integrating Achiral and Chiral Organic Ligands in Zero-Dimensional Hybrid Metal Halides to Boost Circularly Polarized Luminescence.

Chiral zero-dimensional hybrid metal halides (0D HMHs) could combine excellent optical properties and chirality, making them promising for circularly polarized luminescence (CPL). However, chiral 0D HMHs with efficient CPL have been rarely reported. Here, we propose an efficient strategy to achieve simultaneously high photoluminescence quantum yield (PLQY) and large dissymmetry factor (glum ), by integrating achiral and chiral ligands into 0D HMHs. Specifically, three pairs of chiral 0D hybrid indium-antimony chlorides are synthesized by combing achiral guanidine with three types of chiral methylbenzylammonium-based derivatives as the organic cations. These chiral 0D HMHs exhibit near-unity PLQY and large glum values up to around ±1×10-2 . The achiral guanidine ligand is not only essential to crystallize these hybrid indium-antimony chlorides to achieve near-unity PLQYs, but also greatly enhances the chirality induction from organic ligands to inorganic units in these 0D HMHs. Furthermore, the choice of different chiral ligands can modify the strength of hydrogen bonding interactions in these 0D HMHs, to maximize their glum values. Overall, this study provides a robust way to realize efficient CPL in chiral HMHs, expanding their applications in chiroptical fields.

Dicationic Diimine Pt(II) Bis(N-heterocyclic allenylidene) Complexes: Extended Pt···Pt Chains, NIR Phosphorescence, and Chromonics.

Although square-planar Pt(II) complexes are well-known to self-assemble into supramolecules via noncovalent intermolecular Pt···Pt and/or π-π interactions, the self-assembly of dicationic Pt(II) complexes was scarce due to the electrostatic repulsive force. Herein, a series of dicationic diimine bis(N-heterocyclic allenylidene) Pt(II) complexes were synthesized and characterized. Close Pt···Pt and/or π-π contacts are observed in the crystals of these complexes. In particular, complexes 1·2PF6 and 2·2PF6 exhibit one-dimensional packing with extended Pt···Pt contacts of 3.302 and 3.240 Å, respectively. The photophysical properties of these complexes in the solution and solid state were investigated. NIR emission was recorded for complexes 1·2PF6 (λmax = 950 nm) and 2·2PF6 (λmax = 855 nm) in the solid state at 298 K. To explore the aggregate behaviors of these complexes, the counteranion PF6- was exchanged to the large lipophilic anion 2,3,4-tris(dodecyloxy)benzene sulfonate (LA-) and the hydrophilic anion Cl-. Complexes 1·2LA and 2·2LA or 1·2Cl and 2·2Cl could self-assemble with Pt···Pt and/or π-π interactions in the nonpolar or aqueous solutions as well. Further increasing the concentration of 1·2Cl and 2·2Cl in aqueous solution, chromonic mesophases with NIR emission (λmax = 988 nm) were obtained. DFT and TD-DFT calculations were performed to gain deep insight into the dication-dication packings and photophysical properties of the complexes. The σ-donating as well as π-accepting character of the N-heterocyclic allenylidene ligand endows complexes with rigid and electron-delocalized coplanar features, which are conducive to achieving the self-assembling processes associated with Pt···Pt and/or π-π interactions.

Aggregation of phosphorescent Pd(II) and Pt(II) complexes with lipophilic counter-anions in non-polar solvents.

Phosphorescent cationic tridentate C^N^N (HC^N^N = 6-(2-R2,4-R1-phenyl)-2,2'-bipyridine; R1 = R2 = H or F, or R1 = OMe, R2 = H) cyclometallated Pd(II) complexes with an N,N-dimethyl-imidazol-allenylidene ancillary ligand (L) and their corresponding Pt(II) congeners have been synthesized and characterized, following the previously reported preparation of the complex [Pd(6-phenyl-2,2'-bipyridine)L]+. For these cationic Pd(II)/Pt(II) complexes with 2,3,4-tris(dodecyloxy)benzenesulfonate (LA-) counter-anions in mixed CH2Cl2/toluene solvents, uniform square flake or fibre-like aggregates were formed. Corresponding multicolour phosphorescence with obvious metal-metal-to-ligand charge transfer (MMLCT) features gradually changed from red to NIR by manipulating the various fractions of Pd/Pt species. Circular dichroism (CD) and circularly polarized luminescence (CPL) derived from the fibre-like Pd aggregates of [Pd(6-(2,4-difluorophenyl)-2,2'-bipyridine)L]+ in chiroptical CH2Cl2/limonene solvents were achieved with an isodesmic aggregation mode. Dispersive metallophilic interactions are claimed to be the driving force for these photo-functional aggregates.

Circularly polarized near-infrared phosphorescence of chiral chromium(III) complexes.

Homoleptic Cr(III) complexes containing anionic tridentate 1,8-(bisoxazolyl)carbazolide ligands are phosphorescent in deaerated solutions with peak maxima in the range of 813-845 nm. The ligand carbon-centred chirality has been transferred to the helical chirality of the complexes and hence induced circularly polarized NIR-emissions with dissymmetry factor in the scale of 2.0 × 10-3.

The energy gap law for NIR-phosphorescent Cr(III) complexes.

A series of homoleptic Cr(III) complexes containing substituted anionic 1,3-bis(pyridin-2-ylimino)isoindolin-2-ide ligands are phosphorescent with λmax in the 777-970 nm range in degassed fluid solutions. The energy gap law has been successfully applied to the doublet excited states of Cr(III) complexes.

Gold(I) Multi-Resonance Thermally Activated Delayed Fluorescent Emitters for Highly Efficient Ultrapure-Green Organic Light-Emitting Diodes.

Acceleration of singlet-triplet intersystem crossings (ISC) is instrumental in bolstering triplet exciton harvesting of multi-resonance thermally activated delayed fluorescent (MR-TADF) emitters. This work describes a simple gold(I) coordination strategy to enhance the spin-orbit coupling of green and blue BN(O)-based MR-TADF emitters, which results in a notable increase in rate constants of the spectroscopically observed ISC process to 3×109  s-1 with nearly unitary ISC quantum yields. Accordingly, the resultant thermally-stable AuI emitters attained large values of delayed fluorescence radiative rate constant up to 1.3×105 /1.7×105  s-1 in THF/PMMA film while preserving narrowband emissions (FWHM=30-37 nm) and high emission quantum yields (ca. 0.9). The vapor-deposited ultrapure-green OLEDs fabricated with these AuI emitters delivered high luminance of up to 2.53×105  cd m-2 as well as external quantum efficiencies of up to 30.3 % with roll-offs as low as 0.8 % and long device lifetimes (LT60 ) of 1210 h at 1000 cd m-2 .

Two Cholesterol-Containing Pyrene Derivatives: Subtle Spacer Difference, Diverse Stimuli-Responsive Luminescence, Chirality, and Self-Assembly Behaviors.

Two chiral molecules 1 and 2 were designed and synthesized with a pyrene moiety directly linked to a chiral cholesterol moiety and connected through a methylene spacer, respectively. Influence of the spacer on their stimuli-responsive luminescence, chirality, and self-assembly behaviors was systematically investigated. Molecules 1 and 2 had similar aggregation-induced emission enhancement (AIEE) in solution, because of carrying the same fluorescence moiety. Both molecules displayed mechanochromism (MC) property but with different color contrast, whereas only 2 showed mechanoluminescence (ML) activity. When doping in liquid crystal molecule 5CB, both molecules induced the formation of chiral nematic liquid crystals (N*-LCs) with strong circularly polarized luminescence (CPL). Molecule 2 induced single handedness signal, irrespective of doping ratios, while 1-doped N*-LCs showed an inversion of CPL signal from negative to positive upon the increase of doping ratios. Molecules 1 and 2 also self-assembled into different coassemblies with 5CB. Their distinct behaviors were attributed to the influence of the methylene spacer, which caused different molecular conformation and steric bulkiness; accordingly, it changed intermolecular interactions and molecular packing of the two molecules and led to diverse chirality and luminescence. This work provided important model molecules to better understand the molecular structure-property relationship and guide the design of novel functional molecules.

Highly Efficient Au(I) Alkynyl Emitters: Thermally Activated Delayed Fluorescence and Solution-Processed OLEDs.

Two-coordinate donor-metal-acceptor type coinage metal complexes displaying efficient thermally activated delayed fluorescence (TADF) have been unveiled to be highly appealing candidates as emitters for organic light-emitting diodes (OLEDs). Herein a series of green to yellow TADF gold(I) complexes with alkynyl ligands has been developed for the first time. The complexes exhibit high photoluminescence quantum yields (PLQYs) of up to 0.76 in doped films (5 wt % in PMMA) at room temperature. The modifications of alkynyl ligands with electron-donating amino groups together with the use of electron-deficient carbene ligands induce ligand-to-ligand charge transfer excited states that give rise to TADF emission. Spectroscopic and density functional theory (DFT) calculations reveal the roles of electron-donating capability of the alkynyl ligand in tuning the excited-state properties. Solution-processed organic light-emitting diodes (OLEDs) using the present complexes as emitters achieve maximum external quantum efficiency (EQE) of up to 20 %.