Long‐Lived Circularly Polarized Phosphorescence in Helicene‐NHC Rhenium(I) Complexes: The Influence of Helicene,Halogen, and Stereochemistry on Emission Properties

The first enantiopure chiral‐at‐rhenium complexes of the form fac‐ReX(CO)₃(:C^N) have been prepared, where :C^N is a helicene‐N‐heterocyclic carbene (NHC) ligand and X=Cl or I. These have complexes show strong changes in the emission characteristics, notably strongly enhanced phosphorescence lifetimes (reaching 0.7 ms) and increased circularly polarized emission (CPL) activity, as compared to their parent chiral models lacking the helicene unit. The halogen along with its position within the dissymmetric stereochemical environment strongly affect the photophysics of the complexes, particularly the phosphorescence quantum yield and lifetime. These results give fresh insight into fine tuning of photophysical and chiroptical properties of Re‐NHC systems.     

Water‐Soluble Luminescent Cyclometalated Gold(III) Complexes with cis‐Chelating Bis(N‐Heterocyclic Carbene) Ligands: Synthesis and Photophysical Properties

A new class of cyclometalated Au^III complexes containing various bidentate C‐deprotonated C^N and cis‐chelating bis(N‐heterocyclic carbene) (bis‐NHC) ligands has been synthesized and characterized. These are the first examples of Au^III complexes supported by cis‐chelating bis‐NHC ligands. [Au(C^N)(bis‐NHC)] complexes display emission in solutions under degassed condition at room temperature with emission maxima (λ_max) at 498–633 nm and emission quantum yields of up to 10.1 %. The emissions are assigned to triplet intraligand (IL) π→π* transitions of C^N ligands. The Au^III complex containing a C^N (C‐deprotonated naphthalene‐substituted quinoline) ligand with extended π‐conjugation exhibits prompt fluorescence and phosphorescence of comparable intensity with λ_max at 454 and 611 nm respectively. With sulfonate‐functionalized bis‐NHC ligand, four water‐soluble luminescent Au^III complexes, including those displaying both fluorescence and phosphorescence, were prepared. They show similar photophysical properties in water when compared with their counterparts in acetonitrile. The long phosphorescence lifetime of the water‐soluble AuIII complex with C‐deprotonated naphthalene‐substituted quinoline ligand renders it to function as ratiometric sensor for oxygen. Inhibitory activity of one of these water‐soluble Au^III complexes towards deubiquitinase (DUB) UCHL3 has been investigated; this complex also displayed a significant inhibitory activity with IC₅₀ value of 0.15 μM .     

Stereoselective Formation of Facial Tris-Cyclometalated PtIV Complexes: Dual Phosphorescence from Heteroleptic Derivatives

A stereoselective synthetic route to homo- and heteroleptic facial tris-cyclometalated Pt^IV complexes is reported, involving the oxidative addition of 2-(2-pyridyl)- or 2-(1-isoquinolinyl)benzenediazonium salts to cis-[Pt(C^N)₂] precursors, with C^N=cyclometalated 2-(p-tolyl)pyridine (tpy), 2-phenylquinoline (pq), 2-(2-thienyl)pyridine or 1-phenylisoquinoline (piq), to produce labile diazenide intermediates that undergo photochemical or thermal elimination of N₂. The method allows the preparation of derivatives bearing cyclometalated ligands of low π–π* transition energies. The new complexes exhibit phosphorescence in fluid solution at room temperature arising from triplet ligand-centered (³LC) excited states, which, in the cases of the heteroleptic derivatives, involve the ligand with the lowest π–π* gap. The heteroleptic piq derivatives exhibit fluorescence and dual phosphorescence from different ligand-centered excited states in rigid media, demonstrating the potential of cyclometalated Pt^IV complexes as multi-emissive materials.     

Effects of fluorine substituent on properties of cyclometalated iridium(III) complexes with a 2,2′-bipyridine ancillary ligand

Cationic cyclometalated Ir(III) complexes (Ir1-Ir5) with fluorine-substituted 2-phenylpyridine (ppy) derivatives as C^N cyclometalating ligands and 2,2′-bipyridine (bpy) as the ancillary ligand, have been synthesized and fully characterized. The influences of the number and the position of fluorine atoms at the cyclometalating ligands on the photophysical, electrochemical and oxygen sensing properties of the Ir(III) complexes have been investigated systematically. The introduction of fluorine on the C^N cyclometalating ligands of the complexes results in blue-shifts of the maximum emission wavelengths, and increases in the photoluminescence quantum yields (Φ_PL), phosphorescence lifetimes and energy gaps, compared to the non-fluorinated [Ir(ppy)₂(bpy)]⁺PF₆^? (Ir0). Among them, 2-(2,4-difluorophenyl)pyridine-derived Ir4 shows the maximum blue-shift (514 nm vs. 575 nm for Ir0) and the highest Φ_PL (50.8% vs. 6.5% for Ir0). The complex Ir3 with 2-(4-fluorophenyl)-5-fluoropyridine as C^N ligand exhibits the highest oxygen sensitivity and excellent operational stability in 10 cycles within 4000 s.     

Design of Luminescent,Heteroleptic, Cyclometalated PtII and PtIV Complexes: Photophysics and Effects of the Cyclometalated Ligands

Neutral pentafluorophenyl benzoquinolinyl Pt^II [Pt(bzq)(HC^N−κN)(C₆F₅)] ( 1 a – g ) complexes, bearing nonmetalated N-heterocyclic HC^N ligands [HC^N=2,5-diphenyl-1,3,4-oxadiazole (Hoxd) a , 2-(2,4-difluorophenyl)pyridine (dfppy) b , 2-phenylbenzo[d]thiazole (pbt) c , 2-(4-bromophenyl)benzo[d]thiazole (Br-pbt) d , 2-phenylquinoline (pq) e , 2-thienylpyridine (thpy) f , 1-(2-pyridyl)pyrene (pypy) g ], and heteroleptic bis(cyclometalated) Pt^IV fac-[Pt(bzq)(C^N)(C₆F₅)Cl] ( 2 b – g , bzq: benzo[h]quinolinyl) derivatives, generated by oxidation of 1 b – g with PhICl₂, are reported. The oxidation reaction of 1 a evolved with formation of the bimetallic Pt^IV complex syn-[Pt(bzq)(C₆F₅)Cl(μ-OH)]₂ 3 . The crystal structures of 1 a,d,f , 2 b,d,e and 3 were corroborated by X-ray crystallography. A comparative study of the absorption and photoluminescence properties of the two series of complexes Pt^II ( 1 ) and Pt^IV ( 2 ), supported by time-dependent DFT calculations (TD-DFT), is presented. The low-lying transitions (absorption and emission) of Pt^II complexes 1 a – e [solution and polystyrene (PS) films] were assigned to the IL/MLCT mixture located on the cyclometalated Pt(bzq) unit, with minor IL′/ML′CT/LL′CT contributions involving the non-metalated ligand. Complex 1 g , bearing the more delocalized pyridyl pyrene (Hpypy) as an ancillary ligand, shows dual ¹ππ* and ³ππ* (Hpypy) emission in fluid CH₂Cl₂ and dual ³IL/³MLCT [Pt(bzq)] and [³ππ*, Hpypy] phosphorescence at 77 K. Upon oxidation, Pt^IV complexes 2 b – f display (solution, PS) ligand-based phosphorescence that arises from the bzq in 2 b (³LC) or from the second C^N ligand in 2 c – f (³L′C) with some ³LL′CT in 2 f . Despite metalation of the pyrenyl group, 2 g exhibits dual emission ¹ππ*/³ππ* located on the pypy chromophore.     

Electronic structures and photophysical properties of phosphorescent platinum (II) complexes with tridentate C^N*N cyclometalated ligands

To get an insight into the structure–property relationships in a series of strongly phosphorescent platinum(II) complexes with tridentate C^N*N cyclometalated ligands, their electronic structures and electroluminescence properties were systematically investigated via density functional theory and time‐dependent density functional theory. Moreover, the factors related to the radiative and non‐radiative decay process, including the transition electric dipole moment μ(S_n), the energy difference between singlet and lowest triplet excited states ΔE(S_n–T₁) and the spin–orbital coupling matrix elements $?S_n\left|{\stackrel{?}{H}}_{\mathrm{SOC}}\right|T_1?$, as well as the energy gap between T₁ and S₀ states ΔE(T₁–S₀) and absorption–emission Stokes shifts have been calculated. Fine emission color tuning and high phosphorescence quantum yield of phosphorescent complexes may be achieved through introducing five–six‐membered metallacycle geometries and linking a substituent (such as phenyl) at bridge atoms. Additionally, phosphorescent properties of these complexes show a clear dependence on the electronegativity of bridge atoms.     

Synthesis and Characterization of Platinum(IV) Complexes Containing 1-Phenyl-1H-pyrazole and α-Diimine Ligands

The paper deals with the synthesis of a series of cationic [Pt(ppz)₂(N^N)]²⁺ complexes containing deprotonated 1-phenyl-1H-pyrazole as cyclometallating (C^N) ligands and α-diimines (N^N) in the form of water-soluble salts with OTf⁻ (trifluoromethanesulfonate) counter ions. These complexes were obtained from cis-[Pt(ppz)₂Cl₂] through chloride ligands substitution with α-diimines. The complexes were identified by means of NMR spectroscopy and their molecular structures were confirmed by X-ray crystallography. The photophysical properties of these complexes were studied in detail. These complexes showed strong luminescence in MeOH/EtOH 1 : 1 glasses at 77 K but were almost non-emitting in MeCN solutions at room temperature. Their emission properties were compared to analogues Ir^III complexes.     

Theoretical Investigation and Design of Highly Efficient Blue Phosphorescent Iridium(III) Complexes Bearing Fluorinated Aromatic Sulfonyl Groups

Aromatic sulfonyl groups have attracted increasing interest due to their unique electronic features. In this article, a series of Ir^III complexes bearing fluorinated phenylsulfonyl groups were evaluated by density functional theory and time‐dependent density functional theory methods. To explore their phosphorescence efficiencies, factors that determine the radiative decay rate constant, k_r, and the nonradiative decay rate constant, k_nr, were computed. As demonstrated by the results, complex 4 , which has fluorinated phenylsulfonyl groups at the 5‐positions of the phenyl rings for all three C^N ligands, was found to have the highest phosphorescence efficiencies with the largest k_r and smallest k_nr values among these complexes. Moreover, it was found to exhibit significantly blueshifted behavior relative to complex 1 and emits in the blue region, and thus, it can serve as a highly efficient blue emitter for application in organic light‐emitting diodes. These findings successfully illustrated the structure–properties relationship and provided valuable information for the development of future highly efficient blue‐emitting phosphors.     

Synthesis,characterization, and optoelectronic properties of heteroleptic iridium complexes containing substituted 1,3,4-oxadiazole and β-diketone as ligands

The new heteroleptic iridium(III) complexes (BuOXD)₂Ir(tta) and (BuOXD)₂Ir(tmd) [BuOXD?=?2-(4-butyloxyphenyl)-5-phenyl[1,3,4]oxadiazolato-N4,C2, tta?=?1,1,1-trifluoro-4-thienylbutane-2,4-dionato, tmd?=?2,2,6,6-tetramethylheptane-3,5-dionato] have been synthesized and characterized. These complexes have two cyclometalated ligands (C^N) and a bidentate diketone ligand (X) [C^N)₂Ir(X)], where X is a β-diketone with trifluoromethyl, theonyl or t-butyl groups. The color tuning with the change in electronegativity of substituents in the β-diketones has been studied. Photoluminescence spectra of the complexes showed peak emissions at 523 and 549?nm, respectively. The electroluminescent properties of these complexes have been studied by fabricating multi layer devices with device structure ITO/α-NPD/8% iridium complex doped CBP/BCP/Alq₃/LiF/Al. The electroluminescence spectra also showed peak emissions at 526 and 570?nm for (BuOXD)₂Ir(tta) and (BuOXD)₂Ir(tmd), respectively. These metal complexes showed good thermal stability in air to 340°C.     

Strong red emissions induced by Pt–Pt interactions in binuclear cycloplatinated(II) complexes containing bridging diphosphines

A series of dinuclear cycloplatinated(II) complexes with general closed formula of [Pt₂Me₂(C^N)₂(μ‐P^P)] (C^N = 2‐vinylpyridine (Vpy), 2,2′‐bipyridine N‐oxide (O‐bpy), 2‐(2,4‐difluorophenyl)pyridine (dfppy); P^P = 1,1‐bis(diphenylphosphino)methane (dppm), N,N‐bis(diphenylphosphino)amine (dppa)) are reported. The complexes were characterized by means of NMR spectroscopy. Due to the presence of dppm and dppa with short backbones as bridging ligands, two platinum centres are located in front of each other in these complexes so a Pt…Pt interaction is established. Because of this Pt…Pt interaction, the complexes have bright orange colour under ambient light and are able to strongly emit red light under UV light exposure. These strong red emissions originate from a ³MMLCT (metal–metal‐to‐ligand charge transfer) electronic transition. In most of these complexes, the emissions have unstructured bell‐shaped bands, confirming the presence of large amount of ³MMLCT character in the emissive state. Only the complexes bearing dfppy and dppa ligands reveal dual luminescence: a high‐energy structured emission originating from ³ILCT/³MLCT (intra‐ligand charge transfer/metal‐to‐ligand charge transfer) and an unstructured low‐energy band associated with ³MMLCT. In order to describe the nature of the electronic transitions, density functional theory calculations were performed for all the complexes.     

Synthesis,characterization and luminescent properties of copper(I) halide complexes containing biphenyl bidentate phosphine ligand

Copper(I) halide complexes having thermally activated delayed fluorescence (TADF) and phosphorescence have attracted much attention. Here, a series of four-coordinate dinuclear copper(I) halide complexes, [CuX(bpbp)]₂ (bpbp = 2,2′-bis(diphenylphosphino)biphenyl, X = I (1), Br (2) and Cl (3)), were synthesized, and their molecular structures and photophysical properties were investigated. The structural analysis reveals that two copper(I) centers are bridged by two halogen ligands to form a dinuclear structure with a four-membered Cu₂X₂ ring. These complexes exhibit yellow to blue emission in the solid state at room temperature and have peak emission wavelengths at 575–487 nm with microsecond lifetimes (τ = 6.2–19.8 μs) and low emission quantum yields (<0.01%). The emissions of 1–3 originate from MLCT, XLCT, and IL (intraligand) transitions. Three complexes displayed good thermal stability.     

Thiazole Boron Difluoride Dyes with Large Stokes Shift,Solid State Emission and Room-Temperature Phosphorescence

The small Stokes shift and weak emission in the solid state are two main shortcomings associated with the boron-dipyrromethene (BODIPY) family of dyes. This study presents the design, synthesis and luminescent properties of boron difluoro complexes of 2-aryl-5-alkylamino-4-alkylaminocarbonylthiazoles. These dyes display Stokes shifts (Δλ, 77–101 nm) with quantum yields (ϕ_FL) up to 64.9 and 34.7 % in toluene solution and in solid state, respectively. Some of these compounds exhibit dual fluorescence and room-temperature phosphorescence (RTP) emission properties with modulable phosphorescence quantum yields (ϕ_PL) and lifetime (τ_p up to 251 μs). The presence of intramolecular H-bonds and negligible π-π stacking revealed by X-ray crystal structure might account for the observed large Stokes shift and significant solid-state emission of these fluorophores, while the enhanced spin-orbit coupling (SOC) of iodine and the self-assembly driven by halogen bonding, π-π and C−H^…π interactions could be responsible for the observed RTP of iodine containing phosphors.     

Ratiometric luminescent molecular oxygen sensors based on uni-luminophores of C^N Pt(II)(acac) complexes that show intense visible-light absorption and balanced fluorescence/phosphorescence dual emission

Uni-luminophores of C^N cyclometalated Pt(II) complexes with balanced room temperature fluorescence/phosphorescence dual emission were prepared for ratiometric oxygen sensing in both intensity mode and lifetime mode.     

MULTI-SITE PHOSPHORESCENCE OF α, β-ENONES:LEVEL INVERSION IN 6β, 19-EPOXYCHOLEST-4-EN-3-ONE BY SOLVATION AND AGGREGATION

Millisecond time-resolved emission spectroscopy was used to probe the phosphorescence kinetics of the α-β-enone 6β, 19-epoxycholest-4-en-3-one (1) as a function of concentration in several paraffinic and hydroxylic glasses at 77 K. Only in methylcyclohexane/methylcyclopentane glass at low concentration (10^?4M) does the phosphorescence decay exponentially. It is interpreted as emission from the ³n* state. Upon increasing the concentration a second emission grows which is characterized by a longer lifetime, a decreased fine structure and a hypsochromically shifted S₀→¹nπ* excitation spectrum. This phosphorescence is ascribed to ³ππ* emission of aggregates of 1. In hydroxylic glasses the phosphorescence decay is multiexponential, even at 10^?4M concentration; from emission band shapes and lifetimes it follows that both ³nπ* and ³ππ* type emissions are present, the latter increasing with the alcohol concentration in the solvent. The two types of phosphorescence have different excitation spectra: that of the structureless and long-lived ³ππ* emission is shifted to the blue in the S₀→¹nπ* region and to the red in the S⁰→¹ππ* region. This emission is ascribed to complexes of 1 with the alcoholic solvent. The results of time-resolved measurements of the circular polarization of the luminescence are consistent with the assignments given above and indicate that in the H-bonded and possibly also in the free species ³ππ* and ³nπ* states are intermixed to a considerable extent.     

Carboranes Tuning the Phosphorescence of Iridium Tetrazolate Complexes

New iridium tetrazolate complexes containing o‐, m‐, or p‐carboranyl substitution in different positions of a phenylpyridine ligand have been prepared. The carborane isomers and the effect of their substitution position in the tuning of optical properties have been examined. The neutral complexes with the carboranyl substituent on the phenyl ring in meta position relative to the metal exhibit redshifted emission bands in contrast to blueshifts for those with carboranyl in para position. All cationic complexes display evidently blueshifted dual‐peak emission compared with the carborane‐free complex (c‐ TZ ) with a broad single‐peak emission. Introduction of carborane leads to a blueshift over 70 nm relative to c‐ TZ . Carboranes also significantly improve phosphorescence efficiency (Φ_P) and lifetime (τ), that is, Φ_P=0.64 versus 0.21 (c‐ TZ ) and τ=880 ns versus 241 ns (c‐ TZ ). The unique hydrophilic nido‐carborane‐based Ir^III complex nido‐o‐ 1 shows the largest phosphorescence efficiency (abs Φ_P=0.57) among known water‐soluble iridium complexes, long emission lifetime (τ=4.38 μs), as well as varying emission efficiency and lifetime with O₂ content in aqueous solution. Therefore, nido‐o‐ 1 has been used as an excellent oxygen‐sensitive phosphor for intracellular O₂ sensing and hypoxia imaging.     

Ancillary Ligand Effects on Red-Emitting Cyclometalated Iridium Complexes

In this work, a series of ten new red-emitting heteroleptic iridium(III) complexes of the type Ir(C^N)₂(L^X) (C^N=cyclometalating ligand, L^X=monoanionic chelating ancillary ligand) is introduced. The suite of new complexes includes two different cyclometalating ligands and five different ancillary ligands, with the primary goal of investigating the effect of the ancillary ligand structure on the excited-state dynamics. The structural variety of the ancillary ligands permitted investigations of the effects of donor atom identity, chelate ring size, and substituents on the electronic structure and excited state properties. Electrochemical analysis showed that the ancillary ligand has a substantial effect on the energy of the HOMO, whereas the LUMO is left unperturbed. Photoluminescence spectra showed that the ancillary ligand can sometimes strongly influence the emission wavelength, but in all cases is an important determinant of the excited-state dynamics.     

Pincer‐Type Platinum(II) Complexes Containing N‐Heterocyclic Carbene (NHC) Ligand: Structures,Photophysical and Anion‐Binding Properties,and Anticancer Activities

Two classes of pincer‐type Pt^II complexes containing tridentate N‐donor ligands ( 1 – 8 ) or C‐deprotonated N^C^N ligands derived from 1,3‐di(2‐pyridyl)benzene ( 10 – 13 ) and auxiliary N‐heterocyclic carbene (NHC) ligand were synthesized. [Pt(trpy)(NHC)]²⁺ complexes 1 – 5 display green phosphorescence in CH₂Cl₂ (Φ: 1.1–5.3 %; τ: 0.3–1.0 μs) at room temperature. Moderate‐to‐intense emissions are observed for 1 – 7 in glassy solutions at 77 K and for 1 – 6 in the solid state. The [Pt(N^C^N)(NHC)]⁺ complexes 10 – 13 display strong green phosphorescence with quantum yields up to 65 % in CHCl₃. The reactions of 1 with a wide variety of anions were examined in various solvents. The tridentate N‐donor ligand of 1 undergoes displacement reaction with CN^? in protic solvents. Similar displacement of the N^C^N ligand by CN^? has been observed for 10 , leading to a luminescence “switch‐off” response. The water‐soluble 7 containing anthracenyl‐functionalized NHC ligand acts as a light “switch‐on” sensor for the detection of CN^? ion with high selectivity. The in vitro cytotoxicity of the Pt^II complexes towards HeLa cells has been evaluated. Complex 12 showed high cytotoxicity with IC₅₀ value of 0.46 μM , whereas 1 – 4 and 6 – 8 are less cytotoxic. The cellular localization of the strongly luminescent complex 12 traced by using emission microscopy revealed that it mainly localizes in the cytoplasmic structures rather than in the nucleus. This complex can induce mitochondria dysfunction and subsequent cell death.     

Manipulation of Phosphorescence Efficiency of Cyclometalated Iridium Complexes by Substituted o‐Carboranes

A series of [(C^N)₂Ir(acac)] complexes [{5‐(2‐R‐CB)ppy}₂Ir(acac)] ( 3 a – 3 g ; acac=acetylacetonate, CB=o‐carboran‐1‐yl, ppy=2‐phenylpyridine; R=H ( 3 a ), Me ( 3 b ), iPr ( 3 c ), iBu ( 3 d ), Ph ( 3 e ), CF₃C₆H₄ ( 3 f ), C₆F₅ ( 3 g )) with various 2‐R‐substituted o‐carboranes at the 5‐position in the phenyl ring of the ppy ligand were prepared. X‐ray diffraction studies revealed that the carboranyl C?C bond length increases with increasing steric and electron‐withdrawing effects from the 2‐R substituents. Although the absorption and emission wavelengths of the complexes are almost invariant to the change of 2‐R group, the phosphorescence quantum efficiency varies from highly emissive (Φ_PL≈0.80 for R=H, alkyl) to poorly emissive (R=aryl) depending on the 2‐R group and the polarity of the medium. Theoretical studies suggest that 1) the almost nonemissive nature of the 2‐aryl‐substituted complexes is mainly attributable to the large contribution to the LUMO in the S₁ excited state from an o‐carborane unit and 2) the variation in the C?C bond length between the S₀ and T₁ state structures increases with increasing steric (2‐alkyl) and electronic effects (2‐aryl) of the 2‐R substituent and the polarity of the solvent. The solution‐processed electroluminescence (EL) devices that incorporated 3 b and 3 d as emitters displayed higher performance than the device based on the parent [(ppy)₂Ir(acac)] complex. Along with the high phosphorescence efficiency, the bulkiness of the 2‐R‐o‐carborane unit is shown to play an important role in improving device performance.     

Iridium(III) Sensitisers and Energy Upconversion: The Influence of Ligand Structure upon TTA-UC Performance

Six substituted ligands based upon 2-(naphthalen-1-yl)quinoline-4-carboxylate and 2-(naphthalen-2-yl)quinoline-4-carboxylate have been synthesised in two steps from a range of commercially available isatin derivatives. These species are shown to be effective cyclometallating ligands for Ir^III, yielding complexes of the form [Ir(C^N)₂(bipy)]PF₆ (where C^N=cyclometallating ligand; bipy=2,2′-bipyridine). X-ray crystallographic studies on three examples demonstrate that the complexes adopt a distorted octahedral geometry wherein a cis-C,C and trans-N,N coordination mode is observed. Intraligand torsional distortions are evident in all cases. The Ir^III complexes display photoluminescence in the red part of the visible region (668–693 nm), which is modestly tuneable through the ligand structure. The triplet lifetimes of the complexes are clearly influenced by the precise structure of the ligand in each case. Supporting computational (DFT) studies suggest that the differences in observed triplet lifetime are likely due to differing admixtures of ligand-centred versus MLCT character instilled by the facets of the ligand structure. Triplet–triplet annihilation upconversion (TTA-UC) measurements demonstrate that the complexes based upon the 1-naphthyl derived ligands are viable photosensitisers with upconversion quantum efficiencies of 1.6–6.7 %.     

Solid‐State Phosphorescence of trans‐Bis(salicylaldiminato)platinum(II) Complexes Bearing Long Alkyl Chains: Morphology Control towards Intense Emission

Morphology control for intense solid‐state phosphorescence of non‐emissive, but potentially emissive crystals of platinum complexes and the mechanistic rationale are described. A series of trans‐bis(salicylaldiminato)platinum(II) complexes bearing linear alkyl chains ( 1 a : n=5; 1 b : n=8; 1 c : n=12; 1 d : n=14; 1 e : n=16; 1 f : n=18) was synthesized and the solid‐state emission properties were examined by using crystals/aggregates prepared under various precipitation conditions. Crystals of 1 e , prepared using “kinetic” conditions including rapid cooling, high concentrations, and poor solvents, emit intensive yellow phosphorescence (λ_max=545 nm) under UV irradiation at 298 K with an absolute quantum efficiency of 0.36, whereas all the crystals of 1 a – 1 f prepared using “thermodynamic” conditions including slow cooling, low concentrations, and good solvents were either non‐ or less emissive with Φ_298K values of 0.12 ( 1 a ), 0.11 ( 1 b ), 0.10 ( 1 c ), 0.07 ( 1 d ), 0.02 ( 1 e ), and 0.02 ( 1 f ) under the same measurement conditions. The amorphous solid 1 e , prepared by rapid cooling and freeze‐drying, was also non‐emissive (Φ_298K=0.02, 0.02). Temperature‐dependent emission spectra showed that the kinetic crystals of 1 e exhibit high heat‐resistance towards emission decay with increasing temperature, whereas the amorphous solid 1 e is entirely heat‐quenchable. This is a rare example of the change from a non‐emissive crystal into a highly emissive crystal by morphology control through crystal engineering. Emission spectra and powder X‐ray diffraction (XRD) patterns of the emissive, kinetic crystals of 1 e are clearly distinct from those of the less emissive, thermodynamic crystals of 1 a – 1 f . Single‐crystal XRD unequivocally establishes that the thermodynamic crystals of 1 d have a multilayered lamellar structure supported by highly regulated, consecutive π‐stacking interactions between imine moieties, whereas the kinetic crystals of 1 e have a face‐to‐edge lamellar structure with less stacking. These results lead to the conclusion that 1) morphology control of long‐chained complexes exclusively generates a metastable herringbone‐based lamellar packing motif that exhibits intense emission and high heat‐resistance, while 2) a thermodynamically stable, highly regulated, consecutive stacking motif is unfavorable for solid‐state emission.