Highly phosphorescent platinum(II) complexes based on rigid unsymmetric tetradentate ligands

A new class of highly phosphorescent Pt(II) complexes (Pt1–Pt3) based on rigid unsymmetric tetradentate ligands (L1-L3) were designed and synthesized. L1-L3 ligands are an analogue to N,N-di(2-phenylpyrid-6-yl)aniline (L) except that one coordination phenyl group in L is replaced by other motifs with different electron donating/accepting capabilities. The effect associated with the modulation of a single coordination group within each ligand on the photophysical and electroluminescent properties of Pt1–Pt3 was investigated systematically. Among Pt1–Pt3, Pt1 has the highest HOMO due to the presence of a strong electron-donating group (3-methylindole), and exhibits the narrowest bandgap; Pt2 has the lowest HOMO due to the lack of strong donor group within the structure, and shows the widest bandgap. Organic light-emitting diodes (OLEDs) based on these three complexes showed yellowish green to greenish yellow electroluminescence with high efficiency. Notably, the device based on Pt1 at the doping level of 10 wt% achieved a maximum efficiency of 53.0 cd A⁻¹, 35.9 lm W⁻¹ and 16.3% with CIE coordinates of (0.44, 0.53).     

Green Ir(III) complexes with multifunctional ancillary ligands for highly efficient solution-processed phosphorescence organic light-emitting diodes with high current efficiency

Two new highly efficient green emitting heteroleptic Ir(III) complexes, namely, bis[5-(2-ethylhexyl)-8-(trifluoromethyl)benzo[c][1,5]naphthyridin-6(5H)-one]iridium-4-((3,5-di(9H-carbazol-9-yl)benzyl)oxy)picolinate (Ir-HT) and bis[5-(2-ethylhexyl)-8-(trifluoromethyl) benzo[c][1,5]naphthayridin-6(5H)-one]iridium-4-((4-(5-phenyl-1,3,4-oxadiazol-2-yl)benzyl) oxy)picolinate (Ir-ET) were designed and synthesized for solution-processed phosphorescence organic light-emitting diodes (PHOLEDs). These new Ir(III) complexes are based on amide-bridged trifluoromethyl (-CF₃) substituted phenylpyridine unit as main ligand and 1,3-bis(N-carbazolyl)benzene (mCP) unit and 1,3,4-oxadiazole (OXD) unit functionalized picolinate (pic) as an ancillary ligand. These multifunctional groups were attached into the 4-position of pic ancillary ligands via ether linkage. Interestingly, the solution-processed PHOLED device using Ir-HT as a dopant exhibited a maximum external quantum efficiency (EQE_max) of 20.92% and a maximum current efficiency (CE_max) of 64.04 cd A⁻¹. Whereas PHOLED device using Ir-ET displayed a EQE_max of 20.68% and a CE_max of 65.02 cd A⁻¹. This is one of best CE with high EQE for green Ir(III) complexes via solution-processed PHOLEDs using multifunctional ancillary ligands so far.     

Tetradentate Pt(II) 3,6-substitued salophen complexes: Synthesis and tuning emission from deep-red to near infrared by appending donor-acceptor framework

Two novel tetradentate platinum (II) 3,6-substituted salophen complexes of Pt-2 and Pt-3 were synthesized and characterized, in which the substituted group is a donor (D) unit of 4,4′-di(tert-butyl)triphenylamine (Bu^tTPA) for Pt-2 and a donor-acceptor (D-A) framework of Bu^tTPA and benzothiadiazole (BT) for Pt-3. Their thermal, optophysical, electrochemical and electroluminescent properties were primarily investigated. It is found that the emission for this type of tetradentate platinum (II) complexes is tuned from deep red to near infrared by appending D-A framework under photo-excitation. As a result, Pt-3 presented a significant near infrared electroluminescence peaked at 703 nm in its doped polymer light-emitting devices (PLEDs). The maximum external quantum efficiency of 0.88% is observed in the Pt-3 doped PLEDs using a blend of poly(vinylcarbazole) and 1,3-bis(5-(4-(tert-butyl)phenyl)-1,3,4-oxadiazol-2-yl) benzene as the host matrix. Our work indicates that appending D-A framework into tetradentate Pt(II) salophen complex is a useful strategy to get high-performance near infrared emission for this type of tetradentate Pt (II) complexes.     

Modulation of Solid‐State Aggregation of Square‐Planar Pt(II) Based Emitters: Enabling Highly Efficient Deep‐Red/Near Infrared Electroluminescence

The design of square‐planar Pt(II) complexes with highly efficient solid‐state near infrared (NIR) luminescence for electroluminescence is attractive but challenging. This study presents the fine‐turning of excited‐state properties and application of a series of isoquinolinyl pyrazolate Pt(II) complexes that are modulated by steric demanding substituents. It reveals that the bulky substituents do not always disfavor metallophilic Pt···Pt interactions. Instead, π–π stacking among chelates, which are fine‐tuned by the associated substituents, also exerts strong influence to the metal‐metal‐to‐ligand charge transfer (MMLCT) transition character. Theoretical calculations indicate that Pt···Pt contacts become more relevant in the trimers rather than the dimers, especially in their T₁ states, associated with a change from mixed ³LC/³MLCT transition in the monomer/dimer to mixed ³LC/³MMLCT transition character in the trimer. Electroluminescence devices affording intense deep‐red/NIR emission (near 670 nm) with unprecedentedly high external quantum efficiency over 30% are demonstrated. This work provides deep insights into formation MMLCT transition of square‐planar Pt(II) complexes and efficient molecular design for deep‐red/NIR electroluminescence.     

Synthesis and photophysical characterization of an ionic fluorene derivative for blue light-emitting electrochemical cells

A highly fluorescent an ionic fluorene derivative 1 was synthesized and its photophysical, electrochemical and electroluminescence characteristics were investigated. Deep blue emissions were observed for compound 1 in solid as well as in dilute solutions. The synthesized compound shows high fluorescence quantum yield around 77% indicates that compound 1 can perform its role as efficient ionic emitter in LEC devices. Light-emitting electrochemical cell (LEC) devices were fabricated incorporating compound 1 without (device I) and with (device II) ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate (BMIM·PF₆). Devices I and II exhibited blue electroluminescence maximum centered at 455 and 454 nm with CIE coordinates of (0.15, 0.21) and (0.16, 0.22), respectively. Maximum luminance and current efficiency of 1105 cd m⁻² and 0.14 cd A⁻¹ respectively, has achieved for device I while that of device II resulted in 1247 cd m⁻² and 0.14 cd A⁻¹ respectively.     

An asymmetric small molecule based on thieno[2,3-f]benzofuran for efficient organic solar cells

A new asymmetric small molecule, named R3T-TBFO, with 4,8-bis(2-ethylhexyloxy)-substituted thieno[2,3-f]benzofuran (TBF) as central donor block, has been synthesized and used as donor material in organic solar cells (OSCs). With thermal annealing (TA) and solvent vapor annealing (SVA) treatment, the blend of R3T-TBFO/PC₇₁BM shows a higher hole mobility of 1.37 × 10⁻⁴ cm² V⁻¹ s⁻¹ and a more balanced charge mobilities. Using a structure of ITO/PEDOT:PSS/R3T-TBFO:PC₇₁BM/ZrAcac/Al, the device with TA treatment delivered a moderate power conversion efficiency (PCE) of 5.63%, while device after TA + SVA treatment showed a preferable PCE of 6.32% with a high fill factor (FF) of 0.72.     

Synthesis and device properties of mCP analogues based on fused-ring carbazole moiety

Novel mCP analogues consisting of blue phosphorescent host materials with fused-ring, 1,3-bis(5H-benzofuro[3,2-c]carbazol-5-yl)benzene (BFCz) and 1,3-bis(5H-benzo[4,5]thieno[3,2-c]carbazol-5-yl)benzene (BTCz) were designed and synthesized using benzofurocarbazole and benzothienocarbazole donor moieties. BFCz and BTCz exhibit high glass transition temperatures of 147 and 157 °C, respectively, and high triplet bandgaps of 2.94 and 2.93 eV, respectively. To explore the electroluminescence properties of these materials, multilayer blue phosphorescent organic light-emitting diodes (PHOLEDs) were fabricated in the following device structure: indium–tin-oxide (ITO)/PEDOT:PSS/4,4’-cyclohexylidene bis[N,N-bis(4-methylphenyl)aniline] (TAPC)/1,3-bis(N-carbazolyl) benzene (mCP)/host:FIrpic/diphenylphosphine oxide-4-(triphenylsilyl)phenyl (TSPO1)/LiF)/Al. The PHOLEDs with BTCz exhibited efficient blue emission with luminous and quantum efficiencies of 30.9 cd/A and 15.5% at 1000 cd/m², respectively.     

Triphenylamine-based trinuclear Pt(II) complexes for solution-processed OLEDs displaying efficient pure yellow and red emissions

Highly efficient phosphors are critical in solution-processed organic light-emitting devices (OLEDs). Multinuclear Ir(III) complexes containing more than one metal center have showed great potential in fabricating high performance OLEDs, yet the electroluminescent (EL) properties of multinuclear Pt(II) complexes are rarely studied. In this work, two neutral trinuclear Pt(II) complexes are synthesized based on the triphenylamine core bearing three bidentate ligand arms. Both the yellow emitter (PyTPt) and deep-red emitter (IqTPt) exhibit improved photoluminescent quantum yields (PLQYs) compared with their corresponding mononuclear Pt(II) complexes. Furthermore, the PLQYs of PyTPt and IqTPt doped films are increased to 0.63 and 0.47, respectively. The solution-processed pure yellow-emitting device based on PyTPt achieves impressively high external quantum efficiency (EQE), current efficiency (CE), and power efficiency (PE) of 16.92%, 56.74 cd/A and 29.09 lm W⁻¹, respectively, which are among the best performance reported for the OLEDs employing multinuclear Pt(II) complexes. The solution-processed device based on IqTPt shows pure red emission with the peak EQE approaching 9.0%. Both PyTPt and IqTPt display much higher EL efficiencies than their corresponding mononuclear Pt(II) complexes. This work demonstrates that it is an attritive strategy to develop multinuclear Pt(II) complexes for high-performance OLEDs.     

Computational studies on the radiative and nonradiative processes of luminescent N-heteroleptic platinum(II) complexes

Three N-heteroleptic Pt(II) complexes, [Pt(C^C)(O^O)] [O^O = acetylacetonate, C^C = 1-phenyl-1,2,4-triazol-5-ylidene (1), C^C = 4-phenyl-1,2,4-triazol-5-ylidene (2), C^C = 2-phenylpyrazine (3)] have been investigated with density functional theory (DFT) and time-dependent density functional theory (TDDFT). The radiative decay rate constants of complexes 1–3 have been discussed with the oscillator strength (f_n), the strength of spin–orbit coupling (SOC) interaction between the lowest energy triplet excited state (T₁) and singlet excited states (S_n), and the energy gaps between E(T₁) and E(S_n). To illustrate the nonradiative decay processes, the transition states between triplet metal-centered (³MC) and T₁ states have been optimized and were verified with the calculations of vibrational frequencies and intrinsic reaction coordinate (IRC). In addition, the minimum energy crossing points (MECPs) between ³MC and ground states (S₀) were optimized. At last, the potential energy curves relevant to the nonradiative decay pathways are simulated. The results show that complex 3 has the biggest photoluminescence quantum yield because the complex 3 has the biggest radiative decay rate constant and the smallest nonradiative decay rate constant in complexes 1–3.     

3,7-Bis((E)-2-oxoindolin-3-ylidene)-3,7-dihydrobenzo[1,2-b:4,5-b′]dithiophene-2,6-dione (IBDT) based polymer with balanced ambipolar charge transport performance

A novel acceptor building block, 3,7-bis((E)-2-oxoindolin-3-ylidene)-3,7-dihydrobenzo[1,2-b:4,5-b′]dithiophene-2,6-dione (IBDT), is developed to construct a donor-acceptor polymer PIBDTBT-40. This polymer has favorable highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energy levels for balanced ambipolar charge transport. Organic thin film transistors (OTFTs) based on this polymer shows well-balanced ambipolar characteristics with electron mobility of 0.14 cm² V⁻¹ s⁻¹ and hole mobility of 0.10 cm² V⁻¹ s⁻¹ in bottom-gate bottom-contact devices. This polymer is a promising semiconductor for solution processable organic electronics such as CMOS-like logic circuits.     

High mobility ambipolar organic field-effect transistors with a nonplanar heterojunction structure

Ambipolar organic field-effect transistors (OFETs) based on a bilayer structure of highly crystalline small molecules, n-type α,ω-diperfluorohexylquaterthiophene (DFH-4T) and p-type dinaphtho[2,3-b:2′,3′-f]thieno[3,2-b]thiophene (DNTT), are investigated. By employing DFH-4T/DNTT as the bottom/top layers and appropriate high work function (WF) electrodes in a bottom-gate, top-contact configuration, the superior ambipolar characteristics with matched electron and hole mobilities of 1–1.1 cm² V⁻¹ s⁻¹ are achieved. Intriguingly, this high-performance device exhibits a unique feature of an extremely rough, nonplanar heterojunction in the DFH-4T/DNTT combination and a large electron injection barrier from the high WF electrodes to DFH-4T, suggesting some underlying mechanisms for the effective charge transport and injection. The electrical and structural analyses reveal that the crystal packing of the bottom DFH-4T layer supports the growth of a high-quality DNTT crystal network for high-mobility hole transport upon the nonplanar heterojunction, and also enables the formation of an enlarged organic/metal contact surface for efficient electron injection from the high WF electrodes, as the key attributes leading to an overall excellent ambipolar behavior. The effect of intrinsic charge accumulation at the heterojunction interface on the ambipolar conduction is also discussed. Furthermore, a complementary-like inverter constructed with two DFH-4T/DNTT ambipolar OFETs is demonstrated, which shows a gain of 30.     

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

A series of Ir(III) complexes [(CˆN)₂Ir(PˆSiO)], where (CˆN)H is 2-phenylisoquinoline (1), 2-phenylpyridine (2) or 2-(2,4-difluorophenyl)pyridine (3), and (PˆSiO)H is an organosilanolate ancillary chelate with either diphenylsilyl (a) or dimethylsilyl (b) substituent, are investigated by means of the density functional theory/time-dependent density functional theory (DFT/TD-DFT). Their relationship between structure and property is evaluated by the geometries, electronic structure, and absorption and phosphorescence spectra associated with the internal quantum yield. The effect of different substitutions on the ancillary ligand is explored by compare of the complexes 1a (2a/3a) and 1b (2b/3b). Furthermore, five complexes, 2b-1, 2b-2, 2b-3, 2b-4, and 2b-5, are newly designed by introduction of the substitution groups on the phenyl rings of the 2b (See Fig. 1). The theoretical result estimates that the complexes 2b-1, 2b-2, 2b-4, and 2b-5 would be the blue-emitting phosphors. Especially, the complex 2b-1 has a higher quantum yield relative to 2b by comparison of the factors governing the radiative decay rate constants of the emissive state and the feasibility of the deactivation process from the T₁ state via triplet metal-centered (³MC) state.     

2,2-Dicyanovinyl-end-capped oligothiophenes as electron acceptor in solution processed bulk-heterojunction organic solar cells

Three 2,2-dicyanovinyl (DCV) end-capped A-π-D-π-A type oligothiophenes (DCV-OTs) containing dithieno[3,2-b:2′,3′-d]silole (DTSi), cyclopenta[1,2-b:3,4-b′]dithiophene (DTCP) or dithieno[3,2-b:2′,3′-d]pyrrole (DTPy) unit as the central donor part, mono-thiophene as the π-conjugation bridge were synthesized. The absorption spectroscopies, cyclic voltammetry of these compounds were characterized. Results showed that all these compounds have intensive absorption band over 500–680 nm with a LUMO energy level around −3.80 eV, which is slightly higher than that of [6,6]phenyl-C₆₁-butyric acid methyl ester (PC₆₁BM, E_LUMO = −4.01 eV), but lower than that of poly(3-hexylthiophene) (P3HT, E_LUMO = −2.91 eV). Solution processed bulk heterojunction “all-thiophene” solar cells using P3HT as electron donor and the above mentioned oligothiophenes as electron acceptor were fabricated and tested. The highest power conversion efficiency (PCE) of 1.31% was achieved for DTSi-cored compound DTSi(THDCV)₂, whereas PTB7:DTSi(THDCV)₂ based device showed slightly higher PCE of 1.56%. Electron mobilities of these three compounds were measured to be around 10⁻⁵ cm² V⁻¹ s⁻¹ by space charge limited current method, which is much lower than that of PC₆₁BM, and was considered as one of the reason for the low photovoltaic performance.     

Exploring the influence of different ancillary ligands of heteroleptic Ir(III) complexes on the phosphorescent properties: Emissive rule and photodeactivation dynamics

The complexity of emissive process for five heteroleptic Ir(III) complexes (dfpypy)₂Ir(LˆX), where dfpypy = 4-methyl-2',6'-difluoro-2,3'-bipyridine and LˆX = picolinate (1), dipivaloylmethanate (2), picolinic acid N-oxide (3), N,N'-di-tert-butylbenzamidinate (4), or 5-(4′-methylpyridine-2'-yl)-3-trifluoromethyl-1,2,4-triazole (5) (See Fig. 1), is unveiled by density functional theory (DFT) and quadratic response (QR) time-dependent (TD)DFT calculations including spin-orbit coupling (SOC). Besides the emission wavelength, we would like to pay intense attention on the emissive rule. It is found that the emission likely originates from different triplet states rather than only from the lowest Kasha state for complexes 1, 2, 3, and 5, which indicates they obey dual emission scenarios. In contrast, complex 4 follows the Kasha rule. Different from the total qualitative study, the quantum yield is semi-quantitatively determined in this work. The radiative decay rate constants (k_r) from possible emissive states are quantitatively determined by the quadratic response method. The triplet potential energy surfaces are constructed to elucidate the factors that affect the temperature-dependent nonradiative rate constants (k_nr). Complex 4 have the higher quantum yields in all the investigated complexes because of the larger k_r and smaller k_nr. The metal-centered (³MC) triplet state in the deactivation pathways is confirmed to play a vital role in determining the quantum yield.     

Molecular Engineering for Shortening the Pt···Pt Distances in Pt(II) Dinuclear Complexes and Enhancing the Efficiencies of these Complexes for Application in Deep-Red and Near-IR OLEDs

Deep-red (DR)-to-near-infrared (NIR) phosphorescent organic light-emitting diodes (OLEDs) have potentials for application in various fields ranging from phototherapy to sensing. Accordingly, herein, phenylpyridazine-based bidentate ligands are synthesized and subsequently utilized for the preparation of dinuclear Pt(II) complexes ( 1 – 6 ). The molecular structures of 1 – 3 is investigated by single-crystal X-ray diffraction, and the results suggest that these complexes have substantially shortened Pt···Pt distances (2.906–2.911 Å). Complexes 1 – 6 exhibit intense emissions in the NIR region (700–726 nm), high photoluminescence quantum yield (PLQY) (0.11–0.18), and short phosphorescence decay lifetimes (τ = 0.64–0.95 µs) in a CH₂Cl₂ solution. To examine the effect of N-substitution on the dinuclear Pt complexes, the phenylpyrimidine-based Pt(II) emitters 7 and 8 are prepared and discovered to have Pt···Pt distances of 2.933 Å. 7 and 8 demonstrate strong emissions in the 628–650 nm range with high PLQY of 0.52–0.65. Theoretical studies indicate that the functional groups or atoms in the ligands play crucial roles in the formation of emitters with significantly shortened Pt···Pt distances. 3 and 7 are employed as non-doped emitters to fabricate NIR OLEDs, and the resulting OLEDs exhibit electroluminescence peaks at 754 and 692 nm with maximum external quantum efficiencies of 3.0 and 4.4%, respectively.     

Highly efficient thienylquinoline-based phosphorescent iridium(III) complexes for red and white organic light-emitting diodes

Highly efficient 2-(thiophen-2-yl)quinoline-based phosphorescent iridium(III) complexes bearing 2-(3-(trifluoromethyl)-1H-1,2,4-triazol-5-yl)pyridine or picolinic acid as ancillary ligands are designed and synthetised. The variation of ancillary ligands is attempted to finely tune the photophysical properties of these complexes, especially the solution phosphorescent quantum yields (ΦPL), full width at half maximum (FWHM), etc. The picolinic acid-based complex displays the slightly red-shifted dual-peak emission compared to triazolpyridine-based one. The complexes show bright emission with broad FWHM up to 83 nm, and the emissions are in red region with the very high absolute ΦPL up to 0.76 in solution. Moreover, high-performance red and three-color-based white organic light-emitting diodes (OLEDs) with excellent color stability have been fabricated. The maximum external quantum efficiencies of red and white OLEDs can reach 16.2% and 15.1%, respectively. The maximum current efficiency and power efficiency of white OLED are as high as 35.5 cd A⁻¹ and 34.0 lm W⁻¹, respectively. Especially, the designed white OLED exhibits excellent spectral stability under wide operating voltage range, and the 1931 Commission Internationale de L'Eclairage of white OLED only changes from (0.43, 0.42) to (0.44, 0.44), the color rendering index is in a narrow range of 75–77.     

Green and blue–green light-emitting electrochemical cells based on cationic iridium complexes with 2-(4-ethyl-2-pyridyl)-1H-imidazole ancillary ligand

The ionic iridium complexes, [Ir(ppy)₂(EP-Imid)]PF₆ (Complex 1) and [Ir(dfppy)₂(EP-Imid)]PF₆ (Complex 2) are used as the light-emitting material for the fabrication of light-emitting electrochemical cells (LECs). These complexes have been synthesized, employing 2-(4-ethyl-2-pyridyl)-1H-imidazole (EP-Imid) as the ancillary ligand, 2-phenylpyridine (ppy) and 2-(2,4-difluorophenyl)pyridine (dfppy) as the cyclometalated ligands, which were characterized by various spectroscopic, photophysical and electrochemical methods. The photoluminescence (PL) emission spectra in acetonitrile solution show blue–green and blue light emission for Complexes 1 and 2 respectively. However, LECs incorporating these complexes resulted in green (522 nm) light emission for Complex 1 with the Commission Internationale de L’Eclairage (CIE) coordinates of (0.33, 0.56) and blue–green (500 nm) light emission for Complex 2 with the CIE coordinates of (0.24, 0.44). Using Complex 1, a maximum luminance of 1191 cd m⁻² and current efficiency of 1.0 cd A⁻¹ are obtained while that of Complex 2 are 741 cd m⁻² and 0.88 cd A⁻¹ respectively.     

The transition from bipolaron to triplet-polaron magnetoresistance in a single layer organic semiconductor device

We measure the current–voltage–luminescence (I–V–L) and Magneto-Conductance (MC) response of a poly(3-hexyl-thiophene) (P3HT) based device (Au/P3HT(300 nm)/Al) in forward and reverse bias. In reverse bias (<1 V), the negative MC is described by a single non-Lorentzian function, consistent with the bipolaron theory. In forward bias, the transition from negative saturation MC (low bias) to positive saturation MC (high bias) occurs when the current density exceeds ∼10⁻² A cm⁻² and coincides with electroluminescence. Under these conditions the triplet density (∼10¹⁵ cm⁻³) becomes comparable to the hole density (∼10¹⁶ cm⁻³), consistent with the triplet-polaron interaction theory. From the current density dependence of the MC we conclude that in forward bias both mechanisms must be occurring simultaneously, within a given device, and that the overall sign of the MC results from competition between the two mechanisms.     

Pt–Cu Interaction Induced Construction of Single Pt Sites for Synchronous Electron Capture and Transfer in Photocatalysis

Single-atom photocatalysts have shown their fascinating strengths in enhancing charge transfer dynamics; however, rationally designing coordination sites by metal doping to stabilize isolated atoms is still challenging. Here, a one-unit-cell ZnIn₂S₄ (ZIS) nanosheet with abundant Cu dopants serving as the suitable support to achieve a single atom Pt catalyst (Pt₁/Cu–ZIS) is reported, and hence the metal single atom–metal dopant interaction at an atomic level is disclosed. Experimental results and density functional theory calculations highlight the unique stabilizing effect (Pt–Cu interaction) of single Pt atoms in Cu-doped ZIS, while apparent Pt clusters are observed in pristine ZIS. Specifically, Pt–Cu interaction provides an extra coordination site except three S sites on the surface, which induces a higher diffusion barrier and makes the single atom more stable on the surface. Apart from stabilizing Pt single atoms, Pt–Cu interaction also serves as the efficient channel to transfer electrons from Cu trap states to Pt active sites, thereby enhancing the charge separation and transfer efficiency. Remarkably, the Pt₁/Cu–ZIS exhibits a superb activity, giving a photocatalytic hydrogen evolution rate of 5.02 mmol g⁻¹ h⁻¹, nearly 49 times higher than that of pristine ZIS.     

Theoretical studies on cyclometalated platinum(II) complexes based on isoquinolinyl azolate: ππ-stacking interaction and photophysical properties

The photophysical properties of four Pt(II) complexes [Pt(Lx)₂], x = 1–4, (1–4), where Lx are 6-t-butyl-1-(3-trifluoro-methyl-1H-pyrazol-5-yl) isoquinoline (1), 3,5-di-t-butyl-1-(3-trifluoromethyl-1H-pyrazol-5-yl) isoquinoline (2), 6-(2,6-diisopropylphenyl)-1-(3-trifluoro-methyl-1H-pyrazol-5-yl) isoquinoline (3), and 4-(2,6-diisopropylphenyl)-1-(3-trifluoro-methyl-1H-pyrazol-5-yl) isoquinoline (4), are investigated by the density functional theory (DFT) and time-dependent density functional theory (TD-DFT). Furthermore, the binding interaction in Pt_n stack is studied to discover the influence of different cyclometalated ligand. The calculated results rationalize that the complex 1 exhibits a stack of three molecules rather than the infinite aligned stack. Complexes 1 and 3 present the stronger tendency to form the aligned ππ-stacking interaction as compared with complexes 2 and 4. The dimers of other four complexes, 3a (Pt(L3)(Ma), Ma = 5-(2-pyridyl)-3-trifluoromethylpyrazole), 3b (Pt(L3)(Mb), Mb = 5-(4-phenyl-2-pyridyl)-3-trifluoromethylpyrazole), 3c (Pt(L3)(Mc), Mc = 5-(4-tert-butyl-2-pyridyl)-3-trifluoromethylpyrazole), and 5 (Pt(fppz)₂ fppz = 5-(2-pyridyl)-3-trifluoromethylpyrazole), are also studied to investigate the effect of different aromatic ligand or substituents on the ππ-stacking interaction. The emissions of complexes 1–4 originate from various charge transfer states including the intraligand charge transfer (ILCT) and ligand-to-ligand charge transfer (LLCT) together with the metal-to-ligand charge transfer (MLCT). Finally, the items related with the radiative and nonradiative rate constants are examined. Besides the potential energy profile between the lowest triplet state (³MLCT) and metal centered state (³MC), the deactivation process of the ³MC state via the minimum energy crossing point (MECP) between the ³MC and the ground state (¹S₀) potential surfaces is also explored.