Intramolecular Phosphacyclization: Polyaromatic Phosphonium P-Heterocycles with Wide-Tuning Optical Properties

Rationally designed cationic phospha-polyaromatic fluorophores were prepared through intramolecular cyclization of the tertiary ortho-(acene)phenylene-phosphines mediated by Cu^II triflate. As a result of phosphorus quaternization, heterocyclic phosphonium salts 1 c – 3 c , derived from naphthalene, phenanthrene, and anthracene cores, exhibited very intense blue to green fluorescence (Φ_em=0.38–0.99) and high photostability in aqueous medium. The structure–emission relationship was further investigated by tailoring the electron-donating functions to the anthracene moiety to give dyes 4 c – 6 c with charge-transfer character. The latter significantly decreases the emission energy to reach near-IR region. Thus, the intramolecular phosphacyclization renders an ultra-wide tuning of fluorescence from 420 nm ( 1 c ) to 780 nm ( 6 c ) in solution, extended to 825 nm for 6 c in the solid state with quantum efficiency of approximately 0.07. The physical behavior of these new dyes was studied spectroscopically, crystallographically, and electrochemically, whereas computational analysis was used to correlate the experimental data with molecular electronic structures. The excellent stability, water solubility, and attractive photophysical characteristics make these phosphonium heterocycles powerful tools in cell imaging.     

Highly Emissive 9-Borafluorene Derivatives: Synthesis,Photophysical Properties and Device Fabrication

A series of 9-borafluorene derivatives, functionalised with electron-donating groups, have been prepared. Some of these 9-borafluorene compounds exhibit strong yellowish emission in solution and in the solid state with relatively high quantum yields (up to 73.6 % for FMesB-Cz as a neat film). The results suggest that the highly twisted donor groups suppress charge transfer, but the intrinsic photophysical properties of the 9-borafluorene systems remain. The new compounds showed enhanced stability towards the atmosphere, and exhibited excellent thermal stability, revealing their potential for application in materials science. Organic light-emitting diode (OLED) devices were fabricated with two of the highly emissive compounds, and they exhibited strong yellow-greenish electroluminescence, with a maximum luminance intensity of >22 000 cd m⁻². These are the first two examples of 9-borafluorene derivatives being used as light-emitting materials in OLED devices, and they have enabled us to achieve a balance between maintaining their intrinsic properties while improving their stability.     

Synthesis and Chiroptical Properties of Chiral Carbazole-Based BODIPYs

A series of carbazole-based boron dipyrromethenes (BODIPYs) 2 a – g bearing binaphthyl units have been synthesized by the Et₂AlCl-mediated reaction of the corresponding BODIPY difluorides 1 a – g with 1,1′-binaphthalene-2,2′-diol. Substituents such as halogen, nitrile, and amino groups were tolerated under the reaction conditions, and the reaction of the phenylethynyl-substituted 1 h gave (R,R)- 3 h bearing two binaphthyl units. The chiroptical properties of these dyes with different substituents were investigated by UV/Vis, CD, fluorescence, and circularly polarized luminescence (CPL) spectroscopy. The CD spectra showed Cotton effects in the absorption region of the BODIPY moieties. In addition, they showed CPL both in solution and in the solid state. Interestingly, several dyes recorded higher g_lum values in the solid state, probably due to intermolecular interactions. Because (R,R)- 3 h recorded relatively low g_lum values, the diastereomer (R,S)- 3 h was prepared. The (R,S) diastereomer showed intense CPL, which suggests a synergetic effect of the two binaphthyl groups. Finally, chiral carbazole-based BODIPY dimers have been synthesized for the first time and their chiroptical properties were investigated. They showed redshifted fluorescence and CPL, which reached the near-IR (NIR) region in the solid state.     

Vaulted trans‐Bis(salicylaldiminato)platinum(II) Crystals: Heat‐Resistant,Chromatically Sensitive Platforms for Solid‐State Phosphorescence at Ambient Temperature

The synthesis, structure, and solid‐state emission of vaulted trans‐bis(salicylaldiminato)platinum(II) complexes are described. A series of polymethylene ( 1 : n=8; 2 : n=9; 3 : n=10; 4 : n=11; 5 : n=12; 6 : n=13) and polyoxyethylene ( 7 : m=2; 8 : m=3; 9 : m=4) vaulted complexes (R=H ( a ), 3‐MeO ( b ), 4‐MeO ( c ), 5‐MeO ( d ), 6‐MeO ( e ), 4‐CF₃O ( f ), 5‐CF₃O ( g )) was prepared by treating [PtCl₂(CH₃CN)₂] with the corresponding N,N′‐bis(salicylidene)‐1,ω‐alkanediamines. The trans coordination, vaulted structures, and the crystal packing of 1 – 9 have been unequivocally established from X‐ray diffraction studies. Unpredictable, structure‐dependent phosphorescent emission has been observed for crystals of the complexes under UV excitation at ambient temperature, whereas these complexes are entirely nonemissive in the solution state under the same conditions. The long‐linked complex crystals 4 – 6 , 8 , and 9 exhibit intense emission (Φ_77K=0.22–0.88) at 77 K, whereas short‐linked complexes 1 – 3 and 7 are non‐ or slightly emissive at the same temperature (Φ_77K<0.01–0.18). At 298 K, some of the long‐linked crystals, 4 a , 4 b , 5 c , 5 e , 6 c , 6 e , and 9 b , completely lose their high‐emission properties with elevation of the temperature (Φ_298K<0.01–0.02), whereas the other long‐linked crystals, 5 a , 6 a , 9 a , and 9 d , exhibit high heat resistance towards emission decay with increasing temperature (Φ_298K=0.21–0.38). Chromogenic control of solid‐state emission over the range of 98 nm can be performed simply by introducing MeO groups at different positions on the aromatic rings. Orange, yellow‐green, red, and yellow emissions are observed in the glass and crystalline state upon 3‐, 4‐, 5‐, and 6‐MeO substitution, respectively, whereas those with CF₃O substituents have orange emission, irrespective of the substitution position. DFT calculations (B3LYP/6‐31G*, LanL2DZ) showed that such chromatic variation is ascribed to the position‐specific influence of the substituents on the highest‐occupied molecular orbital (HOMO) and lowest‐unoccupied molecular orbital (LUMO) levels of the trans‐bis(salicylaldiminato)platinum(II) platform. The solid‐state emission and its heat resistance have been discussed on the basis of X‐ray diffraction studies. The planarity of the trans‐coordination sites is strongly correlated to the solid‐state emission intensities of crystals 1 – 9 at lower temperatures. The specific heat‐resistance properties shown exclusively by the 5 a , 6 a , 9 a , and 9 d crystals are due to their strong three‐dimensional hydrogen‐bonding interactions and/or Pt???Pt contacts, whereas heat‐quenchable crystals 4 a , 4 b , 5 c , 5 e , 6 c , 6 e , and 9 b are poorly bound with limited interactions, such as non‐, one‐, or two‐dimensional hydrogen‐bonding networks. These results lead to the conclusion that Pt???Pt contacts are an important factor in the heat resistance of solid‐state phosphorescence at ambient temperature, although the role of Pt???Pt contacts can be substituted by only higher‐ordered hydrogen‐bonding fixation.     

Highly Emissive Boron Ketoiminate Derivatives as a New Class of Aggregation‐Induced Emission Fluorophores

A series of boron ketoiminate derivatives that exhibited clear aggregation‐induced emission (AIE) characteristics (in THF: Φ_PL≤0.01; in the solid state: Φ_PL=0.30–0.76) were prepared by the reactions of 1,3‐enaminoketone derivatives with boron trifluoride–diethyl etherate. The structures and optical properties were investigated by UV‐visible spectroscopy, photoluminescent (PL) spectroscopy, and X‐ray single‐crystal measurements. These results indicate that the AIE characteristics were derived from molecular motions of the boron‐chelating rings with a boron? nitrogen (B? N) bond. Furthermore, the optical properties were controllable by steric hindrance of the substituted groups on the nitrogen atom.     

Synthesis,Structure, and Photophysical Properties of the Di‐ and Trinuclear Phosphine‐Diimine Complexes of Copper(I)

Reactions of [Cu(NCMe)₄]⁺ with stoichiometric amount of diphosphine R₂P–(C₆H₄)_n–PR₂, (R = NC₄H₄, n = 1; R = Ph, n = 1, 2, 3) or tri‐phosphine 1, 3, 5‐(PPh₂–C₆H₄–)₃–C₆H₃ ligands give the corresponding di‐ or trinuclear copper(I) acetonitrile‐phosphine complexes 1 – 5 . Substitution of the labile acetonitrile groups with chelating aromatic diimines – 2, 2′‐bipyridine (bpy), 1, 10‐phenanthroline (phen), 5, 6‐dimethyl‐1, 10‐phenanthroline (dmp), 5, 6‐dibromo‐1, 10‐phenanthroline (phenBr₂) – gives the corresponding substituted compounds 6 – 16 . In all complexes 1 – 16 each central Cu^I atom has tetrahedral configuration completed with two N‐ and two P‐donor groups. The compounds obtained were characterized using elemental analysis, ESI‐MS, X‐ray crystallography, and NMR spectroscopy. All phosphine‐diimine compounds 6 – 16 are photoluminescent at room temperature both in dichloromethane solution and in solid state (λ_ex = 385 nm). In CH₂Cl₂ solution the maxima of emission bands are found in a range 540–640 nm, and in solid in a similar range 538–620 nm. Emission of 6 – 16 is assigned to the triplet excited state dominated by the charge transfer transitions with contribution of the MLCT character.     

Optoelectronic,Aggregation, and Redox Properties of Double-Rotor Boron Difluoride Hydrazone Dyes

We develop the chemistry of boron difluoride hydrazone dyes (BODIHYs) bearing two aryl substituents and explore their properties. The low-energy absorption bands (λ_max=427–464 nm) of these dyes depend on the nature of the N-aryl groups appended to the BODIHY framework. Electron-donating and extended π-conjugated groups cause a redshift, whereas electron-withdrawing groups result in a blueshift. The title compounds were weakly photoluminescent in solution and strongly photoluminescent as thin films (λ_PL=525–578 nm) with quantum yields of up to 18 % and lifetimes of 1.1–1.7 ns, consistent with the dominant radiative decay through fluorescence. Addition of water to THF solutions of the BODIHYs studied causes molecular aggregation which restricts intramolecular motion and thereby enhances photoluminescence. The observed photoluminescence of BODIHY thin films is likely facilitated by a similar molecular packing effect. Finally, cyclic voltammetry studies confirmed that BODIHY derivatives bearing para-substituted N-aryl groups could be reversibly oxidized (E_ox1=0.62–1.02 V vs. Fc/Fc⁺) to their radical cation forms. Chemical oxidation studies confirmed that para-substituents at the N-aryl groups are required to circumvent radical decomposition pathways. Our findings provide new opportunities and guiding principles for the design of sought-after multifunctional boron difluoride complexes that are photoluminescent in the solid state.     

Influence of lateral methyl and terminal substituents on the mesophase behaviour of four rings azo-ester liquid crystal compounds

ABSTRACT

The effect of introducing a lateral methyl substitution into the previously investigated laterally neat four-ring analogues, 4-substituted phenylazo phenyl 4?-(4?-alkoxyphenylazo) benzoates (In_a–e), on their mesophase behaviour was investigated for the newly prepared five homologous series of 4-substituted phenylazo phenyl 4?-(3?-methyl-4?-alkoxyphenylazo) benzoates (IIn_a–e). Within each homologous series, the alkoxy group varies between 6, 8, 10, 12, 14, and 16 carbons, while the substituent, X, is a polar group that alternatively changes between the electron-donating (CH₃O and CH₃) groups, and the electron-withdrawing (Br and NO₂) groups, including the unsubstituted homologues (IIn_c). Their mesophase stabilities were determined by DSC and phases identified by PLM. The results showed that independent of the alkoxy-chain length or the polarity of the substituent X, the nematic phase is predominant with relatively high stability and wide temperature ranges. All compounds show a good thermal stability in the mesophases domain, except the nitro and Br substituted derivatives bearing short alkoxy chain length. Comparison of the mesophase behaviour was also made between the present series and corresponding three-ring laterally CH_3-substituted azo/ester analogues. UV-vis absorption spectra revealed that derivatives with electron donating or an electron withdrawing groups exhibited redshifts of the π→π* transition compared with unsubstituded derivative.     

Janus-Type AIE Fluorophores: Synthesis and Properties of π-Extended Coumarin-Bearing Triskelions

Janus-type triskelion-shaped fluorophores comprising coumarins bearing various electron-donating substituents (1aad, 1add, 1ccd, and 1cdd) were successfully synthesized via an intramolecular Ullmann coupling. Density functional theory (DFT) calculations indicated that all the compounds presented two different molecular surfaces, similar to Janus-type molecules. The absorption and fluorescence spectra of asymmetrical derivatives 1aad, 1add, 1ccd, and 1cdd exhibited a bathochromic shift due to their narrow highest occupied molecular orbital (HOMO) –lowest unoccupied molecular orbital (LUMO) gap. Natural transition orbital (NTO) analysis indicated that the excited state orbital overlaps differ among the C₃ symmetrical and asymmetrical dyes. These triskelion-shaped fluorophores were found to form molecular nanoaggregates in THF/H₂O mixtures and demonstrated aggregation-induced emission (AIE) enhancement characteristics as a result of restricting their molecular inversion. These results indicate that Janus-type AIE fluorophores are potentially applicable as solid-state fluorescent chiral materials, which can be optimized by controlling their molecular rearrangement in the solid state.     

Synthesis,characterization, and thermal properties of ring‐opening metathesis polynorbornenes and their hydrogenated derivatives bearing various ester and cyano groups

Doubly functionalized polar norbornenes 3a – 3g substituted by both a variety of ester and cyano groups were polymerized by ring‐opening metathesis polymerization (ROMP) with a Ru carbene complex 2 bearing 3‐bromopyridine as a ligand (third generation Grubbs' catalyst) in a living manner. The successive hydrogenation of the main‐chain double bond in the synthesized living ROMP polymers 4a – 4g with a hydridoruthenium complex was exploited. The comparison of thermal properties of a series of ring‐opening metathesis polymers 4a – 4g with those of their hydrogenated derivatives 5a – 5g revealed the decrease of glass transition temperatures (T_g) but little change of the 5% decomposition temperature (T_d⁵). In all cases examined in this study, a decrease of T_g by hydrogenation was around 20–40 °C, regardless of the ester substitutents. In the presence of the additional PCy₃, triethylamine, and methanol after complete consumption of monomer 3a under the living ROMP condition, the tandem ROMP‐hydrogenation of the resulting polymer 4a generated in situ was attained under a H₂ (9.8 MPa) atmosphere at 80 °C to afford the hydrogenated polymer 5a , retaining the narrow polydispersity of 1.03. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 3314–3325 2008     

Highly Emissive Diborylphenylene‐Containing Bis(phenylethynyl)benzenes: Structure–Photophysical Property Correlations and Fluoride Ion Sensing

A series of 2,5‐bis(dimesitylboryl)‐1,4‐bis(arylethynyl)benzenes 1 – 6 that contain various p‐substituents on the terminal benzene rings, including NPh₂ ( 1 ), OMe ( 2 ), Me ( 3 ), H ( 4 ), CF₃ ( 5 ), and CN ( 6 ) groups, were synthesized, and the effects of the p‐substituents on the absorption and fluorescence properties were investigated both in solution and in the solid state. Linear relationships were obtained not only between the Hammett σ_p⁺ constants of the p‐substituents and the absorption and fluorescence maxima, quantum yields, and excited‐state dynamics parameters in solution, but also between the σ_p⁺ constants and the fluorescence quantum yields in the solid state. An important finding extracted from these results is that the suppressed fluorescence quenching in the solid state is a common feature for the present laterally boryl‐substituted π‐conjugated skeletons. Hence, the diborylphenylene can serve as a useful core unit to develop highly emissive organic solids. In fact, most of the derivatives showed more intense emission in the solid state than in solution. In addition to these studies, the titration experiment of 1 by the addition of nBu₄NF was conducted, which showed the stepwise bindings of two fluoride ions with high association constants as well as a drastic change in the fluorescence spectra, while constantly maintaining high quantum yields (0.61–0.76), irrespective of the binding modes. This result also demonstrated the potential utility of the present molecules as an efficient fluorescent fluoride ion sensor.     

Synthesis and the effects of substitution upon photochromic diarylethenes bearing an isoxazole moiety

A new class of unsymmetrical photochromic diarylethenes bearing an isoxazole moiety was synthesized and the effects of substitution on their optical and electrochemical properties were investigated systematically. Each of the compounds exhibited remarkable photochromism and functioned as a fluorescent photoswitch both in solution and in poly(methyl methacrylate) films. The electron-donating substituents effectively shifted the absorption maximum and the emission peak to a longer wavelength direction, while the electron-withdrawing substituents notably enhanced the fluorescent quantum yields and oxidation onsets of these diarylethene derivatives. As compared to the unsubstituted parent diarylethene, introduction of the electron-donating/withdrawing substituents could efficiently modulate the optical and electrochemical properties of the diarylethenes bearing an isoxazole moiety. All results indicated that the isoxazole moiety and the substitution effects played a very important role during the process of photochromic reaction for these diarylethene derivatives.     

Tuning Electron-Withdrawing Strength on Phenothiazine Derivatives: Achieving 100 % Photoluminescence Quantum Yield by NO2 Substitution

The weak fluorescence (quantum yield <1 % in cyclohexane) of phenothiazine ( PTZ ) impedes its further application. In addition, the nitro group (NO₂) is a well-known fluorescence quencher. Interestingly, we obtained a highly fluorescent chromophore by combining these two moieties, forming 3-nitrophenothiazine ( PTZ-NO₂ ). For comparison, a series of PTZ derivatives bearing electron-withdrawing groups (EWGs; CN and CHO) or electron-donating groups (EDGs; OMe) at the 3-position have been designed and synthesized. The phenothiazines bearing EWGs exhibited enhanced emission compared with the parent PTZ or EDG derivatives. Computational approaches unveiled that for PTZ and PTZ-OMe , the transitions are from HOMOs dominated by π orbitals to LUMOs of mixed sulfur nonbonding–π* orbitals, and hence are partially forbidden. In contrast, the EWGs lower the energy level of the lone-pair electrons on the sulfur atom, thereby suppressing the mixing of the nonbonding orbital with the π* orbital in the LUMO, such that the allowed ππ* transition becomes dominant. This work thus demonstrates a judicious chemical design to fine-tune the transition character in PTZ analogues, with PTZ-NO₂ attaining 100 % emission quantum yields in nonpolar solvent.     

Color‐Tunable Solid‐State Fluorescence Emission from Carbazole‐Based BODIPYs

Several carbazole‐based boron dipyrromethene (BODIPY) dyes were synthesized by organometallic approaches. Thiazole, benzothiazole, imidazole, benzimidazole, triazole, and indolone substituents were introduced at the 1‐position of the carbazole moiety, and boron complexation of each dipyrrin generated the corresponding compounds 1 , 2 a , and 3 – 6 . The properties of these products were investigated by UV/Vis and fluorescence spectroscopy, cyclic voltammetry, X‐ray crystallography, and DFT calculations. These compounds exhibited large Stokes shifts, and compounds 1 , 2 a , and 3 – 5 fluoresced both in solution and in the solid state. Complex 2 a showed the highest fluorescence quantum yield (Φ_F) in the solid state, therefore boron complexes of the carbazole–benzothiazole hybrids 2 b – f , which had several different substituents, were prepared and the effects of the substituents on the photophysical properties of the compounds were examined. The fluorescence properties showed good correlation with the results of crystal‐packing analyses, and the dyes exhibited color‐tunable solid‐state fluorescence.     

Alkynylgold(I) C3-Chiral Concave Complexes: Aggregation and Luminescence

Chiral gold(I) acetylide trinuclear complexes 1 – 3 based on the cyclotribenzylene platform and terminal PR₃ ligands (R=Ph, Et, and Cy, respectively), were characterized and their light emission studied. They exhibited long-lived blue phosphorescence in CHCl₃ and a weak fluorescence in the UV. In MeOH/CHCl₃ mixtures of >1:1 volume ratio, 1 and 2 exhibited a new emission band at ca. 540 nm that developed at the expense of the UV emission. DLS studies demonstrated the presence of molecular aggregates of Ø 30–80 nm. The green emission observed in MeOH-rich solvent mixtures was therefore induced by aggregation, and could originate from Au⋅⋅⋅Au interactions. The AIE spectrum of 3 was observed only in solutions containing 99 % of MeOH, and correlated with its solid state emission. The AIE profiles of the enantiomers of 1 differed from that of rac- 1 , suggesting that the latter is a true racemate.     

First Highly Efficient and Photostable E and C Derivatives of 4,4‐Difluoro‐4‐bora‐3a,4a‐diaza‐s‐indacene (BODIPY) as Dye Lasers in the Liquid Phase,Thin Films,and Solid‐State Rods

A new library of E‐ and C‐4,4‐difluoro‐4‐bora‐3a,4a‐diaza‐s‐indacene (BODIPY) derivatives has been synthesized through a straightforward protocol from commercially available BODIPY complexes, and a systematic study of the photophysical properties and laser behavior related to the electronic properties of the B‐substituent group (alkynyl, cyano, vinyl, aryl, and alkyl) has been carried out. The replacement of fluorine atoms by electron‐withdrawing groups enhances the fluorescence response of the dye, whereas electron‐donor groups diminish the fluorescence efficiency. As a consequence, these compounds exhibit enhanced laser action with respect to their parent dyes, both in liquid solution and in the solid phase, with lasing efficiencies under transversal pumping up to 73 % in liquid solution and 53 % in a solid matrix. The new dyes also showed enhanced photostability. In a solid matrix, the derivative of commercial dye PM597 that incorporated cyano groups at the boron center exhibited a very high lasing stability, with the laser emission remaining at the initial level after 100 000 pump pulses in the same position of the sample at a 10 Hz repetition rate. Distributed feedback laser emission was demonstrated with organic films that incorporated parent dye PM597 and its cyano derivative. The films were deposited onto quartz substrates engraved with appropriate periodical structures. The C derivative exhibited a laser threshold lower than that of the parent dye as well as lasing intensities up to three orders of magnitude higher.     

Evaluation of Anisole‐Substituted Boron Difluoride Formazanate Complexes for Fluorescence Cell Imaging

Evaluation of three subclasses of boron difluoride formazanate complexes bearing o‐, m‐, and p‐anisole N‐aryl substituents (Ar) as readily accessible alternatives to boron dipyrromethene (BODIPY) dyes for cell imaging applications is described. While the wavelengths of maximum absorption (λ_max) and emission (λ_em) observed for each subclass of complexes, which differed by their carbon‐bound substituents (R), were similar, the emission quantum yields for 7 a – c (R=cyano) were enhanced relative to 8 a – c (R=nitro) and 9 a – c (R=phenyl). Complexes 7 a – c and 8 a – c were also significantly easier to reduce electrochemically to their radical anion and dianion forms compared to 9 a – c . Within each subclass, the o‐substituted derivatives were more difficult to reduce, had shorter λ_max and λ_em, and lower emission quantum yields than the p‐substituted analogues as a result of sterically driven twisting of the N‐aryl substituents and a decrease in the degree of π‐conjugation. The m‐substituted complexes were the least difficult to reduce and possessed intermediate λ_max, λ_em, and quantum yields. The complexes studied also exhibited large Stokes shifts (82–152 nm, 2143–5483 cm^?1). Finally, the utility of complex 7 c (Ar=p‐anisole, R=cyano), which can be prepared for just a few dollars per gram, for fluorescence cell imaging was demonstrated. The use of 7 c and 4′,6‐diamino‐2‐phenylindole (DAPI) allowed for simultaneous imaging of the cytoplasm and nucleus of mouse fibroblast cells.     

5,12‐Diacetyl‐5,12‐dihydroquinoxalino[2,3‐b]quinoxalines: Solid‐State Fluorescence,AIE Properties,and Orbital Switching by Substituent Effect

The compound 5,12‐diacetyl‐5,12‐dihydroquinoxalino[2,3‐b]quinoxaline 1 a and its derivatives were prepared, and their solid‐ and solution‐state spectroscopic properties were studied; 1 a shows stronger fluorescence in solution than in the solid state due to aggregation caused by self‐quenching. Phenyl‐ or alkoxy‐substituted derivatives 1 b – d show solid‐state fluorescence with moderate quantum yields of about Φ=0.12–0.15, although the corresponding values are 0.01–0.07 in solution. The spectroscopic properties of alkoxy‐substituted derivatives were hardly changed compared to 1 a and 1 b , although 1 a and 1 b have similar absorption and fluorescence maxima in solution and in the solid state. DFT calculations indicate that orbital switching occurs between HOMO and HOMO‐1 and HOMO‐2 due to orbital interactions with introduced substituents. Crystal structure analysis revealed that the molecules have bent structures around tertiary nitrogen atoms and form a characteristic dimeric structure.     

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.     

Probing the protein–nanoparticle interface: the role of aromatic substitution pattern on affinity

A new class of cationic gold nanoparticles (NPs) has been synthesised bearing benzyl moieties featuring –NO₂ and –OMe groups to investigate the regioisomeric control of aromatic NP–protein recognition. In general, NPs bearing electron-withdrawing groups demonstrated higher binding affinities towards green fluorescent protein (GFP) than NPs bearing electron-donating groups. Significantly, a ～7.5- and ～4.3-fold increase in binding with GFP was observed for –NO₂ groups in meta-position and para-position, respectively, while ortho-substitution showed binding similar to the unsubstituted ring. These findings demonstrated that the NP–protein interaction can be controlled by tuning the spatial orientation and the relative electronic properties of the aromatic substituents. This improved biomolecular recognition provides opportunities for enhanced biosensing and functional protein delivery to the cells.