Synthesis,Characterization, and Spectroscopic Properties of Hexa(4-Bromo-2-Formyl-Phenoxy)Cyclotriphosphazene and Hexa(4-Chloro-2-Formyl-Phenoxy)Cyclotriphosphazene and Fully Substituted Cyclotriphosphazene Derivatives Bearing a Schiff Base at Room Temperature

Abstract

Hexa(4-bromo-2-formyl-phenoxy)cyclotriphosphazene (2) and hexa(4-chloro-2- formyl-phenoxy)cyclotriphosphazene (3) were obtained from the reactions of hexachloro- cyclotriphosphazene (1) with 5-bromosalicylaldehyde and 5-chlorosalicylaldehyde in the presence of (C₂H₅)₃N and K₂CO₃ at room temperature, respectively. The new two organocyclotriphosphazenes bearing formyl groups were reacted with 4-cyano aniline, 2-phenyl aniline, 4-aceto aniline, 5-chloro-2-hydroxy aniline, 2-hydroxy aniline, 4-hydroxy aniline, 2-(4-morpholino)ethyl amine, 4-carboxy aniline, 4-carbomoyl aniline, 2-mercapto aniline, and 5-amino isoquonoline to prepare cyclotriphosphazene derivatives containing a Schiff base at room temperature. However, fully phenoxy-substituted cyclotriphosphazenes containing a Schiff base were isolated from the reactions of the compound 2 and 3 with 5-chloro-2-hydroxy aniline, 2-hydroxy aniline, 4-hydroxy aniline, and 2-(4-morpholino)ethyl amine. The structures of the synthesized compounds were characterized by elemental analysis, IR, and NMR (¹H, ¹³C, ³¹P) spectroscopy. According to the results of the analysis, all synthesized compounds were found to be fully substituted organocyclotriphosphazenes, such as hexa[4-bromo-2-(5-chloro-2-hydroxy-pheyliminomethyl)phenoxy]cyclotriphosphaze (2a). All cyclotriphosphazene derivatives synthesized gave fluorescence emission peaks in range between 300 nm and 410 nm.     

双态发光三苯胺基有机硼配合物的设计、合成与应用

以三(4-溴苯)胺、4-氨基苯硼酸频哪醇酯、4-二乙氨基水杨醛和三氟化硼乙醚溶液为原料,经过Suzuki偶联反应、缩合反应和配位反应,设计、合成了一种新型三枝结构的三苯胺有机硼配合物(TPAB),使用¹H和¹³C NMR对TPAB的结构进行了表征,通过紫外可见吸收光谱和荧光发射光谱详细研究了TPAB溶液和固体态的光物理性能以及不同的外部条件对其发光性能的影响。发现TPAB溶液和固体态都具有较强的荧光发射,在四氢呋喃溶液中的吸收峰位于417 nm,发射峰位于548 nm,荧光量子产率为40.49%,荧光寿命为1.72 ns; TPAB固体的荧光发射峰位于582 nm,荧光量子产率为11.43%,荧光寿命为0.72ns,表明TPAB具有优良的双态发光性能。此外,TPAB具有良好的发光稳定性,不受pH、金属离子、氨基酸和压力的影响。基于化合物优异的发光性能,将其应用于荧光细胞成像,在肝癌细胞(HepG2)中表现出良好的单光子和双光子荧光成像效果。     

双态发光三苯胺基有机硼配合物的设计、合成与应用

以三(4-溴苯)胺、4-氨基苯硼酸频哪醇酯、4-二乙氨基水杨醛和三氟化硼乙醚溶液为原料,经过Suzuki偶联反应、缩合反应和配位反应,设计、合成了一种新型三枝结构的三苯胺有机硼配合物(TPAB),使用 ¹H和 ¹³C NMR对 TPAB的结构进行了表征,通过紫外可见吸收光谱和荧光发射光谱详细研究了TPAB溶液和固体态的光物理性能以及不同的外部条件对其发光性能的影响。发现 TPAB溶液和固体态都具有较强的荧光发射,在四氢呋喃溶液中的吸收峰位于 417 nm,发射峰位于 548 nm,荧光量子产率为 40.49%,荧光寿命为 1.72 ns;TPAB 固体的荧光发射峰位于 582 nm,荧光量子产率为 11.43%,荧光寿命为 0.72ns,表明TPAB具有优良的双光发光性能。此外,TPAB具有良好的发光稳定性,不受pH、金属离子、氨基酸和压力的影响。基于化合物优异的发光性能,将其应用于荧光细胞成像,在肝癌细胞(HepG2)中表现出良好的单光子和双光子荧光成像效果。     

Meso位单取代卟啉及其配合物的合成、表征和光谱性质

设计合成了一系列新型的meso位N,N-二甲氨基苯基或N-苯基咔唑基单取代卟啉(5a~c)及其锌配合物(6a~c),用高分辨质谱、¹H NMR、紫外-可见光谱及X射线单晶衍射方法等对结构进行了表征;研究了卟啉化合物及其配合物的热稳定性及荧光性质。结果表明,这些卟啉化合物及其锌配合物在400~410 nm之间具有强的吸收且具有很好的热稳定性,荧光量子产率在0.05~0.09;另外还分析了meso位不同取代基对光谱性质的影响。     

Meso位单取代卟啉及其配合物的合成、表征和光谱性质

设计合成了一系列新型的meso位N,N-二甲氨基苯基或N-苯基咔唑基单取代卟啉（5a~c）及其锌配合物（6a~c）,用高分辨质谱、¹H NMR、紫外-可见光谱及X射线单晶衍射方法等对结构进行了表征;研究了卟啉化合物及其配合物的热稳定性及荧光性质。结果表明,这些卟啉化合物及其锌配合物在400~410 nm之间具有强的吸收且具有很好的热稳定性,荧光量子产率在0.05~0.09;另外还分析了meso位不同取代基对光谱性质的影响。     

Synthesis,characterization of novel quinoline-2-carboxamide based chalcone derivatives and their molecular docking,photochemical studies

Abstract

Novel series of quinoline-2-carboxamide based chalcone derivatives (5a–g) have synthesized and characterized using ¹H-NMR, 13C-NMR, Mass, and elemental analysis. In-silico molecular docking studies exhibited that synthesized compounds 5a and 5g are good binding energy (?8.46?kcal and ?9.46?kcal) toward the essential requirements of targeted compounds for EGFR receptor-bearing quinazoline inhibitor (PDB ID: 1M17(Lapitinib)). UV-Vis and fluorescence spectroscopy measurements provided a significant effect on the absorption, emission cyclic voltammetry (CV), and highest occupied molecular orbital (HOMO). Lowest unoccupied molecular orbital (LUMO) values of compound 5g are also confirmed band along with intramolecular charge transfer character (D-π-A). The red shift maxima (510?nm) the emission spectra in various solvents with increasing solvent polarity.     

Novel BODIPY-bridged cyclotriphosphazenes

Three new 2-component unsubstituted ( 4P ), diiodo- ( 5P ), and dibromo- ( 6P ) distyryl-BODIPY-bridged cyclotriphosphazene dimers were designed and synthesized. The newly synthesized BODIPY-cyclotriphosphazene systems were characterized by ¹ H, ¹³ C, and ³¹ P NMR spectroscopy. The photophysical properties of the distryl-BODIPYs (4–6) and BODIPY-cyclotriphosphazene dyads ( 4P – 6P ) were studied by UV-Vis absorption and fluorescence emission spectroscopy. In these derivatives, the bino-type cyclotriphosphazene derivative bearing unsubstituted BODIPY unit 4P exhibited high fluorescence and no singlet oxygen generation due to the lack of spin converter. The attachment of heavy atoms (iodine and bromine) enabled the production of singlet oxygen. The bino-type BODIPY-cyclotriphosphazenes ( 5P and 6P ) were also used as triplet photosensitizers in the photooxidation of 1,3-diphenylisobenzofuran to endoperoxide via generation of the singlet oxygen in dichloromethane. The singlet oxygen production of these compounds was also investigated via a direct method and produced a singlet oxygen phosphorescence peak at 1270 nm.     

Pyrene-BODIPY-substituted novel water-soluble cyclotriphosphazenes: synthesis,characterization, and photophysical properties

In the present work, pyrene-boron-dipyrromethene (BODIPY)-substituted novel water-soluble cyclotriphosphazene derivatives (6 and 7) were synthesized by click reactions between a cyclotriphosphazene derivative with a hydrophilic glycol side group (2) and BODIPYs (4 and 5). All of the new compounds (2, 6, and 7) were characterized by Fourier-transform infrared and nuclear magnetic resonance spectroscopy, as well as mass spectrometry and elemental analysis. The photophysical properties of the BODIPY-substituted cyclotriphosphazenes (6 and 7) were investigated by UV-Vis and fluorescence emission spectroscopy in water and water/solvent mixtures. It was found that the target compounds were soluble in water and could be potential candidates as water-soluble fluorescent dyes for the desired applications.     

三苯基咪唑类化合物的合成及其紫外、荧光性质研究

设计合成了四种三苯基咪唑类化合物:4,5-二苯基-2-对甲酰基苯基咪唑(2a),4,5-二(2-硝基苯基)-2-对甲酰基苯基咪唑(2b),N-苄基-4,5-二苯基-2-对甲酰基苯基咪唑(2c)和N-苄基-4,5-二(2-硝基苯基)-2-对甲酰基苯基咪唑(2d),并用FT-IR,NMR和MS进行结构表征.在乙酸乙酯-石油醚溶液中获得了2c的单晶,用X射线单晶衍射法测定了其晶体结构,晶体属于三斜晶系,空间群P1,晶胞参数a=0.73796(15)nm,b=0.90136(18)nm,c=1.6644(3)nm,α=86.87(3)°,β=78.25(3)°,γ=89.94(3)°,V=1.0822(4)nm3,Dc=1.272g/cm3,Z=2,F(000)=436,μ=0.077mm-1,R1=0.0459,wR2=0.1303.研究了四种化合物的紫外与荧光性质,发现官能团硝基与苄基的引入,对其吸收峰和发射峰均有不同程度的影响:在紫外光谱中两种官能团均使吸收峰蓝移;在荧光光谱中苄基使发射峰蓝移而硝基使发射峰红移.测定了2a和2c在不同溶剂中的荧光寿命,其中2a在DMSO中寿命最长,为3.18ns.这些光谱性质为研究其双光子吸收、双光子荧光和非线性光学性质奠定了理论和实验基础.     

Spectral study on the interaction of cryptophane-A and neutral molecules CHnCl4-n (n=0, 1, 2)

Cryptophane-A was synthesized from vanillin by a three-step method and its spectroscopic properties in different organic solvents were determined. Two absorption bands at about 240-250 and 280-290 nm were observed for cryptophane-A. A fluorescence emission peak was obtained at 320-330 nm using a solution of approximately 10(-5)M cryptophane-A. The interaction of cryptophane-A with chlorinated compounds CH(n)Cl(4 - n) (n=0, 1, 2) in dioxane and ethyl acetate solvents were studied in detail by fluorescence spectroscopy, respectively. The results show that cryptophane-A is well suited for inclusion of CH(2)Cl(2) to form a stable 1:1 complex and the binding constant was estimated to be 19+/-2M(-1). These results were also confirmed by (1)H NMR and CPK models. Larger similar molecules such as CHCl(3) and CCl(4) are unable to enter the cavity of cryptophane-A because of their bigger sizes. However, the fluorescence emission of cryptophane-A can be efficiently quenched by CHCl(3) and CCl(4), following the Stern-Volmer relationship.     

新型蓝色上转换荧光分子的合成、表征与双光子吸收性能

设计并合成了3 个新的受体-给体-受体(A-D-A)构型上转换荧光分子,用傅里叶变换红外光谱、核磁共振氢谱、质谱和元素分析进行了表征. 测定了它们在不同溶剂中的线性吸收光谱、单光子荧光光谱和荧光量子产率. 以飞秒激光作为光源,研究了它们的双光子吸收和上转换荧光特性. 结果表明：该类化合物的荧光量子产率为0.20-0.68,双光子吸收截面为16×10^-50-101×10^-50 cm⁴·s·photon^-1,具有较强的蓝色上转换荧光发射.     

Design and Synthesis of Novel Organic Luminescent Materials Based on Pyrazole Derivative

Five new materials based on pyrazole derivatives have been synthesized and characterized as organic light‐emitting devices. This report presents a novel approach to combine pyrazole with aromatic hydrocarbons via methylene. The formed molecules exhibited twisted structures, which resulted in high glass transition temperatures (T_g), which ranged from 83.0 to 101.1°C. They also had high optical band gaps (E_g); most of their optical band gaps are determined by the absorption edge technique as 3.43 to 3.66 eV, evaluated photophysical properties of these synthesized novel chromophores, the optical properties such as maximum absorption and emission wavelengths (λ; nm), molar extinction coefficients (ε; cm^?1·M^?1), Stokes' shifts (Δλ_ST; nm), and quantum yields (φ_F). These compounds exhibited intense absorption bonds between 230 and 350 nm, and the effect of solvent polarity on emission of these pyrazole derivatives was also studied. In addition, they showed blue fluorescence in different solvents and bathochromic shift with the increase in the solvent polarity.     

SPECTROSCOPIC STUDIES OF PURINES—I. FACTORS AFFECTING THE FIRST EXCITED LEVELS OF PURINE*

Abstract— Studies of purine absorption and emission in seven solvents differing greatly in dielectric constant and hydrogen bonding potential, reveal a variety of solvent effects. For example, the resolution of structure in the absorption spectrum, the position and/or intensity of the X₂ absorption band, the intensity of fluorescence, the magnitude of the long wave-lenth tail, and the position of the X₁ absorption band are differentially affected—in the order listed—by the solvents tested. Even though it is possible to correlate the extent of decrease in the n-π* tail with increasing solvent dielectric constant, probably alterations in all of these spectroscopic parameters depend most critically upon the ability of the various solvents to form hydrogen bonds with the hydrogen on N9 and/for with the non-bonding electrons on the purine nitrogens: it is tentatively concluded that the probability of hydrogen bonding is directly correlated with the electronegativity of the aza nitrogens (N7 > N3 > N1). In solvents like isopropanol not all of the non-bonding electrons must be solvated maximally in most purine molecules since there is appreciable fluorescence under conditions where a long wavelength tail is readily observed in the absorption spectrum (alternatively some noa-bonding electrons may not te relevant to fluorescence quenching.) Decreases in fluorescence yield are associated with red shifts in the fluorescence maximum, and in the solvents of highest polarity the fluorescence yield is again small indicating that glycerol and water can enhance radiationless tunneling—presumably by altering Franck-Condon configurations and/or improving electronic-vibrational coupling between solute and solvent. The quantum yield is uniform throughout the atsorption band for a given solvent, but studies in aqueous buffers varying from pH 1 to 11 show that the fluorescence yield is greater for charged than for neutral molecules. Further, the fluorescence excitation peak is red shifted in powders. Since phosphorescence is the predominant emission at 777deg;K and increases in fluorescence can be correlated with the presumed solvation of non-bonding electrons, the singlet excited state of lowest energy in ‘unperturbed’ purine must be n-π* in nature. The shape of the phosphorescence band and the decay lifetime of ? 1 sec at 77°K lead to the conclusion that the emitting triplet is a π-π* state. The eight vibrational structures in phosphorescence emission can be readily grouped into two progressions: there is an average separation of about 1300 cm^-1 between peaks within a given progression, and the two sets are mutually displaced by about 500 cm-^l. Individual vibrational peaks are favoured in different solvents and the whole band may be shifted up to 500 cm^-l. Even larger shifts are observed in charged purine molecules and in powders (up to 3000 cm^-l) and the presumed 0–0 band is not observed.     

Synthesis and fluorescence properties of 2-aryl-3-hydroxyquinolones, a new class of dyes displaying dual fluorescence

A series of 2-aryl-3-hydroxyquinolones (3HQs) with different electron donating aryl substituents at the position 2 were synthesized. Their absorption and fluorescence properties were studied in solvents of medium and high polarity. Almost all the synthesized 3HQs display dual fluorescence in the tested solvents, in line with an excited state intramolecular proton transfer reaction. For N-methyl substituted compounds, the intensity ratio of the two emission bands was found to be exquisitely sensitive to solvent polarity, with a two orders of magnitude change from toluene to dimethylsulfoxide. Consequently, these compounds appear as prospective polarity fluorescent labels for proteins and nucleic acids.     

Synthesis and spectroscopic properties of new 5-oxazolone derivatives containing an N-phenyl-aza-15-crown-5 moiety

Novel 5-oxazolone derivatives containing an N-phenyl-aza-15-crown-5 moiety were synthesized for the first time. The structures of the new derivatives were confirmed by ¹H NMR, ¹³C NMR and FT-IR. In addition, evaluation of the visible absorption and emission properties of the structures were carried out in eight different solvents. The products show intense visible absorption maxima in the range 467-524 nm, and fluoresced strongly, with emission maxima from 496 to 689 nm in all the solvents tested.     

碳纳米粒子：合成及可见光催化降解萘酚绿

以酒石酸和酪氨酸为起始反应物,乙二醇为溶剂,采用溶剂热法一步合成了高发光强度的碳纳米粒子。利用XRD、TEM、FTIR和荧光光谱对碳纳米粒子的物相、形貌和粒径、表面基团及发光性能进行了表征。结果表明,合成的碳纳米粒子为粒径分布集中的球形,粒径10~30nm,分散性好,表面富含-COOH、-OH等官能团,具有激发波长依赖的光致发光特性。考察了反应温度、酒石酸与酪氨酸质量比对碳纳米粒子发光性能的影响。研究了碳纳米粒子/H₂O₂催化体系对萘酚绿的降解性能,结果表明：130mg·L^-1的萘酚绿溶液,可见光照射3.5h降解率可以达到96%。荧光光谱法表征指明降解过程中有羟基自由基生成。     

Synthesis and Photophysical Properties of Some PEG Substitued Titanyl Phthalocyanine Derivatives

Summary: Polyethylene glycol substituted titanyl phthalocyanine was prepared in two steps starting from phthalonitrile and characterized by FT-IR, UV-vis spectrophotometry, and fluorescence spectrophotometry. The titanyl phthocyanine derivatives (TiOPcs) showed high solubility in common organic solvents, such as, CH₃Cl and DMF. These compounds decreased in absorbance intensity with increase of molecular weight of polyethylene glycol at maxima wavelength of visible range. The fluorescence spectra showed a fluorescence emission near 690 nm with a quantum yield of 0.05–0.32 (λ_ex = 625 nm).     

Synthesis of new tripodal receptors—a ‘PET’ based ‘off-on’ recognition of Ag

A new set of tripodal receptors based upon an aromatic platform have been synthesized in high yields. The compounds have been characterized by spectroscopic techniques and by single crystal X-ray crystallography. These receptors are found to have good extraction ability and high transport rate for Ag(I). The receptor with imine linkages exhibits weak fluorescence emission bands at λ_max=413 and 540 nm, upon excitation at λ_max=365 nm. The fluorescence spectrum of the receptor shows enhancement in the intensity of the signal at 413 nm on binding with the Ag⁺ cation. No such significant changes are observed with other metal ions. An absorption at ∼365 nm is typical of an intraligand (π-π^∗) transition involving the imine chromophore, which produces a weak emission band at 413 nm due to quenching caused by PET from a neighboring -OH group. Participation of OH group in coordination to the metal ion reduces PET and an enhancement of fluorescence intensity is observed, signaling recognition of the metal ion.     

Blue-luminescent poly(p-phenylenevinylene) derivatives: Synthesis and effect of side-group size on the optical properties

New conjugated polymers based on separated PPV-type chromophores and incorporating different types of solubilizing side-groups (ethoxy: P1, hexyloxy: P2, dodecyloxy: P3 and benzyloxy: P4) were synthesized via Wittig polycondensation, using a series of bisphenol A-derived di(triphenylphosphonium) salts as starting monomers. The polymers are soluble in common organic solvents and their structures were confirmed by ¹H NMR, ¹³C NMR and FTIR spectroscopies. The optical properties of these materials were investigated by UV–vis absorption and fluorescence spectroscopies. In dilute solution, quasi-identical fluorescence spectra were obtained and all the polymers showed a blue emission (420, 445 nm) and a narrow spectrum. In thin solid films, the polymers show side-group-dependent optical behavior and, whereas the emission remains blue in the case of P2, P3 and P4, a green fluorescence was observed for the ethoxylated polymer P1. From cyclic voltammetry analysis, the electrochemical band gaps were estimated to be 2.99, 3.07, 3.15 and 3.06 eV for P1, P2, P3 and P4, respectively. Single-layer diode devices of the [indium tin oxide/polymer/aluminum] configuration have been fabricated and show relatively low turn-on voltages between 2.6 and 4.9 V.     

Synthesis,structural characterization,and anion interactions of new triazole-linked urea derivative fully substituted cyclotriphosphazene compounds

Three novel fully substituted urea derivative cyclotriphosphazene compounds 5–7 were synthesized by alkyne-azide 1,3-dipolar cycloaddition reaction of propargyl substituted ureas 2–4 with hexaazide substituted cyclotriphosphazene 1 in the presence of Cu(I) catalyst. All compounds were characterized with spectroscopic techniques such as FT-IR, ¹H, ¹³C, and ³¹P nuclear magnetic resonance and mass spectroscopy. Also, the usefulness of compounds 5–7 as anion carriers was investigated by ¹H NMR spectroscopy. For this purpose, ¹H NMR spectra of compounds 5–7 were recorded in the presence of tetrabutylammonium fluoride in DMSO-d₆. It was determined, that the urea protons in the compounds interact with fluoride.