Bio-organic adaptive photonic crystals enable supramolecular solvatochromism

Photonic crystals(PCs)exhibit promising structural coloration properties and possess extensive application prospects in diverse optical fields.However,state-of-the-art inorganic or polymeric PCs show limited adaptivity as their configurations are fixed once formed.Herein,bio-organic adaptive PCs are fabricated via drop-casting of amphiphilic guanine-based peptide nucleic acid selfassembled microspheres.The high formation activation energy of up to 81.8 kJ·mol−1 suggests that the self-assembly step dominates the entire process.Therefore,the configurations along with the structural coloration of the supramolecular PCs are sensitive to self-assembly influencing parameters,showing temperature-encoded structural color evolution and solvent polaritydependent solvatochromism.Our findings demonstrate that the supramolecular PCs are adaptive,thus showing promising potential for detection of organic solvents of different polarities in a visual and real-time manner for environmental protection or optical applications.

Theoretical studies on Ru(fppz)_2(CO)L (L=N-heterocyclic ligand):Electronic structure,absorption,phosphorescence,and solvatochromism

A series of ruthenium(II) complexes Ru(fppz)2(CO)L [fppz = 3-trifluoromethyl-5(2-pyridyl)pyrazole; L = pyridine (1), 4-dimethylaminopyridine (2), 4-cyanopyridine (3)] were designed and investigated theo-retically to explore their electronic structures, absorption, and emissions as well as the solvatochrom-ism. The singlet ground state and triplet excited state geometries were fully optimized at the B3LYP/LANL2DZ and CIS/LANL2DZ level, respectively. The HOMO of 1-3 is composed of dyz(Ru) atom and π(fppz). The LUMO of 1 and 2 is dominantly contributed by π*(fppz) orbital, but that of 3 is con-tributed by π*(L). Absorption and phosphorescence in vacuo, C6H12, and CH3CN media were calculated using the TD-DFT level of theory with the PCM model based on the optimized ground and excited state geometries, respectively. The lowest-lying absorption of 1 and 2 at 387 and 391 nm is attributed to {[dyz(Ru) + π(fppz)] → [π*(fppz)]} transition, but that of 3 at 479 nm is assigned to {[dyz(Ru) + π(fppz)] → [π*(L)]} transition. The phosphorescence of 1 and 2 at 436 and 438 nm originates from 3{[dyz(Ru) + π(fppz)] [π*(fppz)]} excited state, while that of 3 at 606 nm is from 3{[dyz(Ru) + π(fppz)] [π*(L)]} excited state. The calculation results showed that the absorption and emission transition character can be changed from MLCT/ILCT to MLCT/LLCT transition by altering the substituent on the L ligand. The phosphorescence of 1 and 2 does not have solvatochromism, but that of 3 at 606 nm (vacuo), 584 nm (C6H12), and 541 nm (CH3CN) is strongly dependent on the solvent polarity, so introducing elec-tron-withdrawing group on ligand L will induce remarkable solvatochromism.

Surface-state triggered solvatochromism of carbonized polymer dot and its two-photon luminescence

This study reports a new nitrogen-doped carbonized polymer dot(CPD)-based solvatochromic probe.Its color-changing for different solvents was explored in detail by the measurements of photophysical parameters(involving Stokes shifts,fluorescence quantum yield,fluorescence lifetime,radiative decay rate constant,and non-radiative decay rate constant)and the following analyses according to Lippert–Mataga equation and Kamlet–Taft model.The hydrogen bonding effect of the CPD in protonic solvents was semi-quantitatively assessed.It takes charge of the solvatochromic phenomenon,especially in proton solvents.Interestingly,this CPD exhibits two-photon solvatochromism.Moreover,the relations between the photophysical parameters and the surface states of CPD in aprotic and proton solvents were depicted.The results reveal the nitrogen doping in the CPD impacts the up-and down-conversion solvatochromic features from the comparison between N-free and N-doped CPDs in many characterizations.In addition,this N-doped CPD was dispersed into polymer matrices to fabricate tunable solid-state luminescent films,which is another model for evidencing the interactions of the CPD with surroundings.This study is of significance in understanding the surface-state controlled luminescence in the CPDs,and will be beneficial for developing new smart,responsive carbon-based nanoprobes.

Synthesis, Characterization and Solvatochromism Investigation of Mixed Ligand Chelate Copper（Ⅱ） Complexes with Acetyleacetonate and Three Diamine Ligands

The syntheses of three mixed ligand chelate copper（II） complexes of the type [Cu（L）（acac）（H2O）]BPh4 where acac=acetyleacetonate; L=N,N-dimethyl,N′-benzylethane-1,2-diamine （L1）, N,N-dimethyl, N′-2-methylbenzylethane-1,2-diamine （L2） or N,N-dimethyl,N′-2-chlorobenzylethane-1,2-diamine （L3） are reported and characterized by elemental analyses, spectroscopic and molar conductance measurements. The X-ray structure of complex 1 shows that the central copper atom is placed in a distorted square pyramidal geometry made by acac and diamine chelate in the base and a H2O molecule on the apex. The prepared complexes are fairly soluble in a large number of organic solvents and show positive solvatochromism. Calculations of SMLR （stepwise multiple linear regression） method was utilized to find the best model explaining the observed solvatochromic behavior and showed that among different solvent parameters, donor number （DN） is a dominant factor responsible for the shift in the d-d absorption band of the complexes to the lower wavenumber with increasing its values. The importance of substituent effect in diamine ligand on the spectral and SMLR measurements is also discussed.

Synthesis and Non-linear Optical(NLO) Properties of a Series of Alkoxysilane Derivative Chromophores

1 Introduction Nonlinear optical materials（NLO） have drawn a great intrest of some scholars and scientists in the last dacades because of their tremendous potential application in optoelectronic. The fabrication of efficient optoelectron devices is a challenging task because such systems need to meet the stringentable requirements for high optical quality and large and sustainable electro-optical（EO） response. In pursuit of NLO materials with excellent optoelectronic property,

Synthesis of 6-chloro and 6-fluoro-4-hydroxyl-2-quinolone and their azo disperse dyes

In this study,6-chloro-4-hydroxy-2-quinolone and 6-flouro-4-hydroxy-2-quinolone were synthesized from corresponding dianilides.These compounds were coupled with some diazotized aromatic amines to give the corresponding azo disperse dyes.The structures of the quinolone derivatives and new azo dyes were confirmed by UV-vis,FT-IR,;H NMR and elemental analysis.

Synthesis and Characterization of (E)-5-[2-(N-hexylcarbazolyl)vinyl] furan Derivatives with Acceptor Groups

A new series of (E)-5-[2-(N-hexylcarbazolyl)vinyl]furan chromophores with various accepters have been synthesized by the Knoevenagel condensation of (E)-5-[2-(N- hexylcarbazolyl) vinyl]-2-furaldehydes with malononitrile, 1,3-diethyl-2-thiobarbituric acid, or 3-phenyl-5-isoxazol one, respectively. They are characterized by H-1-NMR, FT- IR, UV-VIS, MS and elemental analysis, and have shown strong solvatochromism and high thermal stability.

Synthesis and Electronic Structure of A2B Type Halogen Atoms Substituted H3-Triarylcorroles

Seven electron-deficient A_2 B type H_3-triarylcorroles have been synthesized and characterized. The solvent dependence of the electronic absorption and magnetic circular dichroism（MCD） spectra and a series of TD-DFT calculations have been used to analyze trends in the electronic structures. Significant differences are observed in the optical spectra when solvents of differing polarity are used,which can be assigned to the effect of NH-tautomerism.

A KIND OF FLUORESCENCE PROBE TO STUDY THE KINETICS OF POLYMERIZATION PROCESS

Fluorescence properties of 1-pheny1-3-(4'-nitrophenyl) pyrazoline (PNP) were studied inbulk polymerization process of methylmethacrylate (MMA). The fluorescence intensity of PNPwas enhanced and the emission maximum was blue shifted with the polymerization progress. Inthe period of auto-acceleration of the polymerization the enhancement of fluorescence intensityand blue shift of peak wavelength in spectra could be observed evidently. This means that thesolvatochromic properties of PNP are influenced not only by the solvent polarity but also by theviscosity of the medium (especially by the phase transitiott). In solid state PNP emits from thecharge transfer excited state without solvent relaxation. The transient emission spectra and theresults from Bakhshiev model of solvent relaxation coincide with that from the polymerizationexperiment.

Aggregation Properties of an Amphiphilic Methanofullerene Derivative in THFH_2O Solvent Mixtures

Amphiphilic methanofullerene 1 exhibits strong tendency to form aggregates in THFH2O solvent mixtures. Two different aggregation processes induced by either varying the solvent composition or upon standing have been found. Concentration has great influence on the aggregation process. Paralleling to the UV-Vis changes, an unusual solvatochromism has been observed in these two different processes.

Synthesis and Solvatochromic Behavior of Hexaphenylbenzenes and Indeno[1,2-<i>b</i>]fluorene Derivatives with Hydroxy Groups

Hexakis(4-methoxyphenyl)benzene (HPB-OMe(1)) and hexakis(2,6-dimethyl-4-methoxyphenyl)benzene (HPB-OMe(2)) were synthesized via organometallic complex catalysis. The treatment of HPB-OMe(1) with FeCl3 caused cyclodehydrogenation at two positions to yield an oligophenylene with an indeno[1,2-b]fluorene structure (IF-OMe). Deprotection of the methoxy groups of these compounds was conducted by treatment with BBr3. Deprotonation of the OH groups of HPB-OH(1), HPB-OH(2), and IF-OH through treatment with NaH caused a bathochromic shift in the absorption and photoluminescence (PL) peaks. The bathochromic shift of the deprotonated species increased with the donor number (DN) of the solvents. These observations can be explained as the consequence of intramolecular charge transfer (ICT) from the ONa groups to the inner benzene rings.

The First Hyperpolarizabilities of Merocarbocyanines

The dot products mu(g)beta(CT) of first hyperpolarizability and ground state dipole moment of two merocarbocyanines were measured experimentally with solvatochromism and compared to the values obtained by AM1/FF calculation. The comparable result was also obtained by the measurement of second harmonic generation (SHG) for LB film of dye II. The mu(g)beta(CT) of dye II is larger than that of the well known NLO chromophore 4-N, N-dimethylamino-4'-nitrostilbene (DANS).

Study on the Phase Behavior of Supercritical CO2/Dynol-604/Water System and Solubilization of Methyl Orange in the Microemulsions

It was found that Dynol-604, a non-fluorous and no silicon-containing nonionic surfactant, was soluble in supercritical (SC) CO2. The phase behavior of SC CO2/Dynol-604/water system was studied. The results showed that one-phase water-in-CO2 microemulsions could be formed. The solubilization of methyl orange in the microemulsions proved further the existence of water domain in the microemulsions.

Solvatochromic Probe Based on Nanocellulose Membrane Coated with Zn-terpyridine Complex in a Layer-by-Layer Manner

Solvatochromic materials have recently attracted increasing attention owing to their great significance in the security and sensor fields.In this study,ultrafast explicit and implicit information was collected regarding a fluorescent nanocellulose membrane produced from nanocellulose membranes coated with a Zn-terpyridine complex(Zn-tpy)in a layer-by-layer manner.The fluorescent emissions of the nanocellulose membrane changed from yellow(CIE:x=0.37,y=0.45)to green(CIE:x=0.32,y=0.47)under a dichloromethane environment and 365-nm irradiation.Due to the ease of dichloromethane volatilization,fluorescent emissions quickly returned to the original state.These solvatochromic nanocellulose membranes,with ultrafast explicit and implicit information,exhibited valuable application prospects in anti-counterfeiting techniques.

Synthesis and Spectroscopic Properties of Ferrocenyl Derivative Containing Donor and Acceptor Groups

Much interest has been devoted to organometallic NLO materials. We have become interested in exploring the utility of ferrocenyl group as the conjugating bridge. Thus, we synthesized 1-{{[1,3-(5-methylbenzo)dithiol]-2-yli- dene}methyl}-1’-[2-(p-nitrophenyl)-(E)-ethenyl]ferrocene (1). This new ferrocenyl compound has a donor and an acceptor group in 1,1’-positions. Investigations of the solvatochromic property of the compound revealed that it has polarized structure in a polar solvent, such as DMF. SHG efficiency of the compound was estimated by an SHEW (second-harmonic generation with the evanescent wave) method.

Synthesis and Photophysical Properties of Novel Highly Stable Zero/Bis-Zero Methine Cyanine Dyes Based on N-Bridgehead Heterocycles

Cyanine dyes of zero/bis-zero methine incorporating imid-azo(1,2-a)Pyridine (quinoline) or pyrazino(1,2-a)pyridine (quinoline) with stable C-N bond were synthesized using keto-oxime methylene C-link heterocyclic quaternary salts [1-phenyl-3-methyl-pyrazolino-4-keto-oxime-α-methylene-bis-pyridin-(quinoin)-1(4)-di-ium-iodide(ethiodide) salts and 1-phenyl-3-methyl-pyrazolino- 4-ketooxime-α-methylene-N-2-methyl-bis pyridin (quinoin)-1(4)-di-ium-iodide(ethiodide) salts]. Such heterocyclic precursors and related dyes were identified by elemental and spectral analyses. The absorption spectra properties of such dyes were investigated in 95% Ethanol to attempt and throw some light on the influence of such new heterocyclic nuclei and to compare or evaluate spectral behaviors. The absorption spectra of dyes in different pure solvents were examined in the visible region showing solvatochromism and the colour changes of dyes with solvents having different polarities. This permits a selection of the optimal solvent (fractional solvent) when such dyes are applied as photosensitizers. The spectral behavior of some selected newly synthesized cyanine dyes is observed in mixed solvents of different polarities and progressively increasing quantities of one solvent over the other were studied and showed an increase in the absorbance of CT band with increasing proportion of that solvent. Evidence for hydrogen bond formation between the solute molecules and solvent molecules allows measurement of certain energies such as hydrogen bonding, orientation, and free energies.

A New Method to Investigate the Clustering Phenomena in Supercritical Fluids

The solvatochromic behavior of acetone in supercritical CO? was investigated from 75 bar to 239 bar and at 318.15K. A clustering model is proposed to investigate the formation of solute-solvent and solute-solute clusters, based on the solvatochromic study and some reasonable assumptions. At lower pressures, there were more than one solute molecules in one cluster. At higher pressures, however, each cluster only contained one solute and the clustering of solute-solvent was dominant.

Tunable aggregation-induced fluorescent and pressure-responsive luminescence supramolecular cages achieved by subcomponent self-assembly

Three discrete tetrahedral metallo-supramolecular cages were designed and constructed using truxenepended base ligands.Owing to the synergistic rigidifying effect of unsymmetric cyano-substituted oligo(pphenylene-vinylene)(u-COPV)suspended by the truxene skeleton,the resulting supramolecular cages were confirmed to exhibit significant aggregation-induced emission(AIE)accompanied by an interesting solvatochromic fluorescent behavior as well as a porous honeycomb-like state during aggregation.In particular,the anti-counterfeiting performance and emission behaviors of the cages in the solid state under external hydrostatic pressure were investigated.

Wide emission shifts and high quantum yields of solvatochromic carbon dots with rich pyrrolic nitrogen

Carbon dots(CDs)with solvatochromic emission colors in different solvents have attracted much attention as a new class of luminescent nanomaterial owing to their facile synthesis and low production cost.In this work,we prepared two kinds of CDs with solvatochromic emissions:green emission CDs(G-CDs)and multicolor emission CDs(M-CDs).G-CDs synthesized from o-phenylenediamine exhibited weak photoluminescence emission(quantum yield 2.8%-6.1%)and 39 nm solvatochromic shifts(492-531 nm).In contrast,M-CDs prepared from o-phenylenediamine and 4-aminophenol showed 87 nm solvatochromic shift range(505-592 nm)and much higher photoluminescence quantum yield(18.4%-32.5%).The two CDs exhibited different emission,absorption,and photoluminescence lifetime.The origin of solvatochromic shifts and the formation mechanism of CDs were demonstrated by analyzing the structures and compositions of two CDs.High percentages of pyrrolic nitrogen and amino nitrogen make wider solvatochromic shifts and higher quantum yields.The results were well supported by density functional theory calculations.This effective strategy to expand solvatochromic shift range and improve quantum yields could open a new window to prepare satisfied solvatochromic carbon dots.

Soluble triarylamine functionalized symmetric viologen for all-solid-state electrochromic supercapacitors

Electrochromic supercapacitors have drawn enormous attention due to their ability to monitor the charge and discharge processes through color changes of electroactive materials.However,there are few work on small organic molecules as active materials for all-solid-state electrochromic supercapacitors.Herein,we reported two novel multifunctional symmetric viologens(TPA-bpy and CZ-bpy),which showed different solvatochromic,electrochromic,electroluminochromic and energy storage behaviors despite their similar chemical structures.The different performances between these two viologens were attributed to the difference in the intramolecular charge transfer capability and the solubility in organic solvents.Devices containing TPA-bpy displayed faster response time and higher coloration efficiency due to the introduction of packing-disruptive and three-dimensional triarylamine groups.Moreover,devices containing TPA-bpy also showed energy storage characteristics with an obvious color change from purple to yellow.It showed a wide voltage window(2.0 V),long discharge time(230.3 s at 0.01 mA cm−2),and excellent cycling stability with 90%capacitance retention after 6,000 cycles.The work provides a new and convenient strategy towards the development of novel electrochromic capacitive materials.