- The effect of substituent number on mechanochromic luminescence of β-diketones and the corresponding boron complexes
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In this work, we designed and synthesized a series of β-diketones and the corresponding boron complexes (including mono-substituted, meta-position di-substituted and tri-substituted compounds). The effect of substituent number on their photophysical properties and mechanochromic luminescence (ML) behavior in different states was systematically studied. As verified by experimental and calculated results, the mechanical responsive properties of the six molecules were found structurally dependent, which were mainly modulated by conjugation effect and steric effect derived from different substitution. The di-substituted m-bdk and m-BF2bdk displayed the most prominent ML behavior, while the mono-substituted molecules showed almost no response to mechanical force. Moreover, the tri-substituted compounds (tri-bdk and tri-BF2bdk) showed fast self-erasing properties, highlighting the promising applications in self-erasing or self-healing devices and optical force sensors with high temporal resolution. Our study not only provides an effective strategy for modulating the optical properties, ML performance and recovery time by tuning the substituent number at molecular scale for the first time, but also facilitates the in-depth understanding of structure–property relationships in β-diketonate based dyes.
- Li, Mengwei,Han, Yi,Zhang, Zidan,He, Xuehao,Chen, Yulan
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Read Online
- Liquid crystal behavior, photoluminescence and gas sensing: A new series of ionic liquid crystal imidazole and benzoimidazole bearing chalcone groups, synthesis and characterization
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Four new series of chalcones containing imidazole bromonium and benzimidazole bromonium salts with spacer alkyl chains (Cn, n = 2 and 4) were synthesized and the chemical structure, thermal behavior, photoluminescence and gas sensing were characterized by
- Abbas, Wahaj Raed,Mohammad, Abdulkarim-Talaq
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p. 38444 - 38456
(2021/12/20)
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- Luminescent mesogenic borondifluoride complexes with the Schiff bases containing salicylideneamines and β-enaminoketones core systems
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Three new families of borondifluoride complexes 1a–c derived from salicylideneamines 2a and β-enaminoketonates 2b–c were reported, and their mesomorphic and optical properties were also investigated. One single crystal and molecular structure of nonmesogenic BF2 complex 1c (n = 10) was resolved and the geometry of the central boron atom was tetrahedron. A larger dihedral angle of 81.3° between the two phenyl rings observed in crystal lattice was attributed to the lack of liquid crystallinity. Boron complexes 1a formed monotropic SmA phases, while boron complexes 1b exhibited enantiotropic SmC mesophases. The optical property of the boron complexes was dependent on their molecular structures, and they emitted a blue–to–green emission at λmax = 476–541 nm in the solution and 488–550 nm in the solid state. This is the first group of mesogenic BF2 complexes with the Schiff bases derived from respective salicylideneamines and β-enaminoketones.
- Lei, Zih-Yang,Lee, Gene-Hsiang,Lai, Chung K.
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- Terbium Functionalized Micelle Nanoprobe for Ratiometric Fluorescence Detection of Anthrax Spore Biomarker
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Rapid, sensitive, and selective quantitative detection of pyridine dicarboxylic acid (DPA) as biomarker of anthrax spores is in great demand since anthrax spores are highly lethal to human beings and animals and also potential biological warfare agents. H
- Luan, Ke,Meng, Ruiqian,Shan, Changfu,Cao, Jing,Jia, Jianguo,Liu, Weisheng,Tang, Yu
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p. 3600 - 3607
(2018/03/13)
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- Synthesis and liquid crystalline properties of a new homologous series of 4,5-disubstituted 2H-[1,2,3]-triazoles via azide-chalcone oxidative cycloaddition reaction
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A new homologous series of 4,5-disubstituted 2H-[1,2,3]-triazole derivatives were synthesized from chalcones and sodium azide via oxidative cycloaddition reaction; CuI was used as catalyst. Flexibility in the synthesized molecules was provided by attaching straight alkoxy chains. The synthesized compounds were characterized by elemental analysis, and 1HNMRand 13CNMRand LC-MS spectroscopies . The stability and range of the mesophases increased with the length of the chain on the triazoles. The melting point, transition temperatures, and enantiotropic liquid crystal morphologies were determined by differential scanning calorimetry (DSC) and polarizing optical microscopy (POM) equipped with a hot stage. Journal compilation
- Sowmya,Rai, K. M. Lokanatha
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p. 764 - 768
(2017/07/07)
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- Fluorescent columnar bis(boron difluoride) complexes derived from tetraketonates
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Three new series of bis-(boron difluoride) complexes 1a-c derived from substituted tetraketonates 2a-c are reported, and their mesomorphic and optical properties have been investigated. Two single crystals of mesogenic ligand 2a (n = 6) and nonmesogenic d
- Chen, Ya-Wen,Lin, Yen-Chun,Kuo, Hsiu-Ming,Lai, Chung K.
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p. 5465 - 5477
(2017/07/10)
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- Mechanochromic luminescent difluoroboron beta-diketonates
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The invention provides luminescent solid-state compositions comprising difluoroboron beta-diketonates wherein the compositions can exhibit mechanochromic luminescence. The mechanochromic effect on the luminescence can be reversible, such as thermally reversible. Various solid-state forms of the invention can have emission spectra that differ from the properties of the respective difluoroboron beta-diketonate in solution. The mechanochromic effect can be stimulated by pressure such as handwriting, and can be reversed over a period of minutes to hours at room temperature. The invention also provides methods of making and methods of using the solid-state compositions, such as for sensors and for information displays for use in biological sensing, and in art, design, and consumer products. Compositions of the invention, such as compositions in nanoparticulate form, or contained within a matrix material, can be used in conjunction with fluorescence microscopy to provide information concerning pressures and tensions within and external to living cells, tissues, or organisms.
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Page/Page column
(2015/07/15)
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- Coordination behaviour of new dipyridylpyrazole ligands towards ZnCl 2 and PdCl2 fragments. Crystalline structural characterization and multinuclear NMR studies as evidence of linkage and conformational isomers
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A series of novel N,N,N-donor pyrazole based ligands of the type pypz R(n)py (R(n) = C6H4OCnH 2n+1, n = 1, 12-18) (1-5) bearing two pyridine substituents at the 1- and 3-positions and an alkyloxyphenyl group at the 5-position have been prepared and characterized. The X-ray structure of pypzR(1)py is presented. Coordination of those ligands to MCl2 fragments (M = Zn, Pd) gives rise to complexes of the type [MCl2(pypzR(n)py)] (M = Zn, Pd; R(n) = C6H4OCnH2n+1; n = 1, 12-18) (6-15) which were characterized and studied in the solid state and in solution. In these compounds the ligands were highly versatile as they were metal coordinated in a N,N-bidentate, N,N,N-tridentate fashion or N,N-bidentate fashion with an additional interaction via the third active nitrogen, this different behaviour depending on the metal fragment as well as on the state (solid or in solution) in which the complexes are. The X-ray structures of [ZnCl2(pypzR(1)py)] (6) and [PdCl2(pypz R(1)py)] (11) have also been determined showing distorted trigonal bipyramid and square-planar geometries at the zinc and palladium centres, respectively. In both cases the coordination environment has been confirmed by 13C-and 15N-NMR studies in solid state. In particular, two binuclear M-M stereoisomers "Z"- and "U"-shaped may be established for the Pd derivative. The 1H and 13C-NMR studies in CDCl3 solution of (6) and (11) indicate the presence of monomeric species which exhibit the same or different bidentate coordination of the ligand, respectively, than that observed in solid state. However, DMSO-d6 causes a total dissociation of the ligand in Zn derivatives, while for the related Pd complexes two monomeric linkage isomers (N2,N1′PdCl2 and N2,N1′′PdCl2) were detected.
- Soria, Lorena,Ovejero, Paloma,Cano, Mercedes,Heras, Jose Vicente,Torres, M. Rosario,Claramunt, Rosa,Cornago, Pilar
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p. 9383 - 9394
(2014/03/21)
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- Synthesis and antimicrobial studies of hydroxylated chalcone derivatives with variable chain length
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A series of (E)-1-(4-alkyloxyphenyl)-3-(hydroxyphenyl)-prop-2-en-1-one have been successfully synthesised via Claisen-Schmidt condensation. The synthesised chalcone derivatives consisted of hydroxyl groups at either ortho, meta or para position and differed in the length of the alkyl groups, CnH 2n+1, where n=6, 10, 12 and 14. The structures of all compounds were defined by elemental analysis, IR, 1H- and 13C-NMR. The antimicrobial studies were carried out against wild-type Escherichia coli American Type Culture Collection 8739 to evaluate the effect of the hydroxyl and the alkyl groups of the synthesised chalcones. All the synthesised compounds have shown significant antimicrobial activities. The optimum inhibition was dependent on the position of the hydroxyl group as well as the length of the alkyl chains.
- Ngaini, Zainab,Haris Fadzillah, Siti M.,Hussain, Hasnain
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experimental part
p. 892 - 902
(2012/08/28)
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- Alkyl chain length effects on solid-state difluoroboron β-diketonate mechanochromic luminescence
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Solid-state difluoroboron β-diketonate dyes display reversible mechanochromic luminescence (ML). To test the effects of alkyl chain length on solid state photoluminescence and ML, a series of dyes, BF2dbmOR, with dibenzoylmethane (dbm) ligands and alkoxyl substituents (-OR) were prepared, where R = CnH2n+1 and n = 1, 2, 3, 5, 6, 12, 14, 16, 18. Emission properties were investigated in solution and in the solid state. Fluorescence spectra and lifetimes were nearly identical for dyes in CH2Cl2 solution; whereas, in the solid state, as powders, thin films or spin cast films, emission maxima, and lifetimes were different among the samples. Solid-state ML emission spectra were monitored at room temperature as a function of time for smeared powders on quartz surfaces. The recovery time generally increased with alkyl chain length, ranging from minutes (n = 3) to days (n = 18). Longer chain analogues (n = 6, 12, 14, 16, 18) did not fully return to the original annealed emissive state even after months on quartz, though the dynamics are substrate dependent. Solid-state dyes were also investigated by XRD and DSC (powders), and by AFM (spin cast films).
- Nguyen, Nguyen D.,Zhang, Guoqing,Lu, Jiwei,Sherman, Arianna E.,Fraser, Cassandra L.
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supporting information
p. 8409 - 8415
(2013/01/11)
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- Synthesis and characterization of chalconesubstituted phosphazenes
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A series of mono[(E)-1-(4-alkyloxyphenyl)-3-(4-hydroxy-phenyl)prop-2-en-1- one]cyclotriphosphazenes and hexakis[(E)-1-(4-alkyloxy-phenyl)-3-(4-hydroxy- phenyl) prop-2-en-1-one]cylotriphosphazenes have been synthesized. A convenient synthetic method was pe
- Ngaini, Zainab,Rahman, Norashikin I. Abdul
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experimental part
p. 654 - 658
(2010/08/21)
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- Mechanochromic luminescence quenching: Force-enhanced singlet-to-triplet intersystem crossing for iodide-substituted difluoroboron-dibenzoylmethane- dodecane in the solid state
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A lipid derivative of difluoroboron-iododibenzoylmethane (BF 2dbm(I)OC12H25) was synthesized via Claisen condensation and boronation. Green photoluminescence is observed for the complex in the solid state. Unlike the previ
- Zhang, Guoqing,Lu, Jiwei,Fraser, Cassandra L.
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supporting information; experimental part
p. 10747 - 10749
(2011/02/16)
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- H-Bonded metallomesogens: preparation, characterization, and mesomorphic studies of (3-hydroxypropylimino)propan-1,2-diols
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Two series of new Schiff bases 2 (n=8, 12, 16) derived from (3-hydroxypropyl imino)propan-1, 2-diol with a hydroxyl group at C19/C20-position and their palladium complexes 1 were prepared and their mesomorphic properties investigated
- Chien, Chieh,Chen, Chun-Jung,Sheu, Hwo-Shuenn,Lee, Gene-Hsiang,Lai, Chung K.
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scheme or table
p. 3583 - 3592
(2010/06/21)
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- Mono-, bis-, and tris(crown ether)s assembled around 1,3,5-triaroylbenzene scaffolds
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(Chemical Equation Presented) A concise and experimentally straightforward method for assembling multiple benzo(crown ether) units around 1,3,5-triaroylbenzene scaffolds has been developed. Symmetrical tris(crown ether)s possessing three benzo(15-crown-5)
- Pigge, F. Christopher,Dighe, Mayuri K.,Houtman, Jon C. D.
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p. 2760 - 2767
(2008/09/20)
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- Synthesis, computational modelling and liquid crystalline properties of some [3]ferrocenophane-containing Schiff's bases and β-aminovinylketone: Molecular geometry-phase behaviour relationship
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Rotationally fixed [3]ferrocenophane extends the variety of possible molecular geometries in its derivatives in comparison with unbridged ferrocenes. In this respect molecular geometry-liquid crystalline properties relationship studies in [3]ferrocenophane mesogens are of considerable interest. Different positional isomers of mono- and di-substituted [3]ferrocenophanes which are obtained by incorporating one or two promesogenic building blocks into the cyclopentadienyl rings are reported in this article. A series of mono-substituted [3]ferrocenophane-containing Schiff's bases was synthesized by condensing isomeric p-aminophenyl [3]ferrocenophanes with appropriate aldehydes. Isomers of di-substituted [3]ferrocenophane amines gave rise to a series of azomethines with two promesogenic substituents in the cyclopentadienyl rings. Besides, a β-enaminoketone was prepared from 3-(p-aminophenyl)[3]ferrocenophane. Nematic and smectic mesophases were observed in the synthesized compounds under a polarizing optical microscope. The [3]ferrocenophane-containing β-enaminoketone showed complex mesomorphic behaviour connected with occurrence of the keto-enamine and imino-enol tautomeric equilibrium in this compound. On the base of computational models obtained by semi-empirical quantum chemistry calculations the molecular geometry-phase behaviour relationships were examined. It was demonstrated that mesomorphism of [3]ferocenophane azomethines depends on the spatial orientation of the substituents with respect to the propanediyl bridge in a case of mono-, and as well as to each other in a case of di-substituted derivatives.
- Kadkin, Oleg N.,Han, Haksoo,Galyametdinov, Yuri G.
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p. 5571 - 5582
(2008/03/18)
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- Supramolecular metallomesogens. Self-organization of an H-bonded tetrameric assembly into columnar phase from single component
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The first example of supramolecular metallomesogens derived from palladium complexes exhibiting columnar phase is reported, and the formation of the mesophase is induced by H-bonding in a tetrameric assembly. The Royal Society of Chemistry.
- Wang, Yueh-Ju,Song, Jian-Hong,Lin, Yu-Siang,Lin, Ching,Sheu, Hwo-Shuenn,Lee, Gene-Hsiang,Lai, Chung K.
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p. 4912 - 4914
(2007/10/03)
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- Liquid crystalline N-aryl-β-aminovinyl ketones and their complexes with lanthanides
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Liquid crystalline lanthanide complexes with N-aryl-substituted β-aminovinyl ketones were synthesized for the first time. The complexes give rise to smectic A mesophase and are stable only in the solid state; in going to solution, they dissociate with for
- Turanova,Galyametdinov
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p. 1095 - 1099
(2008/02/05)
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- On the parity in helical twisting power of Ru(III) 1,3-diketonates of C2 symmetry in nematic liquid crystals
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It is demonstrated that the sign of helical twisting power (HTP) of an enantiomeric Ru(III) complex of type [Ru(acac)2L] can be switched by choosing L from either Lper or Lpara, which is elongated either perpendicular or p
- Yoshida, Jun,Sato, Hisako,Yamagishi, Akihiko,Hoshino, Naomi
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p. 8453 - 8456
(2007/10/03)
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- Chemistry of Rh(I) complexes based on mesogenic 3,5-disubstituted pyrazole ligands. X-ray crystal structures of 3,5-di(4-n-butoxyphenyl)pyrazole (Hpzbp2) and [Rh(μ-pzR2)(CO)2]2 (R = C6H4OCnH2n+1, n = 10, 12) compounds. Part II
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Four new 3,5-disubstituted pyrazoles HpzR2 containing long-chain 4-n-alkyloxyphenyl substituents [R = C6H4OCnH2n+1; n=4 (1), 6 (2), 12 (5), 14 (6)] have been prepared and characterised. All of them showed mesomorphic behaviour,the stability and the range of the mesophases increasing with the length of the chain on the pyrazole. The X-ray structure of Hpzbp2 (1) showed a highly linear molecular shape. Related results were deduced for the remained HpzR2 and the structural consequences agree with the observed mesomorphic properties. The mesogenic pyrazoles HpzR2 (1-6) were used as ligands towards [RhCl(CO)2] and [Rh(CO)2] fragments. [RhCl(CO)2(HpzR2)] complexes (7-12) showed some physical properties dependant on the long-chained pyrazoles, and related to different molecular arrays in the solid state. In all cases these compounds evolved to [Rh(μ-pzR2)(CO)2]2 in solution. The pyrazolate Rh(I) complexes [Rh(μ-pzR2)(CO)2]2 (3-18) had the usual boat conformation, as deduced by the crystal structure of two of these derivatives [n =10 (16), 12 (17)]. The packing arrangement has both layer and columnar characteristics. No mesophases have been detected for any of the Rh(I) complexes.
- Torralba,Cano,Campo,Heras,Pinilla,Torres
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p. 150 - 161
(2007/10/03)
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- Smectic bimetallomesogens in β-enaminoketonate copper complexes: The steric effect of a methyl substituent on the core group and the crystal structure
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A systematic study has been made of the liquid crystalline properties of two types of copper complexes derived from enamino-β-ketonate and iminopropyl-β-ketonate Schiff bases that exhibit mesomorphism. These complexes are structurally similar, and all hav
- Lai, Chung K.,Lin, Raymond,Lu, Min-Yi,Kao, Kwo-Cheng
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p. 1857 - 1862
(2007/10/03)
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- Preparation and Coupling Reactions of Alkynyl(phenyl)iodonium Salts Bearing Long Alkoxy Chains. Formation of Liquid-Crystalline Diacetylenes
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Alkynyl(phenyl)iodonium tosylates with long alkoxy chains, such as (octyloxy)-, (decyloxy)-, (dodecyloxy)-, and (tetradecyloxy)phenyl, were prepared by reaction of the corresponding alkynes with hydroxy(tosyloxy)iodobenzene.The alkynyliodonium tosylates w
- Kitamura, Tsugio,Lee, Chi Han,Taniguchi, Hiroshi,Matsumoto, Masaru,Sano, Youich
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p. 8053 - 8057
(2007/10/02)
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- Functionalized 1,1-Ethene Dithiolates as Ligands, II. Nickel(II), Palladium(II) and Platinum(II) Complexes of Substituted β-Keto Dithio Acid Dianions
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para-Substituted β-ketodithiocinnamic acid dianions react with L2MCl2 to give the 1,1-ethene dithiolate complexes L2M (3: M = Ni, L = PBu3, n = 12; 4a,b: M = Pd, L = PPh3, n = 1, 8; 5a: M = Pt, L = PEt3, n = 1; 5b, 5e-g; 5i: M = Pt, L = PPh3, n = 1, 8, 10, 12, 14; 5c,h: M = Pt, L = 1/2 dppe, n = 1, 12; 5j: M = Pt, L = PPh2Tol, n = 12; 6a-c: M = Pt, L = 1/2 dmphen, n = 8, 12, 16); L2Pt (7a,b: L = PPh3, 1/2 dmphen),(Ph3P)2Pt (8) and L2M (9a: M = Pd, L = PPh3; 9b: M = Pt, L = PEt3; 9c: M = Pt, L = PPh3, 9d: M = Pt, L = 1/2 dppe).These compounds have been characterized by their UV, IR, (1)H, (13)C and (31)P NMR spectra.
- Weigand, Wolfgang,Saumweber, Rupert,Schulz, Peter
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p. 1080 - 1088
(2007/10/02)
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- Antirhinovirus agents
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Compounds of the following general structure are useful as antirhinovirus agents: STR1 wherein Y is a bond, oxygen or divalent sulfur; R is a straight or branched hydrocarbon chain having from 6 to 20 carbon atoms and is saturated or unsaturated having from 1 to 4 double bonds when R has from 10 to 20 carbon atoms and 1 or 2 double bonds when R has from 6 to 9 carbon atoms; and R1 is hydrogen or a straight or branched alkyl group of from 1 to 4 carbon atoms.
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