WO2016046779A1 - Complexes polyazamacrocycliques de zinc - Google Patents

Complexes polyazamacrocycliques de zinc Download PDF

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Publication number
WO2016046779A1
WO2016046779A1 PCT/IB2015/057352 IB2015057352W WO2016046779A1 WO 2016046779 A1 WO2016046779 A1 WO 2016046779A1 IB 2015057352 W IB2015057352 W IB 2015057352W WO 2016046779 A1 WO2016046779 A1 WO 2016046779A1
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Prior art keywords
anion
group
zinc
polyazamacrocyclic
general formula
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PCT/IB2015/057352
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English (en)
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Samuele Santarelli
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Eni S.P.A.
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Publication of WO2016046779A1 publication Critical patent/WO2016046779A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
    • C07F3/003—Compounds containing elements of Groups 2 or 12 of the Periodic Table without C-Metal linkages
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
    • C07F3/06—Zinc compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/054—Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means
    • H01L31/055—Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means where light is absorbed and re-emitted at a different wavelength by the optical element directly associated or integrated with the PV cell, e.g. by using luminescent material, fluorescent concentrators or up-conversion arrangements
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/52—PV systems with concentrators

Definitions

  • the present invention relates to a zinc polyazamacrocyclic complex.
  • the present invention relates to a zinc polyazamacrocyclic complex including at least one ligand comprising an aryl group containing at least one amino group or at least one cyano group.
  • Said zinc polyazamacrocyclic complex may advantageously be used as a spectrum converter in luminescent solar concentrators (LSCs) which are in their turn capable of improving the performance of photovoltaic devices (or solar devices) selected, for example, from photovoltaic cells (or solar cells), photovoltaic modules (or solar modules), whether on a rigid or a flexible support.
  • LSCs luminescent solar concentrators
  • the present invention furthermore relates to a luminescent solar concentrator (LSC) including at least one zinc polyazamacrocyclic complex, as well as to a photovoltaic device (or solar device) comprising said luminescent solar concentrator (LSC).
  • LSC luminescent solar concentrator
  • Metals polyazamacrocyclic complexes are known in the art.
  • the present applicant set itself the problem of finding new zinc polyazamacrocyclic complexes, in particular, new zinc polyazamacrocyclic complexes having elevated luminescence quantum efficiency ( ⁇ ) [( ⁇ ) is defined as the ratio between the number of photons emitted and the number of photons absorbed by a luminescent molecule per unit time and has a maximum value of 1].
  • the present applicant has now found zinc polyazamacrocyclic complexes which include at least one ligand comprising an aryl group containing at least one amino group or at least one cyano group and have elevated luminescence quantum efficiency ( ⁇ ). Furthermore, said zinc polyazamacrocyclic complexes have a good molar extinction coefficient ( ⁇ ): in particular, said molar extinction coefficient ( ⁇ ) increases with the number of ligands comprising an aryl group containing at least one amino group or at least one cyano group.
  • the present invention accordingly provides a zinc polyazamacrocyclic complex having the general formula
  • R 1 ( R 2 , R 3 and R 4 , mutually identical or different, represent a hydrogen atom; or represent: a C 1 -C 2 o, preferably Ci-C 10> linear or branched, saturated or unsaturated, alkyl group optionally containing heteroatoms, an optionally substituted cycloalkyl group, an optionally substituted aryl group, an optionally substituted heteroaryl group; provided that at least one of R t R 2 , R3 and R , is an optionally substituted aryl group or an optionally substituted heteroaryl group; l_i and l_ 2 , mutually identical or different, represent an aryl group containing at least one amino group or at least one cyano group; or a dialkyl sulfoxide group having the general formula (R 5 ) 2 SO in which R 5 , mutually identical or different, represent a C 1 -C 20 , preferably Ci-C 10 , linear or branched, saturated or unsaturated, alkyl group
  • dodecylphosphate anion octadecylphosphate anion, phenylphosphate anion, tetraphenylborate anion; preferably a tetrafluoroborate anion.
  • said zinc poiyazamacrocyclic complex having the general formula (la) or (lb) may be in solvated or hydrated form.
  • C C 2 o alkyl group is taken to mean a linear or branched, saturated or unsaturated, alkyl group having from 1 to 20 carbon atoms.
  • Specific examples of a Ci- C 20 alkyl group are: methyl, ethyl, n-propyl, /so-propyl, n-butyl, /so-butyl, i-butyl, pentyl, ethyl-hexyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl.
  • Ci-C 2 o alkyl group optionally containing heteroatoms is taken to mean a linear or branched, saturated or unsaturated, alkyl group having from 1 to 20 carbon atoms, in which at least one of the hydrogen atoms is substituted with a heteroatom selected from: halogens such as, for example, fluorine, chlorine, bromine, preferably fluorine; nitrogen; sulfur; oxygen.
  • halogens such as, for example, fluorine, chlorine, bromine, preferably fluorine; nitrogen; sulfur; oxygen.
  • Specific examples of a C 1 -C 20 alkyl group optionally containing heteroatoms are: fluoromethyl, difluoromethyl, trifluoromethyl,
  • cycloalkyl group is taken to mean a cycloalkyl group having from 3 to 10 carbon atoms. Said cycloalkyl group may optionally be substituted with one or more mutually identical or different groups selected from: halogen atoms, such as for example fluorine, chlorine, preferably fluorine; hydroxyl groups; Ci-C 20 alkyl groups; d- C 20 alkoxy groups; cyano groups; amino groups; nitro groups.
  • cycloalkyl group examples include: cyclopropyl, 2,2-difluorocyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclohexyl, methoxycyclohexyl, fluorocyclohexyl, phenylcyclohexyl.
  • aryl group is taken to mean an aromatic carbocyclic group containing from 5 to 60 carbon atoms.
  • Said aryl group may optionally be substituted with one or more mutually identical or different groups selected from: halogen atoms such as, for example, fluorine, chlorine, bromine, preferably fluorine; hydroxyl groups; d-C 2 alkyl groups; C C 2 alkoxy groups; Ci-C 12 thioalkoxy groups; C 3 -C 24 trialkylsilyl groups; polyethyleneoxy groups; cyano groups; amino groups; C C 2 mono- or di-alkylamine groups; nitro groups.
  • halogen atoms such as, for example, fluorine, chlorine, bromine, preferably fluorine
  • hydroxyl groups such as, for example, fluorine, chlorine, bromine, preferably fluorine
  • hydroxyl groups such as, for example, fluorine, chlorine, bromine, preferably fluorine
  • hydroxyl groups such as, for example, fluorine, chlorine, bromine, preferably fluorine
  • hydroxyl groups such as, for example, fluorine,
  • an aryl group is: phenyl, methylphenyl, trimethylphenyl, methoxyphenyl, trimethoxyphenyl, hydroxyphenyl, phenyloxyphenyl, fluorophenyl, pentafluorophenyl, chlorophenyl, bromophenyl, nitrophenyl,
  • heteroaryl group is taken to mean a penta- or hexa-atomic, also benzo- fused or heterobicyclic, aromatic heterocyclic group, containing from 1 to 60 carbon atoms and from 1 to 4 heteroatoms selected from nitrogen, oxygen, sulfur, silicon, selenium, phosphorus.
  • Said heteroaryl group may optionally be substituted with one or more mutually identical or different groups selected from: halogen atoms such as, for example, fluorine, chlorine, bromine, preferably fluorine; hydroxyl groups; C Ci 2 alkyl groups; d-C 12 alkoxy groups; C 1 -C 12 thioalkoxy groups; C 3 -C 24 trialkylsilyl groups; polyethyleneoxy groups; cyano groups; amino groups; Ci-Ci 2 mono- or di-alkylamine groups; nitro groups.
  • halogen atoms such as, for example, fluorine, chlorine, bromine, preferably fluorine
  • hydroxyl groups such as, for example, fluorine, chlorine, bromine, preferably fluorine
  • C Ci 2 alkyl groups such as, for example, fluorine, chlorine, bromine, preferably fluorine
  • hydroxyl groups such as, for example, fluorine, chlorine, bromine, preferably fluorine
  • C Ci 2 alkyl groups
  • aryl group containing at least one amino group or at least one cyano group is taken to mean an aromatic carbocyclic group containing from 5 to 60 carbon atoms containing at least one amino group or at least one cyano group.
  • Specific examples of an aryl group containing at least one amino group or at least one cyano group are: pyridine, or-picoline, 3-picoline, y-picoline, 2,3-lutidine, 2,4-lutidine, 2,5-lutidine, 2,6- lutidine, 3,4-lutidine, 3,5-lutidine, 2,3,4-collidine, 2,3,5-collidine, 2,3,6-collidine, 2,4,5- collidine, 2,4,6-collidine, aniline, 1 -naphthylamine, 2-naphthylamine, /V-methylaniline, A/,A/-dimethylaniline, 1 -naphthyl-A/-methylamine, 1 -naph
  • polyazamacrocyclic complex has the general formula (la) in which:
  • R R 2 , R 3 and R 4 mutually identical, represent an optionally substituted aryl group, preferably a phenyl;
  • Li represents an A -(2',6'-di-/so-propylphenyl)monoimide of 9-cyanoperylene-3,4- dicarboxylic acid having the formula (II):
  • l_ 2 represents a dimethyl sulfoxide group [(CH 3 ) 2 SO]
  • Y " represents a tetrafluoroborate anion.
  • said zinc polyazamacrocyclic complex has the general formula (la) in which:
  • R L R 2 , R3 and R 4 mutually identical, represent an optionally substituted aryl group, preferably a phenyl;
  • L T and L 2 mutually identical, represent an /V-(2',6'-di-/so-propylphenyl)monoimide of 9-cyanoperylene-3,4-dicarboxylic acid having the formula (II):
  • Y " represents a tetrafluoroborate anion.
  • Said A -(2',6'-di-/so-propylphenyl)monoimide of 9-cyanoperylene-3,4-dicarboxylic acid having the formula (II) is commercially available and is known by the name Lumogen ® F Yellow 170 from BASF.
  • Said zinc polyazamacrocyclic complex having the general formula (la) or (lb) may be obtained according to processes known in the art as described, for example, by Srivastava S. et al. in the above-mentioned “Synthesis and Reactivity in Inorganic and Metal-Organic Chemistry” (2004), vol. 34, no. 9, pp. 1529-1541.
  • said zinc polyazamacrocyclic complex having the general formula (la) or (lb) may be obtained by a process comprising:
  • R 2 , R3 and R 4 have the same meanings described above with at least one zinc compound selected, for example, from zinc tetrafluoroborate heptahydrate
  • Polyazamacrocycles substituted with at least one aryl or heteroaryl group having the general formula (lai) or (lbi) may be obtained by way of processes known in the art as described, for example, in American patent US 5,587,451 ; or by: Tripier R. er a/., in "From new tricyclic bisaminal derivatives to frans-A/./V'-disubstituted cyclams", “Chemical Communication” (2001 ), pp. 2728-2729; Averin A.D. er a/, in "Synthesis of 1 ,3-Bis(trimethylcyclam) and 1 ,3-Bis(trimethylcyclen) Substituted Benzenes",
  • said polyazamacrocycles substituted with at least one aryl or heteroaryl group having the general formula (lai) or (Ibi) may be obtained by a process comprising reacting at least one polyazamacrocycle having the general formula (la 3 ) or (lb 3 ):
  • Ar represents an optionally substituted aryl group, or an optionally substituted heteroaryl group, preferably an aryl group, still more preferably a phenyl
  • X represents a halogen atom selected from fluorine, chlorine, bromine, iodine, preferably bromine; in the presence of at least one strong base, of at least one anhydrous aprotic organic solvent and of at least one catalyst containing copper in oxidation state +1 having the general formula (IV):
  • said zinc polyazamacrocyclic complex having the general formula (la) or (lb) may advantageously be used as a spectrum converter in luminescent solar concentrators (LSCs) which are in their turn capable of improving the performance of photovoltaic devices (or solar devices) such as, for example, photovoltaic cells (or solar cells), photovoltaic modules (or solar modules), whether on a rigid or a flexible support.
  • LSCs luminescent solar concentrators
  • Said luminescent solar concentrators may be prepared, for example, by melt dispersion of said zinc polyazamacrocyclic complex having the general formula (la) or (lb) in polymeric materials such as, for example, polymethyl methacrylate (PMMA), polystyrene (PS), polyvinyl acetate (PVA).
  • PMMA polymethyl methacrylate
  • PS polystyrene
  • PVA polyvinyl acetate
  • the present invention consequently furthermore provides a luminescent solar concentrator (LSC) including at least one zinc polyazamacrocyclic complex having the general formula (la) or (lb).
  • LSC luminescent solar concentrator
  • Said zinc polyazamacrocyclic complex having the general formula (la) or (lb) may be used in said luminescent solar concentrator (LSC) in the following forms: dispersed in the polymer or in the glass, chemically bound to the polymer or to the glass, in solution or in gel form.
  • the luminescent solar concentrator (LSC) may contain a transparent matrix, where the term transparent matrix is taken to mean any transparent material used in the form of a support, binder, or material in which said at least one zinc polyazamacrocyclic complex having the general formula (la) or (lb) is dispersed or embedded.
  • the material used for the matrix is per se transparent to the radiations in question and, in particular, to the radiations having a frequency within the effective spectrum of the photovoltaic device (or solar device) such as, for example, of the photovoltaic cell (or solar cell) in which it is used.
  • Materials which are suitable for the purpose of the present invention may thus be selected from materials which are transparent at least to radiations having a wavelength of ranging from 250 nm to 1100 nm.
  • the transparent matrix usable for the purposes of the present invention may be selected, for example, from polymeric materials or glassy materials. Said matrix is characterised by high transparency and high resistance to heat and to light.
  • Polymeric materials which may advantageously be used for the purpose of the present invention are, for example, polymethyl methacrylate (PMMA), epoxy resins, silicone resins, polyalkylene terephthalates, polycarbonate, polystyrene, polypropylene.
  • Glassy materials which may advantageously be used for the purpose of the present invention are, for example, silicas.
  • said at least one zinc polyazamacrocyclic complex having the general formula (la) or (lb) may be dispersed in the polymer of said matrix by way of, for example, melt dispersion, and subsequent formation of a sheet comprising said polymer and said at least one zinc
  • said at least one zinc polyazamacrocyclic complex having the general formula (la) or (lb) and the polymer of said matrix may be dissolved in at least one solvent, a solution being obtained which is deposited on a sheet of said polymer, a film being formed which comprises said at least one zinc polyazamacrocyclic complex having the general formula (la) or (lb) and said polymer, for example using a doctor blade film coater, after which said solvent is allowed to evaporate.
  • polyazamacrocyclic complex having the general formula (la) or (lb) may be dissolved in at least one solvent, a solution being obtained which is deposited on a sheet of said matrix of the glassy type, a film being formed which comprises said at least one zinc polyazamacrocyclic complex having the general formula (la) or (lb), for example using a doctor blade film coater, after which said solvent is allowed to evaporate.
  • the present invention further provides a photovoltaic device (or solar device) comprising at least one photovoltaic cell (or solar cell) and at least one luminescent solar concentrator (LSC) including at least one zinc polyazamacrocyclic complex having the general formula (la) or (lb).
  • a photovoltaic device or solar device
  • LSC luminescent solar concentrator
  • Said photovoltaic device may be obtained, for example, by assembling the above-stated luminescent solar concentrator with a photovoltaic cell (or solar cell).
  • the above-stated solar concentrator may take the form of a transparent sheet obtained by way of dissolving said at least one zinc polyazamacrocyclic complex having the general formula (la) or (lb) and the polymer of the matrix of polymeric type in at least one solvent, a solution being obtained which is deposited on a sheet of said polymer, a film being formed which comprises said at least one zinc polyazamacrocyclic complex having the general formula (la) or (lb) and said polymer, for example using a doctor blade film coater, after which said solvent is allowed to evaporate.
  • said sheets may then be coupled to a photovoltaic cell (or solar cell).
  • Carbon, hydrogen, nitrogen and sulfur were determined in the compounds obtained by means of a Thermo Fisher model Flash 2000 automatic analyser, while oxygen was determined by means of a Thermo Fisher model AE 1100 automatic analyser.
  • DMSO d6 hexadeuterated dimethyl sulfoxide
  • the chemical shift scale was calibrated relative to the tetramethylsilane (TMS) signal located at 0 ppm.
  • the FT-IR spectra of the compounds obtained were recorded using Nicolet 8700 FT-IR spectrometer from Thermo Scientific.
  • UV-VIS spectra of the compounds obtained were recorded using a LAMBDA 950 UV/VIS/NIR spectrophotometer.
  • DMSO dimethyl sulfoxide
  • the emission spectra of the compounds obtained were recorded using a Horiba/Jobin Yvon FluoroLog-3 modular spectrofluorometer.
  • the compounds obtained were characterised by electrospray ionisation mass spectrometry using an electrospray ionisation (ESI) source on a LTQ-FT Ultra mass spectrometer.
  • ESI electrospray ionisation
  • the mass spectrometer used was equipped both with a linear ion trap which permitted mass tandem (MS n ) experiments and with an ICR cell within a 7 T magnetic field which enabled operation at extremely high resolution (resolving power up to 106).
  • the powder sample to be analyzed was dissolved initially in dimethyl sulfoxide (DMSO) (Aldrich) and subsequently in acetonitrile (ACN) (Aldrich) in such a quantity as to obtain a sample solution of approximately 0.01 mg/ml.
  • Said solution was introduced by means of a syringe pump (flow rate 10 ⁇ /min) into the electrospray ionisation (ESI) source of the LTQ-FT Ultra mass spectrometer.
  • ESI electrospray ionisation
  • the ions produced were firstly detected by a linear ion trap (at low resolution) and, subsequently, by the ICR cell within the 7 T magnetic field in order to achieve high resolution detection of the ions (RP > 400 k).
  • Electrospray ionisation (ESI) source
  • sheath gas flow rate (arbitrary units): 10.0;
  • auxiliary gas flow rate (arbitrary units): 5.0;
  • capillary voltage 45.0 V
  • capillary temperature 270.0°C
  • ICP/MS Inductively Coupled Plasma Mass Spectrometry
  • DCI desorption chemical ionisation
  • HR/MS Thermo LTQ FT-ICR spectrometer operating by direct infusion of the sample to be analyzed by syringe pump and using the electrospray ionisation (ESI) source.
  • ESI electrospray ionisation
  • Atmospheric pressure ionisation (API) source Atmospheric pressure ionisation (API) source:
  • sheath gas flow rate (arbitrary units): 10.0;
  • auxiliary gas flow rate (arbitrary units): 5.0;
  • capillary voltage 12.0 V
  • capillary temperature 275.0°C
  • the flask was then reimmersed in the bath preheated to 1 19°C and the whole was left under stirring (700 rpm) for 26 hours, operating as follows: when 110°C was reached (indicated by the thermometer with ground glass cone), the insufflator tap was opened, still under argon (Ar) flow, for approximately 5 seconds, in order to avoid any increase in pressure due to the increase in temperature, and the tap was subsequently closed again and the flask was kept at said temperature for 26 hours.
  • reaction mixture were taken from the flask and placed in a test tube containing 1 ml of toluene [C 6 H 5 CH 3 ] (Aldrich) and 2 ml of an aqueous solution at pH 14 prepared with potassium hydroxide (Aldrich) [KOH (a q.)] and the whole was placed under stirring, a two-phase system comprising a predominantly organic phase and a predominantly aqueous phase being obtained.
  • the predominantly organic phase was separated and subjected to thin-layer chromatography (TLC) on neutral alumina using dichloromethane [CH 2 CI 2 ] (Aldrich) as eluent and a 254 nm ultraviolet (UV) lamp as detector: said analysis revealed that 1 ,4,8,11-tetraphenyl-1 ,4,8,11- tetraazacyclotetradecane having the formula (lai a ) had formed.
  • TLC thin-layer chromatography
  • reaction mixture was then drowned in a separating funnel containing toluene
  • the powder obtained was placed on a basic alumina plate (Aldrich) so it could be filtered, initially, with n-heptane (Aldrich) to carry away any low-polarity impurities and, subsequently, with an elution gradient up to a 1/1 vol. /vol. mixture of n-heptane
  • tetrahydrofuran THF
  • argon (Ar) flow into a first 50 ml side-arm test tube equipped with a magnetic stirrer bar, tap and stopper: said first test tube, under argon (Ar) flow (with tap open), was stoppered, immersed in a bath preheated to 80°C, and left at said temperature, under magnetic stirring (200 rpm), for 2 minutes, a first solution being obtained.
  • tetrafluoroborate heptahydrate [Zn(BF ) 2 * 7H 2 0] and 14 ml of tetrahydrofuran (THF) were introduced into a second 20 ml test tube: the whole was stirred at ambient temperature (25°C) for 30 seconds, a second solution being obtained. Said first test tube was then opened and said second solution was added dropwise with a Pasteur pipette to said first solution: said first test tube was restoppered, the tap was closed, and the whole was left in the heating bath at 80°C, under magnetic stirring (200 rpm), for 5 hours. Once the stopper had been removed and the solvent allowed to evaporate, said first test tube was then removed from the heating bath and allowed to cool to ambient temperature (25°C).

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Abstract

L'invention concerne un complexe polyazamacrocyclique de zinc ayant la formule générale (Ia) ou (Ib) : qui peut avantageusement être utilisé en tant que convertisseur de spectre dans les concentrateurs solaires luminescents (LSC), qui sont à leur tour capables d'améliorer la performance de dispositifs photovoltaïques (ou de dispositifs solaires) choisis, par exemple, parmi les cellules photovoltaïques (ou les cellules solaires), les modules photovoltaïques (ou les modules solaires), sur un support rigide ou flexible.
PCT/IB2015/057352 2014-09-25 2015-09-24 Complexes polyazamacrocycliques de zinc WO2016046779A1 (fr)

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ITMI2014A001664 2014-09-25

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT201600071723A1 (it) * 2016-07-08 2018-01-08 Eni Spa Complessi poliazamacrociclici di zinco comprendenti derivati xantenici

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5587451A (en) 1993-11-26 1996-12-24 The Dow Chemical Company Process for preparing polyazamacrocycles
WO2011048458A1 (fr) * 2009-10-19 2011-04-28 Eni S.P.A. Compositions photoluminescentes pour des convertisseurs de spectre à efficacité améliorée
CN102827149A (zh) * 2012-09-06 2012-12-19 中国工程物理研究院核物理与化学研究所 富勒烯单大环多胺衍生物中间体及其制备方法
EP2738175A1 (fr) * 2012-11-30 2014-06-04 ENI S.p.A. Procédé pour la préparation de dérivés de benzodithiophène
WO2014108873A1 (fr) * 2013-01-14 2014-07-17 Eni S.P.A. Procédé de préparation de composés de benzohétéro[1,3]diazole disubstitués par des groupes hétéroaryle

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5587451A (en) 1993-11-26 1996-12-24 The Dow Chemical Company Process for preparing polyazamacrocycles
WO2011048458A1 (fr) * 2009-10-19 2011-04-28 Eni S.P.A. Compositions photoluminescentes pour des convertisseurs de spectre à efficacité améliorée
CN102827149A (zh) * 2012-09-06 2012-12-19 中国工程物理研究院核物理与化学研究所 富勒烯单大环多胺衍生物中间体及其制备方法
EP2738175A1 (fr) * 2012-11-30 2014-06-04 ENI S.p.A. Procédé pour la préparation de dérivés de benzodithiophène
WO2014108873A1 (fr) * 2013-01-14 2014-07-17 Eni S.P.A. Procédé de préparation de composés de benzohétéro[1,3]diazole disubstitués par des groupes hétéroaryle

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Title
AVERIN A.D. ET AL.: "Synthesis of 1,3-Bis(trimethylcyclam) and 1,3-Bis(trimethylcyclen) Substituted Benzenes", MACROHETEROCYCLES, vol. 2, no. 3-4, 2009, pages 281 - 285
BELETSKAYA I.P. ET AL.: "Palladium-Catalyzed Arylation of Linear and Cyclic Polyamines", EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, 2005, pages 261 - 280
SRIVASTAVA S. ET AL., SYNTHESIS AND REACTIVITY IN INORGANIC AND METAL-ORGANIC CHEMISTRY, vol. 34, no. 9, 2004, pages 1529 - 1541
SYNTHESIS AND REACTIVITY IN INORGANIC AND METAL-ORGANIC CHEMISTRY, vol. 34, no. 9, 2004, pages 1529 - 1541
TRIPIER R. ET AL.: "From new tricyclic bisaminal derivatives to trans-N,N'-disubstituted cyclams", CHEMICAL COMMUNICATION, 2001, pages 2728 - 2729

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT201600071723A1 (it) * 2016-07-08 2018-01-08 Eni Spa Complessi poliazamacrociclici di zinco comprendenti derivati xantenici

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