4199-88-6

Usage

Uses

Used in Analytical Chemistry:
5-Nitro-1,10-phenanthroline is used as a reagent in redox titrations for the determination of iron ions. 5-Nitro-1,10-phenanthroline forms a stable complex with iron, which exhibits a distinct color change during the titration process, allowing for accurate measurement of iron concentrations.
Used in Synthesis:
5-Nitro-1,10-phenanthroline serves as a precursor for the synthesis of other phenanthroline derivatives, such as 5-amino-1,10-phenanthroline and 5-isothiocyanato-1,10-phenanthroline. These derivatives possess different functional groups and properties, making them suitable for various applications in chemical research and industry.

Biochem/physiol Actions

Platinum chelates of a variety of 5-substituted phenanthrolines, including 5-Nitro-1,10-phenanthroline, were tested for cytotoxicity against L1210 murine leukemia cells. Though all tested compounds had very similar DNA-binding affinities, they exhibited a wide range of cytotoxicity.

Purification Methods

Crystallise the phenanthroline from *benzene/pet ether, until anhydrous. It also crystallises from H2O with m 202o, and EtOAc with m 203o. Its pK2 5 varies from 3.20 to 2.69 with varying MeOH/H2O ratios from 0 to 0.95 moles/L, and from 3.20 to 1.95 in varying EtOH/H2O ratios from 0 to 0.94 moles/L [Ram et al. J Prakt Chem 319 719 1977]. It forms complexes with Cu2+, Zn2+, In2+, Fe2+ , Co2+, Ni2+ . [Beilstein 23 III/IV 1682, 23/8 V 425.]

InChI:InChI=1/C12H7N3O2.H2O/c16-15(17)10-7-8-3-1-5-13-11(8)12-9(10)4-2-6-14-12;/h1-7H;1H2

Synthetic route

1,10-Phenanthroline (66-71-7) → 5-Nitro-1,10-phenanthroline (4199-88-6)

Conditions	Yield
With sulfuric acid; nitric acid at 160℃; for 3h;	100%
With sulfuric acid; nitric acid at 160℃;	99%
With sulfuric acid; nitric acid at 160℃; for 3h;	99%

1,10-phenanthroline-5-carboxylic acid (630067-06-0) → 5-Nitro-1,10-phenanthroline (4199-88-6)

Conditions	Yield
With nitronium tetrafluoborate; silver carbonate In N,N-dimethyl acetamide at 90℃; for 12h; Inert atmosphere; Schlenk technique; regioselective reaction;	81%

1,10-Phenanthroline (66-71-7) → 1,10-phenanthroline-5,6-dione (27318-90-7) + 5-Nitro-1,10-phenanthroline (4199-88-6)

Conditions	Yield
With sulfuric acid; nitric acid for 1.5h; Heating;	A 20% B 18.7 g

5-nitro-8-aminoquinoline (42606-38-2) + glycerol (56-81-5) → 5-Nitro-1,10-phenanthroline (4199-88-6)

Conditions	Yield
With sulfuric acid; orthoarsenic acid

1,10-Phenanthroline (66-71-7) + sulfuric acid (7664-93-9) + sulfur trioxide (7446-11-9) + nitric acid (7697-37-2) → 4,5-Diazafluoren-9-one (50890-67-0) + 5-Nitro-1,10-phenanthroline (4199-88-6)

Conditions	Yield
at 170℃;

1,10-Phenanthroline (66-71-7) + sulfuric acid (7664-93-9) + sulfur trioxide (7446-11-9) + nitric acid (7697-37-2) → 1,10-phenanthroline-5,6-dione (27318-90-7) + 5-Nitro-1,10-phenanthroline (4199-88-6)

Conditions	Yield
at 170℃;

1,2-diamino-benzene (95-54-5) → 5-Nitro-1,10-phenanthroline (4199-88-6)

Conditions	Yield
Multi-step reaction with 2 steps 1: glycerol; H3aso4; aqueous H2SO4 2: H2SO4; concentrated HNO3 View Scheme

1,10-phenanthroline hydrate (5144-89-8) → 5-Nitro-1,10-phenanthroline (4199-88-6)

Conditions	Yield
With sulfuric acid; nitric acid	1.49 g (42%)

5-Nitro-1,10-phenanthroline (4199-88-6) → 1,10-phenanthroline-5-amine (54258-41-2)

Conditions	Yield
With hydrogen; palladium on activated charcoal In methanol under 2280.15 Torr; for 1h;	100%
With 10% Pd/C; hydrogen In methanol under 2280.15 Torr; for 1h;	100%
With hydrazine hydrate; palladium 10% on activated carbon In ethanol for 4h; Reflux;	98%

ammonium pertechnetate (34035-97-7) + 5-Nitro-1,10-phenanthroline (4199-88-6) → TcO3Cl(5-nitro-1,10-phenanthroline)

Conditions	Yield
With hydrogenchloride In methanol 5-nitro-1,10-phenanthroline dissolved in MeOH by gentle heating, cooled to ambient temp., addn. of Tc-compd. with stirring, dropwise addn. of concd. HCl; cooled to -20°C, ppt. collected, washed with MeOH, dried in vac. overnight; elem. anal.;	99%

dichloro(benzene)ruthenium(II) dimer (37366-09-9) + dichloromethane (75-09-2) + 5-Nitro-1,10-phenanthroline (4199-88-6) → [(η6-C6H6)Ru(η2-5-NO2-1,10-phenanthroline)Cl]Cl*0.2CH2Cl2

Conditions	Yield
In dichloromethane inert atm.; 2 equiv of phenanthroline was added to a suspn. of complex in CH2Cl2, the mixt. was stirred for 3 h at room temp.; evapd. to dryness, dissolved in water, filtered, evapd. to dryness; elem. anal.;	99%

[RuCl2(hexamethylbenzene)]2 + 5-Nitro-1,10-phenanthroline (4199-88-6) → [(η6-hexamethylbenzene)Ru(η2-5-nitro-1,10-phenanthroline)Cl]Cl (861392-80-5)

Conditions	Yield
In dichloromethane inert atm.; 2 equiv of phenanthroline was added to a suspn. of complex in CH2Cl2, the mixt. was stirred for 3 h at room temp.; evapd. to dryness, dissolved in water, filtered, evapd. to dryness; elem. anal.;	99%

[ruthenium(II)(η6-1-methyl-4-isopropyl-benzene)(chloride)(μ-chloride)]2 (52462-29-0) + 5-Nitro-1,10-phenanthroline (4199-88-6) → [(η6-p-cymene)Ru(nitrophen)Cl]Cl (861392-79-2)

Conditions	Yield
In dichloromethane inert atm.; 2 equiv of phenanthroline was added to a suspn. of complex in CH2Cl2, the mixt. was stirred for 3 h at room temp.; evapd. to dryness, dissolved in water, filtered, evapd. to dryness; elem. anal.;	99%
In dichloromethane for 2h; Reflux;

5-Nitro-1,10-phenanthroline (4199-88-6) + N-benzyl-N-(methoxymethyl)-N-[(trimethylsilyl)methyl]amine (93102-05-7) → (4bS*,7aS*)-6-benzyl-4b-nitro-5,6,7,7a-tetrahydro-4bH-pyrrolo[3,4-f][1,10]phenanthroline

Conditions	Yield
With trifluoroacetic acid In dichloromethane at 0 - 20℃; for 5h; Inert atmosphere;	99%

potassium tetrakis (thiocyanato)-palladate (II) + 5-Nitro-1,10-phenanthroline (4199-88-6) → (Pd(5-nitro-1,10-phenanthroline)(SCN)2) (65060-51-7)

Conditions	Yield
In ethanol dropwise addn. of stoich. amt. of ligand to Pd-complex (60°C, pptn.); filtration, washing (H2O, EtOH, Et2O), drying (in air); elem. anal.;	96%

ammonium hexafluorophosphate + 5-Nitro-1,10-phenanthroline (4199-88-6) + C116H84Cl2Ir2N8 → C78H65IrN7O2(1+)*F6P(1-)

Conditions	Yield
Stage #1: 5-Nitro-1,10-phenanthroline; C116H84Cl2Ir2N8 In methanol; dichloromethane for 6h; Reflux; Stage #2: ammonium hexafluorophosphate In methanol; dichloromethane for 0.25h;	95%

5-Nitro-1,10-phenanthroline (4199-88-6) + [{(η3-C3H4COOMe)Mo(CO)2(NCMe)(μ-Br)}2] (1360775-94-5) → [(η3-C3H4COOMe)Mo(CO)2(5-NO2-phen)Br] (1394903-11-7)

Conditions	Yield
In dichloromethane at 20℃; for 0.5h; Inert atmosphere;	94%

copper(II) tetrafluoroborate monohydrate + 5-Nitro-1,10-phenanthroline (4199-88-6) + acetonitrile (75-05-8) → [Cu(NO2C12H7N2)2(CH3CN)](2+)*2BF4(1-)=[Cu(NO2C12H7N2)2(CH3CN)](BF4)2

Conditions	Yield
In acetonitrile dissolving of Cu(BF4)2 hydrate (1 equiv.) in CH3CN, addn. dropwise of soln. of NO2C12H7N2 (2 equiv.) in CH3CN; removal of solvent by rotary evapn.;	93.01%

[(η(3)-allyl)(chloro)dicarbonylbis(methyl cyanide)molybdenum(II)] + 5-Nitro-1,10-phenanthroline (4199-88-6) → [(η3-C3H5)Mo(CO)2(5-NO2-phen)Cl] (1394903-08-2)

Conditions	Yield
In dichloromethane at 20℃; for 0.5h; Inert atmosphere;	93%

manganese(II) perchlorate hexahydrate + 5-Nitro-1,10-phenanthroline (4199-88-6) → Mn2(OOCC6H4COO)(C12H7N2(NO2))4(2+)*2ClO4(1-)*2H2O=[Mn2(OOCC6H4COO)(C12H7N2(NO2))4](ClO4)2*2H2O

Conditions	Yield
With piperidinium 2-chloroterephthalate In methanol addn. of soln. of nitrophenanthroline to soln. of Mn salt and piperidinium chloroterephthalate, stirring (6 h, room temp.; pptn.); filtration, washing (EtOH, Et2O), drying (vac.); elem. anal.;	92%

tris(triphenylphosphine) copper(I) bromide + 5-Nitro-1,10-phenanthroline (4199-88-6) → CuBr(PPh3)(5-nitro-1,10-phenanthroline)

Conditions	Yield
In dichloromethane for 2h; Inert atmosphere;	92%

manganese(II) perchlorate hexahydrate + copper(II) perchlorate hexahydrate + N,N'-bis<2-(dimethylamino)ethyl>oxamide (25148-93-0) + 5-Nitro-1,10-phenanthroline (4199-88-6) → [Cu(N,N'-bis[2-(dimethylamino)ethyl]oxamido dianion)Mn(5-nitro-1,10-phenanthroline)2][ClO4]2

Conditions	Yield
With triethylamine In methanol to soln. of oxamide stirred in MeOH added soln. of Cu(ClO4)2*6H2O in MeOH and Et3N; soln. stirred for 30 min at room temp.; filtered; to filtrate added soln. of Mn(ClO4)2*6H2O in MeOH and 5-NO2-1,10-phenanthroline inMeOH under N2; mixt. stirred for 5 h; crystals filtered; washed (MeOH, H2O, Et2O); dried (P2O5, vac.); recrystd. (DMF/EtOH (1:1)); elem. anal.;	90%

chromium(III) nitrate nonahydrate + N,N'-bis(3-aminopropyl)oxamido copper(II) (20102-49-2) + 5-Nitro-1,10-phenanthroline (4199-88-6) → Cu((OCNC3H6NH2)2)Cr(NO2C12H7N2)2(3+)*3NO3(1-)=[Cu((OCNC3H6NH2)2)Cr(NO2C12H7N2)2](NO3)3

Conditions	Yield
With ethyl orthoformate In ethanol elem. anal.;	90%

cis-dichloro(2,2′-bipyridine)ruthenium(II)chloride + 5-Nitro-1,10-phenanthroline (4199-88-6) → [Ru(bipy)2(5-nitro-1,10-phenanthroline)]Cl2

Conditions	Yield
In water suspn. of bis(2,2'-bipyridine)RuCl2 and 5-nitro-1,10-phenanthroline in water refluxed for 1 h; resulting soln. cooled and filtrated; filtrate evapd. under vac. and residue dissolved in methanol and repptd. into abs. diethyl ether; chromy., NMR;	90%

dichlorotetrakis(dimethylsulfoxide)ruthenium(II) + 5-Nitro-1,10-phenanthroline (4199-88-6) + water (7732-18-5) → cis,cis-[RuCl2(DMSO)2(5-nitro-1,10-phenanthroline)]

Conditions	Yield
In toluene for 2h; Reflux;	90%

ammonium hexafluorophosphate + 5-Nitro-1,10-phenanthroline (4199-88-6) + C116H84Cl2Ir2N8 → C70H49IrN7O2(1+)*F6P(1-)

Conditions	Yield
Stage #1: 5-Nitro-1,10-phenanthroline; C116H84Cl2Ir2N8 In methanol; dichloromethane for 6h; Reflux; Stage #2: ammonium hexafluorophosphate In methanol; dichloromethane for 0.25h;	90%

copper(II) nitrate trihydrate + gadolinium(III) nitrate hexahydrate + 5-Nitro-1,10-phenanthroline (4199-88-6) + N,N'-bis(3-dimethylaminopropyl)oxalamide (25148-90-7) → [Cu(N,N'-bis[3-(dimethylamino)propyl]oxamido)Gd(5-nitro-1,10-phenanthroline)2(NO3)](NO3)2

Conditions

Yield

With triethylamine In methanol; ethanol addn. of soln. of Cu(NO3)2*3H2O and Et3N (2 equiv.) in MeOH to stirred soln. of (Me2NC3H6NHCO)2 in MeOH; stirring at room temp. for 30 min; filtration, addn. of soln. of Gd(NO3)3*6H2O and 5-NO2-phen (2 equiv.) in EtOH to filtrate, pptn., reflux for 9 h; crystn., filtration, washing several times with MeOH, water and Et2O, drying over P2O5 under reduced pressure, recrystn. from DMF/EtOH (1:3); elem. anal.;

89%

ammonium hexafluorophosphate + 5-Nitro-1,10-phenanthroline (4199-88-6) + C116H84Cl2Ir2N8 → C78H65IrN7O2(1+)*F6P(1-)

Conditions	Yield
Stage #1: 5-Nitro-1,10-phenanthroline; C116H84Cl2Ir2N8 In methanol; dichloromethane for 6h; Reflux; Stage #2: ammonium hexafluorophosphate In methanol; dichloromethane for 0.25h;	89%

chromium(III) nitrate nonahydrate + piperidinium terephthalate + 5-Nitro-1,10-phenanthroline (4199-88-6) → [Cr2(OCOC6H4COO)(C5H3NC2HNO2C5H3N)4](4+)*4NO3(1-)=[Cr2(OCOC6H4COO)(C5H3NC2HNO2C5H3N)4](NO3)4

Conditions	Yield
With ethyl orthoformate In ethanol; acetonitrile addn. of a soln. of chromium salt in abs. EtOH to a stirred soln. of piperidinium terephthalate in CH3CN, addn. of ethyl orthoformate, addn. ofa soln. of bpy in abs. EtOH, refluxing for 2 h; filtration, washing with EtOH and Et2O several times, drying over P2O5 in vac., recrystn (DMF); elem. anal.;	88%

manganese(II) perchlorate hexahydrate + 5-Nitro-1,10-phenanthroline (4199-88-6) → (O2NC6H3(COO)2)(Mn(C12H7N2NO2)2)2(2+)*2ClO4(1-) = [(O2NC6H3(COO)2)(Mn(C12H7N2NO2)2)2](ClO4)2

Conditions	Yield
With piperidinium 4-nitrophthalate salt In methanol stirring (room temp., 6 h); ppt. washing (methanol, Et2O), drying (vac.); elem. anal.;	88%

copper(II) nitrate trihydrate + 4,4,4-trifluoro-1-(2-furanyl)-1,3-butanedione (326-90-9) + 5-Nitro-1,10-phenanthroline (4199-88-6) → C20H11CuF3N4O8

Conditions	Yield
Stage #1: copper(II) nitrate trihydrate; 4,4,4-trifluoro-1-(2-furanyl)-1,3-butanedione In methanol at 20℃; for 4h; Stage #2: 5-Nitro-1,10-phenanthroline In methanol at 20℃; for 24h;	88%

Ethyl isocyanoacetate (2999-46-4) + 5-Nitro-1,10-phenanthroline (4199-88-6) → Ethyl 2H-dibenzoisoindole-1-carboxylate (144991-44-6)

Conditions	Yield
With 1,8-diazabicyclo[5.4.0]undec-7-ene In tetrahydrofuran for 4h; Ambient temperature;	87%
With 1,8-diazabicyclo[5.4.0]undec-7-ene In tetrahydrofuran at 20℃;	76%
With 1,8-diazabicyclo[5.4.0]undec-7-ene In tetrahydrofuran Ambient temperature;	53%

5-Nitro-1,10-phenanthroline (4199-88-6) + ethyl 2-cyanoacetate (105-56-6) → Ethyl 2H-dibenzoisoindole-1-carboxylate (144991-44-6)

Conditions	Yield
With 1,8-diazabicyclo[5.4.0]undec-7-ene In tetrahydrofuran for 8h; Ambient temperature;	87%

ferrous(II) sulfate heptahydrate + 2-chloroterephthalate piperidinium salt + 5-Nitro-1,10-phenanthroline (4199-88-6) → C56H31ClN12O12Fe2(2+)*SO4(2-) (262278-48-8)

Conditions	Yield
In methanol mixt. in MeOH was stirred at room temp. for 6 h under N2; filtered, washed with MeOH and Et2O, dried over P2O5 under reduced pressure, recrystd. from DMF-EtOH; elem. anal.;	87%

neodymium(III) perchlorate hexahydrate + piperidinium isophthalate + 5-Nitro-1,10-phenanthroline (4199-88-6) → Nd2((OOC)2C6H4)((O2N)C12H7N2)4(ClO4)2(2+)*2ClO4(1-)*H2O=[Nd2((OOC)2C6H4)((O2N)C12H7N2)4(ClO4)2](ClO4)2*H2O + perchlorate(1-) (14797-73-0)

Conditions	Yield
In ethanol; acetonitrile dropwise addn. of soln. of Ln(ClO4)2 (in EtOH) and sol. of nitrophenanthroline (in MeCN) to soln. of isophthalate (in EtOH) (stirring), refluxing (18 h; pptn.); filtration, washing (EtOH, MeCN, Me2O), drying (over P2O5, vac.), recrystn. (DMF/EtOH 2 : 1); elem. anal.;	A 87% B n/a

ammonium hexafluorophosphate + [iridium(III)(μ-chloro)(2-phenylpyridine)2]2 + 5-Nitro-1,10-phenanthroline (4199-88-6) → [Ir(2-phenylpyridine(-H))2(5-nitro-1,10-phenanthroline)](hexafluorophosphate) (958242-91-6)

Conditions	Yield
In methanol; dichloromethane (N2); refluxing soln. of iridium compd. and phenanthroline deriv. in 2:1mixt. of CH2Cl2 and methanol for 5-6 h, cooling to room temp., addn. of hexafluorophosphate salt, stirring for 15 min; filtration, evapn., dissolving in CH2Cl2, filtration, layering with ether, cooling to 0°C for overnight, isolation of crystals, elem. anal.;	87%

copper(II) choride dihydrate + 5-Nitro-1,10-phenanthroline (4199-88-6) + (S,S)-1,2-diaminocyclohexane (21436-03-3) + potassium perchlorate → [copper(II)((1S,2S)-diaminocyclohexane)(5-nitro-1,10-phenanthroline)](perchlorate)2 monohydrate

Conditions	Yield
In ethanol; water at 60℃; for 3.5h;	87%

Upstream product

• 66-71-7 1,10-Phenanthroline 
• 42606-38-2 8-amino-5-nitroquinoline 
• 56-81-5 glycerol 
• 7664-93-9 sulfuric acid 
• 7446-11-9 sulfur trioxide 
• 7697-37-2 nitric acid 
• 5144-89-8 1,10-phenanthroline hydrate 
• 630067-06-0 1,10-phenanthroline-5-carboxylic acid 
• 95-54-5 1,2-diamino-benzene 

Downstream Products

• 54258-41-2 1,10-phenanthroline-5-amine 
• 27318-90-7 1,10-phenanthroline-5,6-dione 
• 168646-53-5 5-nitro-6-amino-1,10-phenanthroline 
• 229622-33-7 [Cu(5-nitro-1,10-phenanthroline)(salicylaldehydate)]NO₃ 
• 172545-34-5 Cu(H₂NC₆H₄COO)2(C₁₂H₇N₂NO₂) 
• 1174520-51-4 [Ir(cyclometallated 4,5-diphenyl-2-methyl-thiazole)2(5-nitro-1,10-phenanthroline)][PF₆] 
• 1334168-60-3 [Cu(2-phenyl-3-hydroxy-4(H)-quinoline^(1-))(5-nitro-1,10-phenanthroline)]NO₃*H₂O 

Relevant academic research and scientific papers

Synthesis, photophysical properties, and theoretical studies on pyrrole-containing bromo Re(I) complex

Two bromo rhenium(I) carbonyl complexes with the formula of [Re(CO)3(L)Br], where L = 1,10-phenanthroline (Phen-Re) and 5-(1H-pyrrol-1-yl)-1,10-phenanthroline (Pyph-Re), were successfully synthesized with the aim to analyze the effect of the pyrrole (Py) moiety on the photophysical properties of Pyph-Re. It was found that the triplet metal-to-ligand charge-transfer dπ (Re) → π*(N-N) emission of Phen-Re and Pyph-Re centered at ca. 527 nm with the luminescence quantum yield (LQY) of 0.015 and ca. 578 nm with the LQY of 0.011, respectively. At the same time, the geometrical structures of the ground state and the absorption spectral properties of Phen-Re and Pyph-Re were also calculated with the 6-31G* basis set employed on C, H, N, O, and Br atoms, and LANL2DZ adopted on Re atom. According to the experimental and theoretical analysis, the red-shift of the photoluminescent spectrum and the lower LQY of Pyph-Re should be mainly attributed to the narrower energy gap between the highest occupied molecular orbital and the lowest unoccupied molecular orbital and the more LLCT transition ration of Pyph-Re, respectively.

Luminescent ruthenium(II) polypyridyl functionalized gold nanoparticles; Their DNA binding abilities and application as cellular imaging agents

The synthesis and photophysical and biological investigation of Ru(II)-polypyridyl stabilized water-soluble, luminescent gold nanoparticles (AuNPs) are described. These structures bind to DNA and undergo rapid cellular uptake, being localized within the cell cytoplasm and nucleus within 4 h.

A shining proposal for the detection of dissolved O2 in aqueous medium: Self-calibrated optical sensing via a covalent hybrid structure of carbon-dots&Ru

O2 is a life-supporting gas and has been widely recognized as an important analyte in life science, medical care and environmental science. Optical sensing for gaseous oxygen has been widely reported owing to the simple, cost-effective and easy-to-go procedure. On the other hand, optical sensors for dissolved oxygen in aqueous media have been rarely reported, since most of them are incompatible with water, leading to poor sensitivity and linearity. In this effort, we tried the combination of Ru(II)-bpy complex and carbon dots (CDs) via covalent bonds, where bpy = bipyridine. A hybrid structure, named as Ru@CD, was constructed for the detection of dissolved oxygen, using Ru(II)-bpy as sensing probe and CDs as water-compatible supporting matrix. Ru@CD was carefully characterized to confirm its hybrid structure. Detailed analysis suggested that its emission showed self-calibrated sensing signals for dissolved oxygen. A good linearity of 99.1% was realized. Its sensitivity (3.18) was higher than most literature values for dissolved oxygen detection. Its working equation was confirmed as a corrected Stern-Volmer equation (Lehrer mode). Good selectivity and signal stability were observed.

Synthesis and characterization of a Eu-containing polymer precursor featuring thenoyltrifluoroacetone and 5-acrylamido-1,10-phenanthroline

A polymerizable ligand, 5-acrylamido-1,10-phenanthroline (L), was synthesized. Its Eu(III) complex with 2-thenoyltrifluoroacetone (HTTA) was prepared and characterized by elemental analysis, IR, MS, and 1H NMR spectra. The photophysical properties of the complex were studied in detail by using UV, luminescence spectra, luminescence lifetime and quantum yield. The complex shows a remarkable luminescence quantum yield at room temperature (40.1%) upon ligand excitation and a long 5D0 lifetime (590 μs), which makes it not only a promising light-conversion molecular device but also an excellent luminescent polymer precursor.

Synthesis and characterization of luminescent SiO2@Eu(phen–Si) core–shell nanospheres

Four core–shell structured nanometre luminescent composites with different kernel sizes and different shell layer thicknesses (SiO2(500)@Eu (phen–Si)(50), SiO2(500)@Eu (phen–Si)(15), SiO2(250)@Eu (phen–Si)(5) and SiO2(250)@Eu (phen–Si)(10)) were made by changing synthesis conditions. Here, initial subscript numbers in parentheses refer to the particle size of the SiO2 core, whereas the final subscript numbers in parentheses refer to shell layer thickness. In these composites, silica spheres of 500?nm or 250?nm were identified as the core. The shell layer was composited of silicon, 1,10-phenanthroline and europium perchlorate, abbreviated as Eu(phen–Si); the chemical formula of phen–Si was phen-N-(CONH (CH2)Si(OCH2CH3)3)2. The composites were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), and infrared spectroscopy. The monodispersed spherical SiO2 showed characteristics of a regular microstructure and a smooth surface, as well as the advantage of dispersity, shown by SEM. The Eu(phen–Si) complex was able to self-assemble into monodispersed SiO2 spheres, as seen using TEM. Fluorescence spectra indicated that the four composites had excellent luminescence properties. Furthermore, composites composed of a SiO2 core and a 250?nm kernel size exhibited stronger fluorescence than 500?nm kernel-sized composites. Fluorescence properties were affected by shell thickness: the thicker the shell, the greater the fluorescence intensity. For the four composites, quantum yield values and fluorescence lifetime corresponded to fluorescence emission intensity data as quantum yield values and fluorescence lifetime were higher, and luminescence properties increased.

In situ generation of self-enhanced luminophore by β-lactamase catalysis for highly sensitive electrochemiluminescent aptasensor

This work described a new electrogenerated chemiluminescence (ECL) aptasensor for ultrasensitive detection of thrombin (TB) based on the in situ generating self-enhanced luminophore by β-lactamase catalysis for signal amplification. Briefly, a ruthenium complex (Ru-Amp), including two regions of [Ru(phen)2(cpaphen)]2+ and ampicillin (Amp), was synthesized as a self-enhanced ECL luminophore, which can produce an ECL signal through intramolecular interactions. Then, carbon nanotubes (CNTs) were used for immobilization of Ru-Amp via π-π stacking interactions to form the Ru-Amp@CNTs nanocomposite. Using poly(ethylenimine) (PEI) as a linkage reagent, Au nanocages (AuNCs), owing to their electronic property and large surface areas, were decorated to the CNTs to form the Ru-Amp@CNTs-PEI-AuNCs nanocomposites, which were further used to immobilize thrombin binding aptamer II (TBA II) to form a signal probe (Ru-Amp@CNTs-PEI-AuNCs-TBA II). Through "sandwich" tactics, TBA II bioconjugates, TB and TBA I were immobilized onto the gold nanoparticles modified electrode. Then, with the enzyme catalysis of β-lactamase, a novel self-enhanced ECL luminophore (Ru-AmpA) was in situ produced, which could exhibit a significant enhancement of ECL signal, due to the structure transformation of an amide bond into a secondary amine. A sandwich ECL assay for TB detection was developed with excellent sensitivity of a concentration variation from 1.0 fM to 1.0 pM and a detection limit of 0.33 fM. Therefore, the self-enhanced ECL luminophore, combining the further enhancement by in situ enzymatic reaction, is expected to have potential applications in biotechnology and clinical diagnosis.

Preparation and valence tautomeric behavior of a cobaltdioxolene complex with a new TTF-functionalized phenanthroline Ligand

In this study, a new tetrathiafulvalene-functionalized phenanthroline ligand (TTF-phen) and a mononuclear cobalt(II) complex with a redox active 3,6-di-tert-butylsemiquinonato (3,6-dtsq) ligand was synthesized. Magnetic measurementsand IR spectroscopy suggested that the Co complex [Co(3,6- dtsq)2(TTF-phen)] exhibited thermally induced valence tautomerismin the temperature range 130400 K. This complex is the first example of a valence tautomeric complex with a TTFfunctionalized ligand.

Memristors Based on an Iridium(III) Complex Containing Viologen for Advanced Synaptic Bionics

Memristors with nonvolatile memory properties are expected to open the era of neuromorphic computing. However, it remains a huge challenge to develop memristors with high uniformity, high stability, and low power consumption for advanced synaptic bionics. Herein, an electroactive iridium(III) complex Ir-vio was designed and synthesized by incorporating a viologen moiety into its N?N ligand. Complex Ir-vio showed multiple redox states and high sensitivity to an electrical stimulus. Importantly, two-terminal memristors with Ag/Ir-vio/W structure were successfully fabricated by the solution-processable method, which exhibited multilevel storage characteristics with a low switching threshold voltage of 0.5 V and high ON1/ON2/ON3/OFF current ratio of 105/103/102/1 at a low reading bias of 0.05 V. Moreover, the memristors can mimic synaptic plasticity, indicating that they can act as artificial synapses to construct brain-inspired neural networks. The memristive mechanisms can be ascribed to the interconversion among different charge-transfer and redox states under various electrical stimulus. To the best of our knowledge, this work is the first experimental demonstration of memristors based on iridium(III) complexes, opening a new era for the development of synaptic bionic devices based on organometallic compounds.

A highly selective off-on red-emitting phosphorescent thiol probe with large stokes shift and long luminescent lifetime

(Figure presented) An OFF-ON red-emitting phosphorescent thiol probe is designed by using the 3MLCT photophysics of Ru(II) complexes, i.e., with Ru(II) as the electron donor. The probe is non-luminescent because the MLCT is corrupted by electron transfer from Ru(II) to an intramolecular electron sink (2,4-dinitrobenzenesulfonyl). Thiols cleave the electron sink, and the MLCT is re-established. Phosphorescence at 598 nm was enhanced by 90-fold, with a 143 nm (5256 cm-1) Stokes shift and a 1.1 μs luminescent lifetime.

Photophysical properties of lanthanide complexes with 5-nitro-1,10- phenanthroline

Five novel lanthanide (Eu3+, Tb3+, Sm 3+,Dy3+, and Gd3+) complexes with 5-nitro-1,10-phenanthroline (phenNO2) have been synthesized and characterized by elemental analysis, IR, UV, and luminescence spectra. Thetriplet state energy of phenNO2 was determined to be 20,048 cm-1 via the phosphorescence spectra of phenNO2 and its gadolinium complex. The photophysical properties of these complexes indicated that the triplet state energy of the ligand is suitable for the sensitization of the luminescence of Eu3+ and Sm3+, especially the former. Springer-Verlag 2010.