Syntheses of Alkaline Earth and Lanthanide Cryptates with Pyridine-Based Group

New alkaline earth metal cryptates [ML]（NO3）2 ·2H2O （M=Ca^2＋, Sr^2＋, Ba^2＋; L = 1, 4,12,15,18, 26, 31, 39, 42, 43, 44-undecaazapentacyclo- [ 13.13.13.1^6,10 .1^20,24 .1^33,37 ]-tetratetraconta -4, 6, 8, 10（44）, 11, 18, 20, 22, 24（43）, 25, 31, 33, 35, 37（42）, 38-pentadecaene） were synthesized by [2 ＋ 3 ] template condensation of tris（2-aminoethyl） amine with 2, 6-diformylpyridine, and then by transmetallation reactions of the calcium cryptate [CaL] （NO3）2·2H2O with corresponding lanthanide ions; three lanthanide cryptates [ LnL] （NO）3·3H2O （Ln = Eu, Gd, Tb） were synthesized and characterized by physical methods. The crystal structure of the terbium cryptate [TbL] （NO）3·3H2O was studied by X-ray analysis. The central atom was coordinated by three pyridyl and six imino nitrogen atoms and exhibited a distorted tricapped trigonal prismatic coordination geometry.

Synthesis of Lanthanide Cryptates by Transmetalation Reaction

New lanthanide cryptates [LnL](ClO_4)_3 (Ln=Eu 3+, Ce 3+, Pr 3+, Sm 3+, Gd 3+, Tb 3+; L=1, 4, 12, 15, 18, 26, 31, 39, 42, 43, 44-undecaazapentacyclo-[13.13.13.1 6, 10.1 20, 24.1 33, 37]-tetratetraconta-4, 6, 8, 10(44), 11, 18, 20, 22, 24(43), 25, 31, 33, 35, 37(42), 38-penta decaene) were synthesized by transmetalation reaction of lanthanide perchlorates with its barium cryptate which was obtained by [2+3] template condensation of tren with 2,6-diformylpyridine in the presence of barium perchlorate, and characterized by elemental analysis, IR and electrospray mass spectrum.

Study on Fluorescence Properties of Eu(Ⅲ) Cryptates

The mononuclear cryptate [Eu(H 3L F)(NO 3)(H 2O)](NO 3) 2 and the heterodinuclear cryptate [EuZnL F(DMF)](ClO 4) 2 were synthesized and characterized. The triplet state energy of the cryptand (H 3L F) was studied by phosphorescence spectrum. The fluorescent properties of Eu(Ⅲ) cryptates in MeOH solution show that the cryptand (H 3L F) can sensitize the Eu(Ⅲ) ion to luminescence and the introduction of the Zn(Ⅱ) ion into the mononuclear Eu(Ⅲ) cryptate resulted in blue shift of three ligand centered bands, increase of molar absorption coefficient and increase of the luminescence intensity of Eu(Ⅲ).

Circularly polarized luminescence of enantiopure carboline-based europium cryptates under visible light excitation

The enantiomers of carboline-based cryptates were successfully resolved by chiral HPLC.These complexes show high configurational stability under harsh conditions and their absolute configuration was determined by comparing theoretical and expe rimental electronic circular dichroism spectra.The e nantiopure cryptates exhibit strong circularly polarized luminescence with a maximum dissymmetry factor glum=0.25 for the f-f transition 5 D0→7 F1(λ=594 nm)under visible light excitation atλgx=400 nm.

Synthesis and Crystal Structure of a New Mononuclear Cadmium(Ⅱ) Cryptate Derived from the Condensation of Tri(2-aminoethyl)amine with Glyoxal

A new mononuclear cadmium（Ⅱ） cryptate has been synthesized by [2＋3] Schiff base condensation of tri（2-aminoethyl）amine with glyoxal in the presence of Cd（ClO4）2·6H2O. The crystal structure, spectral characterization and molar conductivity show that cadmium（Ⅱ） is sixcoordinated （N6） into a distorted octahedral geometry.

The crystal structure of a novel basket binuclear silver (Ⅰ) cryptate

The metal complexes of polyaza cryptand have attracted much attentionowing to their special structure, unusual photo-chemical, electrical and catalyticproperties. Recently, Lehn and Nelson synthesized successively a series ofcryptands and crypatates with high yield by (2+3) schiff-base condensation of tris(2-aminoethyl)amine and aryl dialdehyde. But so far, little work about the analogueswith larger cavities and flexible chains condensed by tris (3-aminopropyl) amine (abbr.