碲杂冠醚及其铂配合物的合成

本文通过双(2-羟基乙基)碲醚与二醇的二对甲苯磺酸酯缩合, 首次合成了一类新型的冠醚-碲杂冠醚及其中一个碲杂冠醚与二氯化铂的配合物,并对碲杂冠醚的合成方法.结构特征以及配位性能等进行了讨论.     

Inclusion [2]complexes based on the cryptand/diquat recognition motif

Seven diquat-based inclusion [2]complexes were studied by proton NMR spectroscopy, electrospray ionization mass spectrometry, and X-ray analysis. The hosts used in these inclusion [2]complexes are bis(5-hydroxymethyl-1,3-phenylene)-32-crown-10, a bis(m-phenylene)-26-crown-8-based cryptand, and five bis(m-phenylene)-32-crown-10-based cryptands. Bis(m-phenylene)-32-crown-10-based cryptands have been proved to be able to complex diquat much more strongly than bis(m-phenylene)-32-crown-10 itself and one containing a pyridyl moiety has one of the highest K_a values reported to date. These hosts form 1:1 complexes with diquat in solution and in the solid state. It was found that the improved binding from bis(m-phenylene)-32-crown-10 to bis(5-hydroxymethyl-1,3-phenylene)-32-crown-10 was due to a supramolecular cryptand structure formed by chelation of the two terminal OH moieties of bis(5-hydroxymethyl-1,3-phenylene)-32-crown-10 with a water molecule as a hydrogen-bonding bridge.     

冠醚共缩聚物的合成与性能

双冠醚化合物对某些金属离子比单冠醚具有更好的络合性能和选择性,它们合成、应用研究越来越受到人们的重视,本工作采用2,6-二羟甲基对甲氧基苯酚为缩合剂与芳香族冠醚缩聚,得到一系列具有双冠醚结构特征的新酚醛型聚苯并冠醚(简称聚冠醚),聚冠醚合成容易,并呈现了比相应单冠醚更优越的络合萃取能力和富集效率。     

Synthesis of chiral azamacrocycles using the bis(α-chloroacetamide)s derived from chiral 1,2-diphenylethylenediamine

Optically active diphenyl-substituted tetraaza-12-crown-4 diamide ( 10 ), tetraaza-15-crown-5 diamide ( 12 ), tetraaza-18-crown-6 diamide ( 11 ), and hexaaza-18-crown-6 diamide ( 9 ) ligands were prepared by treating the appropriate secondary diamines with the (R,R)- and (S,S)- forms of 1,2-bis(N-methyl-α-chloracetamido)-1,2-diphenylethane ( 20 ). Macrocyclic diamides 9 and 10 were reduced to form the optically active diphenyl-substituted hexaaza-18-crown-6 ( 13 ) and tetraaza-12-crown-4 ( 14 ), respectively. Reduction of macrocyclic diamide ligands 11 and 12 gave a complex mixture of products from which the desired tetraaza-15-crown-5 and 18-crown-6 compounds could not be isolated. Dichloride 20 was prepared by treating the chiral forms of 1,2- diphenylethylenediamine with chloroacetic anhydride or chloroacetyl chloride. The crystal structures for the (R,R)-form of dichloride 20 and the (S,S)-forms of macrocycles 10 and 11 are reported.     

酚醛冠醚共缩聚物的合成与性能

用2,6-二羟甲基-4-苯基苯酚分别与二苯并-18-冠-6(2B18C6)、二苯并-24-冠-8(2B24C8)、二苯并-30冠-10(2B30C10)、苯并-15-冠-5(B15C5)、苯并-18-冠-6(B18C6)缩聚合成了五种酚醛型冠醚共聚物。我们用聚冠醚的氯仿溶液萃取苦味酸碱金属盐水溶液,研究了它们对金属离子的络合性能。结果表明,聚冠醚(PB15C5)和(PB18C6)的萃取能力和选择性显著优于相应的单冠醚。     

铁系元素冠醚配合物的研究 Ⅹ.CoCl_2·Co(NO_3)_2与冠醚固态配合物的合成与性质

本文研究了COCl_2·6H_2O与二苯并-24-冠-8(L_c)。二苯并-30-冠_10(LD),4'-碘苯并-15-冠-5(L_E)和4'-溴苯并-15-冠-5(L_F);Co(NO_3)_2·6H_2O与苯并-15-冠-5(L_A)、L_E和L_F之间的反应,合成了7个尚未见报道的配合物,通过元素分析、摩尔电导、红外、紫外、差热-热重、X-射线粉末衍射等确定了它们的组成,比较分析了配体和配合物的有关性质。     

Self-assembly, structures, and photophysical properties of 4,4'-bipyrazolate-linked metallo-macrocycles with dimetal clips

By employing functional diimine ligands coordinated dipalladium(II,II) or diplatinum(II,II) clips as corners and the coplanar 4,4'-bipyrazolate dianion (L(2-)) ligand as linker, a series of bipyrazolate-bridged metallo-macrocycles, namely, [M8L4](NO3)8 (M = Pd(dmbpy), 1; Pd(bpy), 2; Pt(bpy), 3a; Pd(phen), 4; Pt(phen), 5; Pd(15-crown-5-phen), 6; Pd(18-crown-6-phen), 8; Pd(benzo-24-crown-8-phen), 10a; Pt(15-crown-5-phen), 7a, Pt(18-crown-6-phen), 9a; Pt(benzo-24-crown-8-phen), 11a) and [M6L3](NO3)6 (M = Pt(bpy), 3b; Pt(15-crown-5-phen), 7b; Pt(18-crown-6-phen), 9b; Pd(benzo-24-crown-8-phen), 10b; Pt(benzo-24-crown-8-phen), 11b), have been synthesized through a directed self-assembly approach that involves spontaneous deprotonation of the 1H-bipyrazolyl ligands in aqueous solution. All these compounds have a crown-shaped cavity that can serve as host to solvent molecules and anions. The structures are characterized by elemental analysis, (1)H and (13)C NMR, ESI-MS, and in the cases of 1a (the BF4(-) salt of 1), 2a (the BF4(-) salt of 2), and 3b by single-crystal X-ray diffraction analysis. Photophysical properties for complexes 1 and 2 are discussed.     

Azacrown ethers containing oximic and Schiff base sidearms - potential heteronuclear metal ion receptors

A simple synthetic pathway for the preparation of oxime- and Schiff base-containing aza- and diazacrown ethers is reported. N-Methoxymethyl-substituted aza-15-crown-5 and aza-18-crown-6 as well as N,N′-bis(methoxymethyl)-substituted diaza-18-crown-6 were treated with 5-bromosalicylaldehyde to produce the N-(2′-hydroxy-3′-carbonyl-5′-bromobenzyl)-substituted aza-15-crown-5 (8), aza-18-crown-6 (9) and N,N′-bis(2′-hydroxy-3′-carbonyl-5′-bromobenzyl)-substituted diaza-18-crown-6 (10) compounds. Compounds 8 and 10 were treated with hydroxylamine to give oxime-substituted ligands 12 and 13. A series of bis-Schiff base-containing diaza-18-crown-6 ligands were prepared by reacting 10 with 2-hydroxyaniline (to form 14), 5-nitro-2-hydroxyaniline (15), 2-aminopyridine (16), 2-hydrazinopyridine (17) and N-aminomorpholine (18). Compounds 12–18 are potential complexing agents for simultaneous binding of soft transition and hard alkali or alkaline earth metal ions in one molecule. These new oxime- and Schiff base-containing ligands interacted strongly with Na⁺ and K⁺ in methanol. The interaction of the aromatic portions of 9, 10, and 12–15 with transition metal ions was shown by the UV spectra of the metal ion complexes in 50% aqueous DMF. The X-ray structure of 10 is reported.     

The first [2]pseudorotaxane and the first pseudocryptand-type poly[2]pseudorotaxane based on bis(meta-phenylene)-32-crown-10 and paraquat derivatives

By the self-assembly of a bis(meta-phenylene)-32-crown-10 bearing two electron-donating groups (carbazoles) with electron-accepting paraquat derivatives, the first [2]pseudorotaxane and the first pseudocryptand-type poly[2]pseudorotaxane based on bis(meta-phenylene)-32-crown-10 were isolated as crystalline solids as shown by X-ray analyses.     

Bis(meta-phenylene)-32-crown-10-based cryptand/diquat inclusion [2]complexes

Bis(meta-phenylene)-32-crown-10-based cryptands have been proved to complex diquat much more strongly than bis(meta-phenylene)-32-crown-10 itself; in fact, one containing a pyridyl moiety has one of the highest Ka values yet reported.     

Conductance Study of the Thermodynamics of Binding of Some Macrocyclic Polyethers with Tl+ Ion in Dimethylformamide-Acetonitrile Mixtures

The complexation reactions between Tl⁺ ion and dibenzo-30-crown-10 (DB30C10), dibenzo-24-crown-8 (DB24C8), dibenzo-21-crown-7 (DB21C7), and aza-18-crown-6 (A18C6) were studied in different dimethylformamide-acetonitrile mixtures at various temperatures. The formation constants of the resulting 1 : 1 complexes were determined from the molar conductance-mole ratio data and found to vary in the order A18C6 > DB30C10 > DB21C7 > DB24C8. The enthalpy and entropy of complexation were determined from the temperature dependence of the formation constants.     

New 13-vertex metallacarborane sandwich compounds; synthetic and structural studies

Reduction of 1,12-closo-C2B10H12 followed by reaction with the appropriate metal halide and metathesis with either [K(18-crown-6)]Br or [BTMA]Cl ([BTMA] = [C6H5CH2N(CH3)3]+) affords isolable salts of the supraicosahedral metallacarborane sandwich anions [4,4-M-(1,10-closo-C2B10H12)2]n- in moderate to good yield. Compounds prepared are [BTMA][4,4-Co-(1,10-closo-C2B10H12)2] ( 1), [K(18-crown-6)][4,4-Co-(1,10-closo-C2B10H12)2] ( 2), [K(18-crown-6)]2[4,4-Ni-(1,10-closo-C2B10H12)2] ( 3), [K(18-crown-6)]2[4,4-Fe-(1,10-closo-C2B10H12)2] ( 4), [BTMA]2[4,4-Fe-(1,10-closo-C2B10H12)2] ( 5) and [K(18-crown-6)]2[4,4-Ti-(1,10-closo-C2B10H12)2] ( 6). Oxidation of the iron(II) species 4 and 5 with FeCl3 in THF generates the iron(III) analogues [K(18-crown-6)][4,4-Fe-(1,10-closo-C2B10H12)2] ( 7) and [BTMA][4,4-Fe-(1,10-closo-C2B10H12)2] ( 8), respectively. All diamagnetic compounds were characterised spectroscopically and the structures of 1, 3, 4, 6, 7 and 8 were established by single crystal X-ray diffraction. All anions have the anticipated cluster structures with two docosahedral 13-vertex cages joined at the central metal atom (the common degree-six vertex 4). Carbon atoms occupy the degree-four vertex 1 and the degree-five vertex 10. 11B NMR spectroscopy suggests the anions have, on the NMR timescale, C2h symmetry in solution at room temperature, consistent with free rotation, or at least substantial libration, of cage units about the long molecular axis. In the solid state the relative conformations of the two cages may be rationalised by simple bonding arguments, the single exception being the conformation of 4, in which both cages are subject to directional B-H...K+ interactions to the [K(18-crown-6)]+ counterion. The salts 3, 6 and 7 also show B-H...K+ interactions but involving one cage only.     

Oxonium ions from aqua regia: isolation by hydrogen bonding to crown ethers

The preparation and structures of a variety of oxonium ion tetrachloroaurate(III) salts isolated from aqua regia are reported. The new compounds are [(H(5)O(2))(2)(12-crown-4)(2)][AuCl(4)](2) (1), [(H(7)O(3))(15-crown-5)][AuCl(4)] (2), [(H(5)O(2))(benzo-15-crown-5)(2)][AuCl(4)] (3), [(H(3)O)(18-crown-6)][AuCl(4)] (4), [(H(5)O(2))(dibenzo-24-crown-8)][AuCl(4)] (5), [(H(5)O(2))(4-nitrobenzo-15-crown-5)(2)][AuCl(4)] (6), [(H(3)O)(4-nitrobenzo-18-crown-6)][AuCl(4)] (7), [(H(11)O(5))(tetrachlorodibenzo-18-crown-6)(2)][AuCl(4)] (8), and [(H(7)O(3))(dinitrodibenzo-30-crown-10)][AuCl(4)] (9). A significant correlation between the degree of proton hydration and crown ether size is observed. Aryl crown ethers are nitrated in concentrated aqua regia, but nonnitrated products may be obtained in a dilute solution of aqua regia by reaction with aqueous HAuCl(4).     

Synthesis of substituted 14-crown-4 compounds

Seventeen new substituted 14-crown-4 derivatives 3-10, 35-40, 42, 45 and 46 are described. A series of nine compounds 2-10 with two, three or four substituents in the 6- and/or 13-positions was synthesized in good yields from the appropriate diols and ditosylates using improved cyclization conditions. The solid state structures of 6,6,13,13-tetra(benzyloxymethyl)-14-crown-4 ( 8 ) and lithium thiocyanate complexes of trans- and cis-6,13-bis(spiro-2,2-dichlorocyclopropyl)-14-crown-4 ( 45 ) and ( 46 ), respectively, have been determined.     

Synthesis and Properties of 5-Chloro-8-hydroxyquinoline-Substituted Azacrown Ethers: A New Family of Highly Metal Ion-Selective Lariat Ethers

New 5-chloro-8-hydroxyquinoline (CHQ)-substituted aza-18-crown-6 (4), diaza-18-crown-6 (1), diaza-21-crown-7 (2), and diaza-24-crown-8 (3) ligands, where CHQ was attached through the 7-position, and aza-18-crown-6 (11) and diaza-18-crown-6 (10) macrocycles, where CHQ was attached through the 2-position, were prepared. Thermodynamic quantities for complexation of these CHQ-substituted macrocycles with alkali, alkaline earth, and transition metal ions were determined in absolute methanol at 25.0 degrees C by calorimetric titration. Two isomers, 1 and 10, which are different only in the attachment positions of the CHQ to the parent macroring, exhibit remarkable differences in their affinities toward the metal ions. Compound 1 forms very stable complexes with Mg(2+), Ca(2+), Cu(2+), and Ni(2+) (log K = 6.82, 5.31, 10.1, and 11.4, respectively), but not with the alkali metal ions. Ligand 10 displays strong complexation with K(+) and Ba(2+) (log K = 6.61 and 12.2, respectively) but not with Mg(2+) or Cu(2+). The new macrocycles and their complexes have been characterized by means of UV-visible and (1)H NMR spectra and X-ray crystallography. New peaks in the UV spectrum of the Mg(2+)-1 complex could allow an analytical determination of Mg(2+) in very dilute solutions in the presence of other alkali and alkaline earth metal cations. (1)H NMR spectral and X-ray crystallographic studies indicate that ligand 10 forms a cryptate-like structure when coordinated with K(+) and Ba(2+), which induces an efficient overlap of the two hydroxyquinoline rings. Such overlapping forms a pseudo second macroring that results in a significant increase in both complex stability and cation selectivity.     

CRYSTAL AND MOLECULAR STRUCTURE OF { CNa(15-crown-5)]_n [Cd(SCN)_3]}_n

<正> The complex [Na(15-crown-5)] [Cd(SCN)3] (15-crown-5 = C10H20 O5) crysializes in monoclinic space group P21/c with a=10. 219(2) ,b= 10. 575(2) ,c= 20. 572(2) A ,β=98. 45(1)°,V= 2198. 7A3,Mr=529. 89,Z = 4,Dx=1. 600g/cm3,F (000) -1052,μ= 15. 708cm-1. The structure was solved by direct methods with the final R=0. 064. Results of structure analysis indicate that the Na ion is bonded by 15-crown-5 to form a complex cation and the Cd(Ⅱ) is bonded by six SCN ion to form an anion chain with a distorted octahedral coordination.     

Functionalized large ring crown ethers

Reactions of 3,6,9,12-tetraoxa-7-(benzyloxymethyl)-1,14-tetradecanediol with appropriate ditosylates followed by hydrogenolysis produce hydroxymethyl-27-crown-9 and hydroxy- methyl-30-crown-10. Alkali metal cation complexation by lipophilic dodecyl ether derivatives of these crowns is examined.     

Large-ring,chromogenic benzocrown compounds

Eight novel, large-ring chromogenic benzocrown compounds have been synthesized. Two incorporate 19-and 20-membered crown units with six ring oxygens. Six others contain large rings ranging from 21-crown-7 to 30-crown-10. For all six benzocrown compounds, the 4′-(2″,4″-dinitro-6″-trifluoromethylphenyl)amino group was employed as the chromogenic unit. In addition, 4′-picrylamino and 4′-(2″,6″-dinitro-4″-trifluoromethylphenyl)amino groups were also attached to benzo-21-crown-7.     

Specific features of the chemical behavior of acetylenic derivatives of benzocrown ethers

4"-Ethynylbenzo-12-crown-4 (8), 4"-ethynylbenzo-15-crown-5 (9), and 4"-ethynylbenzo-18-crown-6 (10) were synthesized by cross-coupling of the corresponding aryl iodides 1—3 with 2-methylbut-3-yn-2-ol (4a) followed by the retro-Favorsky cleavage of the resulting carbinols. Unlike the corresponding benzo-12-crown-4 derivative (5a), the cleavage of tertiary acetylenic alcohols of benzo-15-crown-5 (6a) and benzo-18-crown-6 (7a) requires more than one molar equivalent of KOH. Aminoalkylation of crown ether 8 gives Mannich bases, independently of the reaction conditions and the nature of amine. The aminomethylation of acetylenic crown ethers 9 and 10 with paraform—piperidine (morpholine) in the presence of CuCl yields 1,4-disubstituted buta-1,3-diynes (19, 20) rather than Mannich bases.     

Interlayer Energy Transfer from Naphthalene to Anthracene Chromophores Organized in Langmuir—Blodgett Films

Interlayer energy transfer between 2,3-naphthol-10-hexadecylaza-15-crown-5(NC16) and N-[1-(9-methoxyanthryl)] decylaza-15-crown-5(A10C) within multilayer Langmuir-Blodgett films has been studied by steady-state fluorescence spectra. The donor and acceptor could be separated precisely by inserting stearic acid (SA) spacers. The efficiency of the energy transfer increases with the decrease in the donor-acceptor distance by a quadratic manner, suggesting the donor excitations are delocalized in the layer.