离子液体中微波辅助的 Lewis 酸催化纤维素制备 5-羟甲基糠醛

 以离子液体 1-丁基-3-甲基咪唑氯为溶剂, 以 CrCl3•6H2O 为催化剂, 直接转化纤维素生成 5-羟甲基糠醛 (HMF). 考察了微波辐射条件、反应温度、反应时间及催化剂用量对 HMF 产率的影响. 结果表明, 在最佳条件下, HMF 产率可达 55%.     

若干镧系络合物的空间群

摘要 藉助模拟强度精修将九个镧系络合物晶体结构的空间群作了修正 .（ 1） NaN[Nd(DMSO)5(H2O)3]Cl3· 3H2O从 P1修正为 P;（ 2） Er(ClO4)3· 6(CH3)2NC(O)N(CH3)2从 P修正为 R;（ 3） Nd(O3SCF3)3· DMF· 6H2O从 P1修正为 R3m;(4)[NaNCCH3][Nd{S2CN(CH2CH3)2}4]从 P修正为 C 2/c;(5)[(CH3)2NCS2]3La· 2DMSO从 Cc修正为 C 2/c;（ 6） Yb(C9H7)2· 2THF从 Cc修正为 C 2/c;（ 7） [(C6H5)3Ge]2Yb· 4THF从 P21修正为 P 2;(8)TlPr(C36H44N4)2从 Pna2,修正为 Pnma;(9)[CuLaSm(C4O4)4(H2O)16]· 2H2O从 P2修正为 P2.（ 8）、（ 9）两个络合物结构从非心修正到有心时,不仅改进了键长与键角值,而且影响到分子结构特征的描述 .     

Anomalous conformational change in 1-butyl-3-methylimidazolium tetrafluoroborate-D2O mixtures

We have investigated the effect of deuterated water on the conformational equilibrium between the gauche and trans conformers of the [bmim] cation in mixtures of water and 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF(4)]), an ionic liquid, at room temperature. A comparison of the results obtained from solutions made with H(2)O and with D(2)O highlights an anomalous conformational change in the D(2)O solution showing an extended N-shaped behavior. The gauche conformer of the [bmim] cation in D(2)O increased up to x = ~50 (D(2)O mol %); however, it decreased up to higher water concentrations of x = ~85 before again increasing drastically toward x = ~100. We provide spectroscopic evidence that the anomalous conformational dynamics of the [bmim] cation in D(2)O is directly related to the H/D exchange reaction of the C-H group at position 2 of the imidazolium ring.     

Multinuclear and dynamic NMR study of trans-[Pt(Cl)(PHCy2)2(PCy2)], [Pt(Cl)(PHCy2)3][BF4], [Pt(Cl)(PHCy2)3][Cl], trans-[Pt(Cl)(PHCy2)2[P(S)Cy(2)]], and trans-[Pt(Cl)(PHCy2)2[P(O)Cy2]]. Influence of intramolecular P=O...H-P and Cl...H-P interactions on restricted rotation about Pt-P bond. X-ray structure of trans-[Pt(Cl)(PHCy2)2[P(O)Cy2]

Dynamic NMR experiments on trans-[Pt(Cl)(PHCy2)2[P(X)Cy2]]z where X is a lone pair (1, z = 0), H (2, z = +1), S (3, z = 0), or O (4, z = 0) show that the rotation around the P(X)-Pt bond is hindered for all molecules studied, with deltaG++ ranging from 8.2 to 11.0 kcal/mol. The highest value of the series was calculated for trans-[Pt(Cl)(PHCy2)2[P(O)Cy2]] (4) where intramolecular P=O...H-P interactions act as a molecular brake at room temperature. Single-crystal X-ray diffraction confirms the presence of both intra and intermolecular P=O...H interactions in solid 4. In the case of [Pt(Cl)(PHCy2)3]Cl, multinuclear NMR analysis indicates the presence of a P-H...Cl- interaction in aromatic or halogenated solvents which could have also a minor effect on the rotational barrier around the P(X)-Pt bond.     

Rotational dynamics of water and benzene controlled by anion field in ionic liquids: 1-butyl-3-methylimidazolium chloride and hexafluorophosphate

The rotational correlation time (tau(2R)) is determined for D(2)O (polar) and C(6)D(6) (apolar) in 1-butyl-3-methylimidazolium chloride ([bmim][Cl]) and hexafluorophosphate ([bmim][PF(6)]) by measuring (2)H (D) nuclear magnetic resonance spin-lattice relaxation time (T(1)) in the temperature range from -20 to 110 degrees C. The tau(2R) ratio of water to benzene (tau(WB)) was used as a measure of solute-solvent attraction. tau(WB) is 0.73 and 0.52 in [bmim][Cl] and [bmim][PF(6)], respectively, whereas the molecular volume ratio is as small as 0.11. The slowdown of the water dynamics compared to the benzene dynamics in ionic liquids is interpreted by the Coulombic attractive interaction between the polar water molecule and the anion. As for the anion effect, the rotational dynamics of water solvated by Cl(-) is slower than that solvated by PF(6) (-), whereas the rotational dynamics of benzene is similar in the two ionic liquids. This is interpreted as an indication of the stronger solvation by the anion with a larger surface charge density. The slowdown of the water dynamics via Coulombic solvation is actually significant only at water concentrations lower than approximately 9 mol dm(-3) at room temperature, and it is indistinguishable at temperatures above approximately 100 degrees C. The quadrupolar coupling constants determined for D(2)O and C(6)D(6) in the ionic liquids were smaller by a factor of 2-3 than those in the pure liquid state.     

Effect of ionic liquid on polyaniline chemically synthesised under falling-pH conditions

This study investigates the effect of the ionic liquid 1-butyl-3-methyl imidazolium chloride ([bmim]Cl) on the morphological, structural, and electronic properties of polyaniline (PANI) products synthesised by the falling-pH method. Products were characterised by SEM, FT-IR, UVVIS, N₂-physisorption, and conductivity measurements. The [bmim]Cl addition strongly influenced the PANI morphology, specific surface area, porosity, and conductivity. Depending on the [bmim]Cl: ANI ratio and the synthesis pH, a wide range of PANI nanostructures could be prepared, with rod-like, and fibre-like elongated structures being the dominant morphology under most experimental conditions. Samples prepared in the presence of [bmim]Cl exhibit specific areas of ca 22–35 m² g^?1. The conductivity of the final products depends on the [bmim]Cl: ANI ratio. Temperature dependence of conductivity in the temperature range from 77 K to 300 K was also studied.     

1-丁基-3-甲基咪唑磷钨酸盐的制备及其对酯化反应的催化性能

以溴化1-丁基-3-甲基咪唑盐([bmim]Br)和磷钨酸(H3PW12O40)为原料制备了1-丁基-3-甲基咪唑磷钨酸盐([bmim]3PW12O40)催化剂,并用傅里叶变换红外光谱、热重分析-差示扫描量热法、正丁胺电位滴定及元素分析等技术对催化剂进行了表征,考察了催化剂对乙醇与乙酸酯化合成乙酸乙酯反应的催化活性.结果表明,[bmim]3PW12O40中有3个结晶水,并保持有H3PW12O40的Keggin结构和酸强度,[bmim]3PW12O40的酸量明显少于H3PW12O40的酸量.在乙醇与乙酸酯化合成乙酸乙酯反应中,[bmim]3PW12O40催化剂具有较高的催化活性和较好的重复使用性能.     

Synthesis, structure and reactivity of cuboidal-type cluster aqua complexes with W3PdS4 4+ core

The reaction of PdCl(2) with [W3S4(H2O)9]4+ in the presence of hypophosphorous acid in 2 M HCl gives cuboidal cluster [W3(PdCl)S4(H2O)9]3+ (1) which undergoes condensation and crystallises from Hpts solutions as edge-linked double cubane cluster [{W3PdS4(H2O)9}2](pts)(8).19H2O (pts = p-toluenesulfonate) (1'). The substitution of Cl- in (1) by different ligands was explored. The Pd atom in the cluster shows an exceptionally high reactivity in the isomerisation of the hydrophosphoryl H2P(O)(OH), HP(O)(OH)2, HPPh(O)(OH) and HPPh2(O) molecules into the corresponding hydroxo tautomers HP(OH)2, P(OH)3, PhP(OH)2 and Ph2P(OH) stabilised by coordination at Pd. The reactions were followed by UV-Vis spectrophotometry and 31P NMR. Formation constants of the 1 : 1 coordination of [M3(PdCl)S4(H2O)9]3+ (M = Mo, W) with HP(OH)2 and As(OH)3 were obtained. The structures of cucurbit[6]uril (C36H36N24O12, CUC[6]) adducts [W3(PdP(OH)3)S4(H2O)8Cl]-(C36H36N24O12)Cl3.12.5H2O (2), and [W3Pd(PhP(OH)2)S4(H2O)7Cl2]2(C36H36N24O12)Cl4.9H2O (3) were determined by single-crystal X-ray diffraction.     

Synthesis, chemistry and structures of complexes of the dioxovanadium(V) halides VO2F and VO2Cl

[VO2F(L-L)] (L-L = 2,2'-bipyridyl, 1,10-phenanthroline, Me2N(CH2)2NMe2) and [VO2F(py)2] (py = pyridine) have been prepared from the corresponding [VOF3(L-L)] or [VOF3(py)2] and O(SiMe3)2 in MeCN solution. VO2F (itself made from VOF3 and O(SiMe3)2 in MeCN) forms [Me4N][VO2F2] with [Me4N]F, but does not react with neutral N- or O-donor ligands. VO2Cl, prepared from VOCl3 and ozone, reacts with 2,2'-bipyridyl or 1,10-phenanthroline to form [VO2Cl(L-L)], with pyridine or pyridine-N-oxide (L) to produce [VO2Cl(L)2], and with OPPh3 or OAsPh3 (L') gives [VO2Cl(L')]. A second product from the OPPh3 system is the ionic [VO2(OPPh3)3][VO2Cl2] containing a trigonal bipyramidal cation. Neither VO2F nor VO2Cl form isolable complexes with MeCN, thf or MeO(CH2)2OMe, and both are reduced by P-, As-, S- or Se-donor ligands. [Ph4As][VO2X2] (X = F or Cl) react with 2,2'-bipyridyl to form [VO2X(2,2'-bipyridyl)], but similar reactions with weaker O-donor ligands fail. The complexes have been characterised by IR, multinuclear NMR (1H, 19F, 51V or 31P) and UV-visible spectroscopy. X-ray crystal structures are reported for [VO2F(py)2], [VO2Cl(L)2] (L = py or pyNO) and [VO2(OPPh3)3][VO2Cl2].     

Association of ionic liquids in solution: a combined dielectric and conductivity study of [bmim][Cl] in water and in acetonitrile

Ion association of the ionic liquid [bmim][Cl] in acetonitrile and in water was studied by dielectric spectroscopy for salt concentrations c ≤ 1.3 M at 298.15 K and by measurement of molar electrical conductivities, Λ, of dilute solutions (c ≤ 0.006 M) in the temperature range 273.15 ? T/K ≤ 313.15. Whilst acetonitrile solutions of [bmim][Cl] exhibit moderate ion pairing, with an association constant of K°(A) ≈ 60 M(-1) and increasing with temperature, [bmim][Cl] is only weakly associated in water (K°(A) ≈ 6 M(-1)) and ion pairing decreases with rising temperature. Only contact ion pairs were detected in both solvents. Standard-state enthalpy, entropy and heat capacity changes of ion association were derived, as well as the activation enthalpy of charge transport and the limiting conductivity of the cation, λ(∞)?([bmim](+)). These data, in conjunction with effective solvation numbers obtained from the dielectric spectra, suggest that the solvation of [bmim](+) is much weaker in water than in acetonitrile.     

离子液体[bmim]Cl-CrCl2促进的Reformatsky反应研究

用无水氯化铬(CrCl2)和氯化1-丁基-3-甲基咪唑([bmim]Cl)制备了离子液体[bmim]Cl-CrCl2, 考察了CrCl2与[bmim]Cl物质的量比以及离子液体与底物物质的量比对Reformatsky反应的影响, 研究了[bmim]Cl-CrCl2促进不同底物发生的Reformatsky反应. 结果表明, 离子液体[bmim]Cl-CrCl2不仅能促进醛、酮与α-溴代酸酯的反应, 以极好的产率得到β-羟基酸酯; 而且能较好地诱导α-溴代苯乙酮与醛、酮的反应, 以较高的产率得到β-羟基酮. 该离子液体经处理后可以重复使用, 是一种Reformatsky反应的绿色化学方法.     

ε-己内酯在咪唑型离子液体中开环聚合

报道ε-己内酯在咪唑型离子液体([bmim][Cl])和氧化苯乙烯中的开环聚合.离子液体同时起到了溶剂和催化剂的作用,并且能够回收和循环使用.氧化苯乙烯(SO)是开环聚合起始剂,氢核磁谱分析表明聚己内酯(PCL)端基含有一个SO单元.所得PCL的数均分子量为4.22～6.86kDa,分子量分布小于1.3.该体系无需金属催化剂,减少了有机溶剂的使用.     

Synthesis, spectral and catalytic activity of some manganese(II) bis-benzimidazole diamide complexes

Four Mn(II) complexes bound to a neutral bis-benzimidazole diamide ligand N,N'-bis(2-methyl benzimidazolyl 2,2'-oxy-diethanamide) (GBOA) have been synthesized and characterized. Anionic ligand associated with the complexes varies as Cl- CH3COO-, SCN- and ClO4-. X-ray structure of one of the complexes [Mn(GBOA)2(H2O)2]Cl(2)·4H2O was solved and shows that the Mn(II) ion is hexacoordinate. Two equatorial positions are occupied by benzimidazole imine nitrogen atoms while the other two sites are occupied by amide carbonyl oxygens. The imine nitrogen and carbonyl oxygens are bound to Mn(II) by different arms of the two ligands while axial sites are occupied by two water molecules. Two Cl- anions are outside the coordination sphere and form an extensive 3D H-bonded network. Axially distorted octahedral geometry is confirmed for all the four complexes by low temperature EPR spectroscopy. Distortion parameter D was found to be similar for [Mn(GBOA)2(H2O)2]Cl(2)·4H2O and [Mn(GBOA)2(H2O)2]·(CH3COO)2·H2O. Cyclic voltammograms have been obtained for all the four complexes and E(1/2) values are dependent on the anionic ligand being in the coordination sphere or outside. [Mn(GBOA)2(H2O)2]Cl(2)·4H2O and [Mn(GBOA)2(H2O)2]·(CH3COO)2·H2O carry out the selective oxidation of N-benzyldimethylamine, and 1-methyl-pyrollidine to their respective carbonyl products with catalytic efficiency of 35-50%.     

Synthesis, structures, and electrochemistry of gold(III) ethylenediamine complexes and interactions with guanosine 5'-monophosphate

[Au(en)Cl(2)]Cl.2H(2)O, where en = ethylenediamine (1,2-diaminoethane), has been synthesized, and its structure has been solved for the first time by the single-crystal X-ray diffraction method. The complex has square-planar geometry about Au(III), and the anionic Cl- is located in the apical position and at a distance of 3.3033(10) A compared to 2.2811(9) and 2.2836(11) A for the coordinated Cl-. [Au(en)Cl2]Cl.2H2O belongs to the space group Pbca with a = 11.5610(15) A, b = 12.6399(17) A, c = 13.2156(17) A, alpha = beta = gamma = 90 degrees , and Z = 8. Bond lengths of Au-N are 2.03 A. [Au(en)Cl2]Cl.2H2O is less thermally stable than [Au(en)2]Cl3 because of the replacement of two Cl ligands by a second en ligand in the latter. Cyclic voltammetry shows that the formal potential of Au(III)/Au(0) becomes more negative in the series [AuCl4]-, [Au(en)Cl2]+, and [Au(en)2]3+. 1H, 13C, and 31P NMR reveal that in an aqueous solution [Au(en)Cl2]+ bonds to guanosine 5'-monophosphate, 5'-GMP (1:1 mole ratio), via N7, although the stability is not very high. NMR data also indicate that N7-O6 or N7-phosphate 5'-GMP chelation, as found in some gold(III) nucleotide complexes, is not present. The gold(III) complex undergoes hydrolysis at pH >2.5-3.0 and, therefore, N1 coordination to 5'-GMP is not observed. No direct coordination between 5'-GMP and [Au(en)2]Cl3 is observed.     

Structural and functional characteristics of rhenium clusters derived from redox chemistry of the triangular [ReIII3(mu-Cl)3] core unit

The present study investigates structural and functional aspects of the redox chemistry of rhenium(III) chloride [Re3Cl9] (1) in aqueous and organic solvents, with emphasis on the dioxygen-activating capabilities of reduced rhenium clusters bearing the Re3(8+) core. Dissolution of 1 in HCl (6 M) generates [Re3(mu-Cl)3Cl9]3- (2a), which can be isolated as the tetraphenylphosphonium salt (2b). Anaerobic one-electron reduction of 1 by Hg in HCl (6-12 M) produces [(C6H5)4P]2[Re3(mu-Cl)3Cl7(H2O)2].H2O (3), the structure of which features a planar [Re3(mu-Cl)3Cl3] framework (Re3(8+) core), involving two water ligands that occupy out-of-plane positions in a trans arrangement. Compound 3 dissociates in the presence of CO, yielding [(C6H5)4P]2[ReIII2Cl8] (4) and an unidentified red carbonyl species. In situ oxidation (O2) of the reduced Re3(8+)-containing cluster in HCl (6 M) produces quantitatively 2a, whereas oxidation of 3 in organic media results in the formation of [(C6H5)4P]4[(Re3(mu-Cl)3Cl7(mu-OH))2].2CH2Cl2 (5). The structure of 5 reveals that two oxygen ligands (hydroxo units) bridge asymmetrically two Re3(9+) triangular clusters. The origin of these hydroxo units derives from the aquo ligands, rather than O2, as shown by 18O2 labeling studies. The hydroxo bridges of 5 can be replaced by chlorides upon treatment with Me3SiCl to afford the analogous [(C6H5)4P]4[(Re3(mu-Cl)3Cl7(mu-Cl))2].10CH2Cl2 (6). The reaction of 5 with Hg in HCl (6 M)/tetrahydrofuran regenerates compound 3. Complexes 1-3 exhibit nitrile hydratase type activity, inducing hydrolysis of CH3CN to acetamide. The reaction of 3 with CH3CN yields [(C6H5)4P]2[Re3(mu-Cl)3Cl6.5(CH3CN)1.5(CH3C(O)NH)0.5] (7), the structure of which is composed of [Re3(mu-Cl)3Cl7(CH3CN)2]2- (7a) and [Re3(mu-Cl)3Cl6(CH3CN)(CH3C(O)NH)]2- (7b) (Re3(8+) cores) as a disordered mixture (1:1). Oxidation of 7 with O2 in CH3CN affords [(C6H5)4P]2[Re3(mu-Cl)3Cl7(CH3C(O)NH)].CH3CN (8) and small amounts of [(C6H5)4P][ReO4] (9). Compound 8 is also independently isolated from the reaction of 2b with wet CH3CN, or by dissolving 5 in CH3CN. In MeOH, 5 dissociates to afford [(C6H5)4P]2[Re3(mu-Cl)3Cl8(MeOH)].MeOH (10).     

Melting and freezing behaviors of prototype ionic liquids, 1-butyl-3-methylimidazolium bromide and its chloride, studied by using a nano-Watt differential scanning calorimeter

1-Butyl-3-methylimidazolium bromide ([bmim]Br) and its chloride ([bmim]Cl) are representative prototypes of ionic liquids. We investigated the melting and freezing behaviors of [bmim]Br and [bmim]Cl by using a homemade differential scanning calorimeter (DSC) with nano-Watt stability and sensitivity. The measurements were carried out at heating and cooling rates slow enough to mimic quasi-static processes. Their thermal behaviors of melting and freezing show characteristic features such as a wide pre-melting range and excessive supercooling and individual behaviors of single crystals even for the same substance. The melting temperatures of [bmim]Br and [bmim]Cl were determined from the broad DSC traces and discussed in relation to the crystal structure. We suggest that the observed characteristics are due to the dynamics of the cooperative change between gauche-trans (GT) and trans-trans (TT) conformations of the butyl group in the [bmim]+ cation.     

The Reaction of the Bis-spirocyclic Phosphazene [N 3 P 3 (O 2 C 12 H 8 ) 2 Cl 2 ] (O 2 C 12 H 8 = 2,2′-Dioxybiphenyl) with Thiophenols,in the Presence of Alkali Carbonates

The reactions of the spirocyclic phosphazene [N 3 P 3 (O 2 C 12 H 8 ) 2 Cl 2 ] (O 2 C 12 H 8 = 2,2'-dioxybiphenyl) with the thiophenols HS--C 6 H 4 --R and M 2 CO 3 (M = K or Cs) in refluxing acetone gave respectively the spirocyclic substituted derivatives [N 3 P 3 (O 2 C 12 H 8 ) 2 (SC 6 H 4 --R) 2 ] R = H ( 2a ), Br ( 2b ), OMe ( 2c ), NO 2 ( 2d ). The reaction is a two-step process the second of which is much faster than the first and the monosubstituted intermediate [N 3 P 3 (O 2 C 12 H 8 ) 2 (SC 6 H 4 --R)Cl] cannot be detected. By contrast, in the analogous reactions with the phenols HO--C 6 H 4 --R and M 2 CO 3 (M = K or Cs) in acetone or THF, to give the known derivatives [N 3 P 3 (O 2 C 12 H 8 ) 2 (OC 6 H 4 --R) 2 ], the first step is faster although both are very dependent on R, M and the solvent. Thus, in the case of the phenol HO--C 6 H 4 --OMe the reaction conditions could be adjusted to give the useful synthetic intermediate monosubstituted derivative [N 3 P 3 (O 2 C 12 H 8 ) 2 (OC 6 H 4 --OMe)Cl] ( 3 ). The reaction of [N 3 P 3 (O 2 C 12 H 8 ) 2 Cl 2 ] with the bifunctional reagent mercaptophenol HS--C 6 H 4 --OH was not specific and led to mixtures of cyclic and oligomeric products.     

Isolation and detailed characterization of the trans-[(H2O)2FeCl4](-) anion: stabilization of novel iron(III) species by large organic cations

1,2-Diaminoethane (en) and FeCl3 give (enH2) [FeCl5(H2O)] (1) in concentrated HCl, extending the aquapentachloroferrate(III) series. For 1: C2H12N2Cl5OFe, orthorhombic, P2(1)2(1)2(1), a = 14.531(6) A, b = 10.772(4) A, c = 6.888(2) A, Z = 4. Diazabicyclo[2.2.2]octane dihydrochloride (DABCO-2HCl) and FeCl3 in concentrated HCl form a tetrachloroferrate(III) derivative whose subsequent ethanol treatment (restricted water access) results in the formation of a compound of composition (DABCOH2)2 [FeCl4(H2O)2]Cl3 (2). This contains the trans-[FeCl4(H2O)2](-) anion, in which the trans-Fe-O distances are 2.049(4) A. For 2: C12H32N4Cl7O2Fe, orthorhombic, Pnma, a = 16.378(3) A, b = 7.3323(6) A, c = 19.431(3) A, Z = 4. A combination of 57Fe M?ssbauer spectroscopy and ac susceptibility data confirm uncanted 3D antiferromagnetic ground states with T(Néel) approximately 3.4 K for (enH2)[FeCl5(H2O)] and approximately 2.0 K for [DABCOH2]2[FeCl4(H2O)2]Cl3.     

3-exo-tet Cyclization of 2,2-disubstituted 1,3-dihalopropanes with indium in aqueous and ionic liquid solvent system

The 3-exo-tet cyclization of 2,2-disubstituted 1,3-dihalopropanes with In powder in THF solution of 20% H₂O, dioxane solution of 20% H₂O, and ionic liquids, such as [bmim]Br, [bmim]Cl, and [bmin]BF₄, respectively, was efficiently carried out to form the corresponding 1,1-disubstituted cyclopropanes in good yields. The cyclopropanation of 2,2-disubstituted 1,3-dihalopropanes with In powder in ionic liquids, such as [bmim]Br, [bmim]Cl, and [bmin]BF₄, was markedly accelerated compared with that in a THF solution of 20% H₂O and a dioxane solution of 20% H₂O. The mechanism was proposed to involve the radical 3-exo-tet cyclization of the formed 3-halopropyl radical.     

Polyphosphate ions encapsulated in oxothiomolybdate rings: synthesis, structure, and behavior in solution

Cyclic oxothiomolybdates containing polyphosphate ions were prepared by simple reactions in aqueous medium of the corresponding polyphosphate ions and the cyclic precursor K(2)I(2)Mo(10)S(10)O(10)(OH)(10)(OH(2))(5).15H(2)O. K(5)[Cl(P(2)O(7)]Mo(12)S(12)O(12)(OH)(12)(H(2)O)(4)].22H(2)O (1) was isolated from concentrated chloride solution (2.5 mol.L(-1)). 1 reveals a remarkable complex containing two different substrates encapsulated in a dodecanuclear ring, a H-bonded Cl(-) ion, and a covalently bonded [P(2)O(7)] group. The chloride ion in 1 can be selectively removed for a monohydrogenophosphate group yielding K(6)[(HPO(4))(P(2)O(7))Mo(12)S(12)O(12)(OH)(12)(H(2)O)(2)].19H(2)O (2), a mixed species containing a [P(2)O(7)] and a [HPO(4)] group. The substitution is accompanied by a significant change of the ring, which adopts a "pear-shape" conformation. In the presence of triphosphate ion, the "heart-shaped" decanuclear ring Rb(3)[(H(2)P(3)O(10))Mo(10)S(10)O(10)(OH)(10)].17.5H(2)O (3) is formed containing a linear [P(3)O(10)] group intimately embedded in the inorganic cyclic host. The three compounds were structurally characterized by single-crystal X-ray diffraction. The behaviors of 1, 2, and 3 in solution were studied by (31)P NMR. Variable temperature experiments, supported by a two-dimensional COSY (31)P experiment, revealed that the supramolecular interaction existing between the chloride ion and the ring in solid 1 is maintained in solution. Nevertheless, 1 remains labile, and successive equilibria were evidenced and interpreted as an ion-pair association involving a halide ion (Cl, Br, or I), responsible for the conformational change of the [P(2)O(7)] group within the cavity. The influence of the nature of the halide guest (Cl(-), Br(-), and I(-)) on the successive equilibria was studied, and the thermodynamic constant related to the postulated equilibrium was determined. The stability of the supramolecular association decreases in the order Cl > Br > I. In solution, a phosphate exchange is observed for 2 while for 3 the absence of temperature dependence of the (31)P NMR spectrum confirms the conformation of the host-guest system is blocked. Elemental analysis and infrared characterizations are also supplied.