Oxidative properties of iodine-adducts of propylthiouracil and methimazole: direct synthesis of mercury(II) complexes from the reaction with liquid mercury

The I(2)-adducts of drugs propylthiouracil (PTU) and methimazole (MeImSH) oxidize liquid mercury in dichloromethane to separate in good yield the neutral complexes [HgI(2)(PTU)(2)·MeOH] (1), [HgI(2)(PTU)(2)·HgI(2)] (2), and [Hg(2)I(4)(MeImSH)(2)] (3). The single crystal X-ray diffraction analysis of 1-2 shows that the Hg(II) center is coordinated by two sulfur atoms and by two iodine atoms in a tetrahedral geometry. In complex 2 almost linear molecules of HgI(2) result encapsulated in the crystal packing enfolded by the hydrophobic propyl appendages of coordinated units of PTU. X-ray analysis of complex 3 shows the presence of dimeric [Hg(2)I(4)(MeImSH)(2)] molecules to form Hg(2)S(2)I(4) cores. The intra- and intermolecular hydrogen bonds concerning PTU and MeImSH have been evaluated. The oxidation of Hg(0) to Hg(II) requires a two-electron transfer process accomplished by an oxidative addition from the "activated" iodine moiety. The oxidizing and complexing properties of PTU-I(2) and MeImSH-I(2) have been interpreted considering the S-donor to I(2) interaction that leads to a charge separation between the sulfur-bound iodine atom S-I and the terminal I atom. Compounds 1, 2, and 3 react with tetraethylammonium iodide to separate the compound (Et(4)N)(2)[HgI(4)] with the release of free PTU and MeImSH, respectively. The reported dissolution technique could be applied to the recovery of mercury from waste electrical and electronic equipment (WEEE) scrap, the nature of complexes 1-3 makes it possible the easy separation of the mercury as tetraiodomercurate anion and the recycling of the donors.     

酸性介质中碘离子在铂电极上的电化学氧化行为

采用循环伏安法研究了酸性介质中碘离子在铂电极上不同电位区间, 不同酸度下的电化学反应行为. 结果表明, 当极化电位较低(小于0.6 V(vs Hg/Hg2SO4))时, 碘离子在铂电极上发生2I--2e→I2电氧化反应, 反应产物通过I2+I-=I-3被进一步溶解, 整个反应属于E-C(electrochemical-chemical)模式. 电氧化过程中可以形成碘膜, 其也可以被碘离子溶解. 当极化电位升高至0.6 V(vs Hg/Hg2SO4)或以上时, 碘离子会直接电氧化为高价态碘化合物, I-+3H2O→IO-3+6H++6e, 而析出的碘膜并不发生再氧化反应; 在电化学还原过程中, 出现了两个还原峰, 分别对应于I2、I-3的还原反应; 在无碘膜时, 碘离子电氧化过程受溶液中碘离子的液相扩散步骤控制; 碘膜形成后, 主要受碘膜中碘离子的固相扩散控制; 酸度对于碘离子的电化学氧化过程有很大的影响, 其线性极化曲线的起峰电位及电流峰值电位均随酸浓度升高而负移.     

Spectrophotometric determination of iodine species in table salt and pharmaceutical preparations

A sensitive spectrophotometric method for the determination of iodine species like iodide, iodine, iodate and periodate is described. The method involves the oxidation of iodide to ICl(2)(-) in the presence of iodate and chloride in acidic medium. The formed ICl(2)(-) bleaches the dye methyl red. The decrease in the intensity of the colour of the dye is measured at 520 nm. Beer's law is obeyed in the concentration range 0-3.5 microg of iodide in an overall volume of 10 ml. The molar absorptivity of the colour system is 1.73 x 10(5) l mol(-1) cm(-1) with a correlation coefficient of -0.9997. The relative standard deviation is 3.6% (n=10) at 2 microg of iodide. The developed method can be applied to samples containing iodine, iodate and periodate by prereduction to iodide using Zn/H(+) or NH(2)NH(2)/H(+). The effect of interfering ions on the determination is described. The proposed method has been successfully applied for the determination of iodide and iodate in salt samples and iodine in pharmaceutical preparations.     

On the intercalation of the iodine-iodide couple on layered double hydroxides with different particle sizes

Molecular iodine was intercalated from nonaqueous solution into microsized ZnAl-layered double hydroxide (LDH) in the iodide form, generating the I(3)(-)/I(-) redox couple into the interlayer region. Chloroform, ethanol, acetonitrile, or diethyl ether were used as solvents to dissolve the molecular iodine. The intercalation compounds were characterized by thermogravimetric analysis, X-ray powder diffraction, UV-vis spectroscopy, and scanning and transmission electron microscopy. The stability of iodine-solvent adducts and the iodine concentration affected the LDH iodine loading, and samples with I(2)/I(-) molar ratio ranging from 0.14 to 0.82 were prepared. Nanosized, well dispersible LDH, synthesized by the urea method in water-ethylene glycol media, were also prepared and successfully functionalized with the I(3)(-)/I(-) redox couple applying the conditions optimized for the micrometric systems.     

In-capillary derivatization and determination of iodine in sodium chloride solution

A new capillary electrophoretic (CE) method was developed for the simple and selective determination of iodine in 0.5 mol l(-1) NaCl. The proposed method is based on the in-capillary derivatization of iodine with thiosulfate ions using the zone-passing technique and direct photometric detection of the iodide and tetrathionate formed. The optimal conditions for the separation and derivatization reaction were established by varying the concentration of iodine, electrolyte pH and applied voltage. The optimized separations were carried out in phosphate electrolyte (pH 6.86) using direct photometric detection at 253.7 nm. Common photometric detection absorbing anions such as Cl(-), NO(2)(-), S(2)O(3)(2-) did not give any interference. Valid calibration (r(2) = 0.994) is demonstrated in the range 16.5-198.1 mg l(-1) of iodine. The detection limit (calculated according to K. Doerffel, Statistik in der analytischen Chemie, 1990) was 11.53 mg l(-1) (by iodide peak area) and 8.45 mg l(-1) (by tetrathionate peak area). The proposed system was applied to the determination of iodine after oxidation of iodide in underground water.     

Influence of ion pairing on the oxidation of iodide by MLCT excited states

The oxidation of iodide to diiodide, I(2)˙(-), by the metal-to-ligand charge-transfer (MLCT) excited state of [Ru(deeb)(3)](2+), where deeb is 4,4'-(CO(2)CH(2)CH(3))(2)-2,2'-bipyridine, was quantified in acetonitrile and dichloromethane solution at room temperature. The redox and excited state properties of [Ru(deeb)(3)](2+) were similar in the two solvents; however, the mechanisms for excited state quenching by iodide were found to differ significantly. In acetonitrile, reaction of [Ru(deeb)(3)](2+*) and iodide was dynamic (lifetime quenching) with kinetics that followed the Stern-Volmer model (K(D) = 1.0 ± 0.01 × 10(5) M(-1), k(q) = 4.8 × 10(10) M(-1) s(-1)). Excited state reactivity was observed to be the result of reductive quenching that yielded the reduced ruthenium compound, [Ru(deeb(-))(deeb)(2)](+), and the iodine atom, I˙. In dichloromethane, excited state quenching was primarily static (photoluminescence amplitude quenching) and [Ru(deeb(-))(deeb)(2)](+) formed within 10 ns, consistent with the formation of ion pairs in the ground state that react rapidly upon visible light absorption. In both solvents the appearance of I(2)˙(-) could be time resolved. In acetonitrile, the rate constant for I(2)˙(-) growth, 2.2 ± 0.2 × 10(10) M(-1) s(-1), was found to be about a factor of two slower than the formation of [Ru(deeb(-))(deeb)(2)](+), indicating it was a secondary photoproduct. The delayed appearance of I(2)˙(-) was attributed to the reaction of iodine atoms with iodide. In dichloromethane, the growth of I(2)˙(-), 1.3 ± 0.4 × 10(10) M(-1) s(-1), was similar to that in acetonitrile, yet resulted from iodine atoms formed within the laser pulse. These results are discussed within the context of solar energy conversion by dye-sensitized solar cells and storage via chemical bond formation.     

In Process Citation

A method is described for the microanalytical determination of arsenic, antimony and copper in organic compounds. These compounds are decomposed in a mixture of sulphuric and nitric acids. The decomposition products are then oxidized by hydrogen peroxide in the case of arsenic and by potassium permanganate in the case of antimony in order to obtain AsO(4)(3-) or SbO(4)(3-) ions respectively. In the case of copper, Cu(2+) ions are obtained directly as a decomposition product. Iodine generated by constant-current electrolysis of potassium iodide contained in the solution is the titrating reagent, with sodium thiosulphate solution as intermediate reagent, and amperometric end-point detection. The iodine consumption is measured coulometrically.     

Structure of solvated mercury(II) halides in liquid ammonia, triethyl phosphite and tri-n-butylphosphine solution

Liquid ammonia, trialkyl phosphites, and especially trialkylphosphines, are very powerful electron-pair donor solvents with soft bonding character. The solvent molecules act as strongly coordinating ligands towards mercury(ii), interacting strongly enough to displace halide ligands. In liquid ammonia mercury(ii) chloride solutions separate into two liquid phases; the upper contains tetraamminemercury(ii) complexes, [Hg(NH(3))(4)](2+), and chloride ions in low concentration, while the lower is a dense highly concentrated solution of [Hg(NH(3))(4)](2+) entities, ca. 1.4 mol dm(-3), probably ion-paired by hydrogen bonds to the chloride ions. Mercury(ii) bromide also dissociates to ionic complexes in liquid ammonia and forms a homogeneous solution for which (199)Hg NMR indicates weak bromide association with mercury(ii). When dissolving mercury(ii) iodide in liquid ammonia and triethyl phosphite solvated molecular complexes form in the solutions. The Raman nu(I-Hg-I) symmetric stretching frequency is 132 cm(-1) for the pseudo-tetrahedral [HgI(2)(NH(3))(2)] complex formed in liquid ammonia, corresponding to D(S) = 56 on the donor strength scale. For the Hg(ClO(4))(2)/NH(4)I system in liquid ammonia a (199)Hg NMR study showed [HgI(4)](2-) to be the dominating mercury(ii) complex for mole ratios n(I(-)) : n(Hg(2+)) > or = 6. A large angle X-ray scattering (LAXS) study of mercury(ii) iodide in triethyl phosphite solution showed a [HgI(2)(P(OC(4)H(9))(3))(2)] complex with the Hg-I and Hg-P bond distances 2.750(3) and 2.457(4) A, respectively, in near tetrahedral configuration. Trialkylphosphines generally form very strong bonds to mercury(ii), dissociating all mercury(ii) halides. Mercury(ii) chloride and bromide form solid solvated mercury(ii) halide salts when treated with tri-n-butylphosphine, because of the low permittivity of the solvent. A LAXS study of a melt of mercury(ii) iodide in tri-n-butylphosphine at 330 K resulted in the Hg-I and Hg-P distances 2.851(3) and 2.468(4) A, respectively. The absence of a distinct I-I distance indicates flexible coordination geometry with weak and non-directional mercury(ii) iodide association within the tri-n-butylphosphine solvated complex.     

Incorporation of flow injection analysis or capillary electrophoresis with resonance Rayleigh scattering detection for inorganic ion analysis

Resonance Rayleigh scattering (RRS) has been explored as a detection (RRSD) technique for capillary electrophoresis (CE) or flow injection analysis (FIA) of inorganic ions. The detection was achieved through a scattering probe of ion-association complex formed from rhodamine B (Rh B) and iodine. The probe scatters strongly at 630 nm when oxidants such as Cr(2)O(7)(2-), MnO(4)(-) and ClO(-) present in a mixed solution of Rh B and iodide. The scattering disappears once iodine is reduced by reductants. Oxidant or reductant species in a sample can thus be detected by positive or negative RRS signal. To verify the RRSD, FIA-RRSD was first constructed and continuous measurement of testing samples containing Cr(2)O(7)(2-), MnO(4)(-) and/or ClO(-) was performed. The detection limits reached a level of decade nM and a linear range was found between peak height and concentration at the range of 0.255-2.04microM for Cr(2)O(7)(2-), 0.158-3.16microM for MnO(4)(-), and 1.18-9.43microM for ClO(-), with linear regression coefficients of all above 0.99. The run-to-run relative standard deviation of peak height was less than 3% (n=6). CE-RRSD was then set up and studied, using a capillary of 75microm i.d.x33cm filled with a running buffer of 50mM citrate and 25mM Tris (pH 3.32) and worked under -12kV at room temperature. The CE eluent was at-line conducted into a stream of rhodamine B and iodine flowing inner a wide tube by plugging the capillary outlet into the wide tube. Different mixtures prepared from Cr(2)O(7)(2-), MnO(4)(-) and ClO(-) were successfully separated and detected by the CE-RRSD.     

Titrimetric determination of microgram amounts of lead by thiocyanate amplification after precipitation as lead hexathiocyanatochromate(III)

Lead (25–200 μg) is precipitated as Pb₃[Cr(SCN)₆]₂. The filtered precipitate is treated with 10% carbonate solution, and the thiocyanate dissolved is oxidized by iodine to sulphate at pH 8.2. After acidification, the excess of iodine is extracted into chloroform, and the iodide ion retained in the aqueous solution is amplified by bromine oxidation and subsequent treatment with more iodide. The method provides 152 iodine atoms for each original lead ion. Only Bi³⁺ and Cu²⁺ interfere seriously.     

长寿命高选择性液膜碘离子电极的研究

合成了PVC-双硫腙-Hg(Ⅱ)载体.以该载体物质制备了高选择性碘离子电极,其选择性次序为:I^-》ClO₄^->SCN^->NO₂^-》Sal^-～Br^->NO₃^->Cl^-.电极对碘离子的线性响应范围为1×10^-3～5×10^-7mol/L,检测下限为2×10^-7mol/L,斜率为(59±1)mV/decade(16℃).并研究了电极的响应机理,表明系碘离子与载体中金属汞原子直接作用.将该电极应用于食盐中碘的测定,取得了满意的结果.     

Head-space flow injection for the on-line determination of iodide in urine samples with chemiluminescence detection

A simple head-space (HS) flow injection (FI) system with chemiluminescence (CL) detection for the determination of iodide as iodine in urine is presented. The iodide is converted to iodine by potassium dichromate under stirring in the closed HS vial, and the iodine is released from urine by thermostatting and is carried in a nitrogen flow through an iodide trapping solution. The concomitant introduction of aliquots of iodine, luminol and cobalt(II) solutions by means of a time-based injector into an FI system allowed its mixing in a flow-through cell in front of the detector. The emission intensity at 425 nm was recorded as a function of time. The salting-out of the standard solutions affected the gas-liquid distribution coefficient of iodine in the HS vial. The typical analytical working graphs obtained under the optimized experimental conditions were rectilinear from 0 to 5 mg l(-1) iodine, achieving a precision of 2.3 and a relative standard deviation of 1.8 for ten replicate analyses of 50 and 200 microg l(-1) iodine. However, a second-order process becomes significant at higher iodine concentrations (from 10 to 40 mg l(-1)). The detection limit of the method is 10 microg l(-1) (80 ng) iodine when 8 ml samples are taken. Data for the iodide content of 10 urine samples were in good agreement with those obtained by a conventional catalytic method, and recoveries varied between 101 and 103% for urine samples spiked with different amounts of iodide. The analysis of one sample takes less than 20 min. In the present study the iodide levels found for 100 subjects were 86.8 +/- 19.0 (61-125) microg l(-1), which is lower than the WHO's optimal level (150-300 microg per day).     

Photoinduced electron transfer and solvation dynamics in aqueous clusters: comparison of the photoexcited iodide-water pentamer and the water pentamer anion

Upon photoexcitation of iodide-water clusters, I(-)(H(2)O)(n), an electron is transferred from iodide to a diffuse cluster-supported, dipole-bound orbital. Recent femtosecond photoelectron spectroscopy experiments have shown that, for photoexcited I(-)(H(2)O)(n) (n≥ 5), complex excited-state dynamics ultimately result in the stabilization of the transferred electron. In this work, ab initio molecular dynamics simulations of excited-state I(-)(H(2)O)(5) and (H(2)O)(5)(-) are performed, and the simulated time evolution of their structural and electronic properties are compared to determine unambiguously the respective roles of the water molecules and the iodine atom in the electron stabilization dynamics. Results indicate that, driven by the iodine-hydrogen repulsive interactions, excited I(-)(H(2)O)(5) rearranges significantly from the initial ground-state minimum energy configuration to bind the excited electron more tightly. By contrast, (H(2)O)(5)(-) rearranges less dramatically from the corresponding configuration due to the lack of the same iodine-hydrogen interactions. Despite the critical role of iodine for driving reorganization in excited I(-)(H(2)O)(5), excited-electron vertical detachment energies appear to be determined mostly by the water cluster configuration, suggesting that femtosecond photoelectron spectroscopy primarily probes solvent reorganization in photoexcited I(-)(H(2)O)(5).     

New spot-test for silver(I) based on double iodide formation with bismuth(III)

The formation of an intense brownish-maroon or maroon-red product by the interaction of silver(I) and bismuth(III) solution in the presence of iodide forms the basis of a new and specific spot-test procedure for silver. The test is conducted on a spot plate with 2 or 3 drops of 2% potassium iodide solution, 1 drop of 1% bismuth(III) nitrate solution, and 1 drop of test solution. Limit of detection is 0.01 mug; limit of dilution is 1:5 x 10(6). Most cations and anions do not interfere. Only Tl(I), Cs, S(2)O(2-)(3), EDTA, pyridine, excess of thiourea, oxidizing ions (NO(-)(2), IO(-)(3), IO(-)(4), MnO(-)(4), BrO(-)(3), and S(2)O(2-)(8)) and ions such as Cl(-), Br(-), I(-), SCN(-), and N(-)(3) which cause precipitation of silver, interfere. The product formed is most probably Ag(2)BiI(5).     

Iodine emission in the presence of humic substances at the water's surface

Humic substances that preferentially adsorb at the air/water interfaces of water or aerosols consist of both fulvic and humic acid. To investigate the chemical reactivity for the heterogeneous reaction of gaseous ozone, O(3)(g), with aqueous iodide, I(-)(aq), in the presence of standard fulvic acid, humic acid, or alcohol, cavity ring-down spectroscopy was used to detect gaseous products, iodine, I(2)(g) and an iodine monoxide radical, IO(g). Fulvic acid enhanced the I(2)(g) production yield, but not the IO(g) yield. Humic acid, n-hexanol, n-heptanol, and n-octanol did not affect the yields of I(2)(g) or IO(g). We can infer that the carboxylic group contained in fulvic acid promotes the I(2)(g) emission by supplying the requisite interfacial protons more efficiently than water on its surface.     

Flash-quench technique employed to study the one-electron reduction of triiodide in acetonitrile: evidence for a diiodide reaction product

The one-electron reduction of triiodide (I(3)(-)) by a reduced ruthenium polypyridyl compound was studied in an acetonitrile solution with the flash-quench technique. Reductive quenching of the metal-to-ligand charge-transfer excited state of [Ru(II)(deeb)(3)](2+) by iodide generated the reduced ruthenium compound [Ru(II)(deeb(-))(deeb)(2)](+) and diiodide (I(2)(?-)). The subsequent reaction of [Ru(II)(deeb(-))(deeb)(2)](+) with I(3)(-) indicated that I(2)(?-) was a product that appeared with a second-order rate constant of (5.1 ± 0.2) × 10(9) M(-1) s(-1). After correction for diffusion and some assumptions, Marcus theory predicted a formal potential of -0.58 V (vs SCE) for the one-electron reduction of I(3)(-). The relevance of this reaction to solar energy conversion is discussed.     

Chemical enhancement method for the determination of mercury by spectrophotometry after iodide extraction

A selective and sensitive spectrophotometric method for the determination of 0.08-2.5 ppb of mercury(II) is described. Mercury is extracted as tetraiodomercury(II)-Cd-phenanthroline ion-pair into benzene and selectively stripped into EDTA. The iodide associated with mercury present in the stripping is oxidized to iodate and then treated with excess iodide to give iodine. The iodine formed is extracted into benzene and equilibrated with iodate in acidic medium in the presence of chloride and Rhodamine 6G for the formation of ICI(-)(2) species and its extraction as ion-pair with Rhodamine 6G. Determination is completed by measuring the absorption of the extract at 535 nm. The coefficient of variation is 1.5% for 10 determinations of 200 ng of mercury. The method has been applied to establish the mercury content of natural waters and chloralkali plant effluent.     

Evidence of two-dimensional superconductivity in the single crystalline nanohybrid of organic-bismuth cuprate

A coordination compound of HgI(2)(pyridine)(2) can be successfully intercalated into a single crystalline Bi(2)Sr(2)CaCu(2)O(y) high-T(c) superconductor through an interlayer complexation reaction between pyridine molecules and bismuth cuprate pre-intercalated with mercuric iodide. X-ray diffraction and X-ray absorption spectroscopic results clearly demonstrate that the single crystalline nature of the pristine bismuth cuprate remains unchanged even after the intercalation of organic complex as well as those of iodine and mercuric iodide. According to the angle-dependent dc magnetization measurements, the intercalation of bulky organic molecules completely blocks superconductive currents along the c-axis, whereas a superconducting transition along the in-plane direction still occurs in the organic intercalate. In the case of the iodine or mercuric iodide intercalates with smaller lattice expansions, an out-of-plane diamagnetic transition is not wholly quenched but significantly depressed by the intercalation, confirming the reduction of interlayer interaction. The present finding can provide straightforward evidence of the two-dimensionality of high temperature superconductivity in the present cuprate-based nanohybrid material.     

Absence of a signature of aqueous I(2P(1/2)) after 200-nm photodetachment of I-(aq)

Ultrafast pump-broadband probe spectroscopy was used to study the transient photoproducts following 200-nm photodetachment of I(-)(aq). Resonant detachment at 200 nm in the second charge-transfer-to-solvent (CTTS) band of I(-)(aq) is expected to produce an electron and iodine in its spin-orbit excited state, I*((2)P(1/2)). The transients in solution following photodetachment were probed from 200 to 620 nm. Along with strong absorption in the visible region due to solvated electrons and a strong bleach of the I(-)(aq) ground-state absorption, a weaker transient absorption near 260 nm was observed that is consistent with a previously assigned ground-state I((2)P(3/2)) charge-transfer band. However, no evidence was found for an equivalent I*(aq) charge-transfer absorption, and I((2)P(3/2)) was produced within the instrument response. This suggests either that I* is electronically relaxed in less than 300 fs or that excitation in the second CTTS band does not in fact lead to I*. The consequences for previous experimental work where I*(aq) production has been postulated, as well as for halogen electron ejection mechanisms, are discussed. In addition, the broad spectral coverage of this study reveals in the bleach recovery the rapid cooling of the solvent surrounding the re-formed iodide after geminate recombination of the iodine with the solvated electron.     

Hydrocarbon-Soluble Mercuracarborands: Syntheses, Halide Complexes, and Supramolecular Chemistry

The syntheses of macrocyclic species composed of carborane derivatives joined via their carbon vertices by electrophilic mercury atoms are described. The reaction of closo-1,2-Li(2)[C(2)B(10)H(10)(-)(x)()R(x)()] with HgI(2) gives Li(2)[(1,2-C(2)B(10)H(10)(-)(x)()R(x)()Hg)(4)I(2)] [R = Et, x = 2 (5.I(2)Li(2)); R = Me, x = 2 (6.I(2)Li(2)); R = Me, x = 4 (7.I(2)Li(2))]. 6.I(2)(K.[18]dibenzocrown-6)(2) crystallizes in the monoclinic space group C2/m [a = 28.99(2) ?, b = 18.19(1) ?, c = 13.61(1) ?, beta = 113.74(2) degrees, V = 6568 ?(3), Z = 4, R = 0.060, R(w) = 0.070]; 7.I(2)(NBu(4))(2) crystallizes in the monoclinic space group P2(1)/c [a = 12.77(1) ?, b = 21.12(2) ?, c = 20.96(2) ?, beta = 97.87(2) degrees, V = 5600 ?(3), Z = 2, R = 0.072, R(w) = 0.082]. The precursor to 7, closo-8,9,10,12-Me(4)-1,2-C(2)B(10)H(8) (4), is made in a single step by reaction of closo-1,2-C(2)B(10)H(12) with MeI in trifluoromethanesulfonic acid. The free hosts 5, 6, and 7 are obtained by reaction of the iodide complexes with stoichiometric quantities of AgOAc. A (199)Hg NMR study indicates that sequential removal of iodide from 5.I(2)Li(2) and 6.I(2)Li(2) with aliquots of AgOAc solution leads to formation of two intermediate host-guest complexes in solution, presumed to be 5(6)ILi and 5(2)(6)(2).ILi. Crystals grown from a solution of 6.I(2)Li(2) to which 1 equiv of AgOAc solution had been added proved to be an unusual stack structure with the formula 6(3).I(4)Li(4) [tetragonal, I4/m, a = 21.589(2) ?, c = 21.666(2) ?, V = 10098 ?(3), Z = 2, R = 0.058, R(w) = 0.084]. Addition of 2 equiv of NBu(4)Br ion to 5 or 6 gives 5.Br(2)(NBu(4))(2) and 6.Br(2)(NBu(4))(2), respectively, while addition of 1 equiv of KBr to 6 forms 6.BrK. 5.Br(2)(NBu(4))(2) crystallizes in the triclinic space group P&onemacr;, [a = 10.433(1) ?, b = 13.013(1) ?, c = 15.867(2) ?, alpha = 91.638(2) degrees, beta = 97.186(3) degrees, gamma = 114.202(2) degrees, V = 1492 ?(3), Z = 1, R = 0.078, R(w) = 0.104]. The hosts 5 and 6 form 1:1 supramolecular adducts with the polyhedral anions B(10)I(10)(2)(-) and B(12)I(12)(2)(-) in solution.