Spinodal decomposition and phase separation kinetics in nanoclay–biopolymer solutions

Intensity of light, I(q,t), scattered from homogeneous aqueous solutions, of nanoclay (Laponite) and protein (gelatin‐A), was studied to monitor the temporal and spatial evolution of the solution into a phase‐separated nanoclay–protein‐rich dense phase, when the sample temperature was quenched below spinodal temperature, T_s (=311 ± 3 K). The zeta potential data revealed that the dense phase comprised charge‐neutralized intermolecular complexes of nanoclay and protein chains of low surface charge. The early stage, t < 500 s, of phase separation could be described adequately through Cahn‐Hilliard theory of spinodal decomposition where the intensity grows exponentially, I(q, t) = I₀ exp.(2R(q)t). The wave vector, q dependence of the growth parameter, R(q) exhibited a maxima independent of time. Corresponding correlation length, 1/q_c = ξ_c was found to be ≈75 ± 5 nm independent of quench depth. In the intermediate regime, anomalous growth described by I(q, t) ～ t^α with α = 0.1 ± 0.02 independent of q was observed. Rheological studies established that there was a propensity of network structures inside the dense phase. Isochronal temperature sweep studies of the dense phase determined the melting temperature, T_m = 312 ± 4 K, which was comparable with the spinodal temperature. The stress‐diffusion coupling prevailing in the dense phase when analyzed in the Doi‐Onuki model yielded a viscoelastic correlation length, ξ_v determined from low‐frequency storage modulus, G ′₀ ≈ k_B T/ξ, which was ξ_v ≈ 35 ± 3 nm indicating 2ξ_v ≈ ξ_c. It is concluded that the early stage of phase separation in this system was sufficiently described by linear Cahn‐Hilliard theory, but the same was not true in the intermediate stage. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 555–565, 2010     

INO thermodynamic properties and ultraviolet spectrum

The equilibrium I₂(g) + 2NO(g) = 2INO(g) has been studied at room temperature by ultraviolet absorption spectroscopy. The equilibrium constant has been measured as K_p = (2.7 ± 0.3) × 10^?6 atm^?1 at 298 K. Third-law calculations lead to ΔH°_f,298 (INO) = 120.0 ± 0.3 kJ/mol. The relative absorption spectrum of INO has been measured between 225 and 300 nm. Quantitative measurements gave ?(λ_max = 238 nm) = (1.79 ± 0.5) × 10⁴ L/mol·cm and ?(410 nm) = 234.7 ± 21 L/mol·cm.     

Conformation of comb‐like liquid crystal polymers in isotropic solution probed by small‐angle neutron scattering

The conformational characteristics of a comb‐like side‐chain liquid crystal polysiloxane (SCLCP), dissolved in deuterated chloroform, were evaluated by small‐angle neutron scattering (SANS) measurements over a wide q range. SANS studies were carried out on specimens with constant backbone length (DP = 198) and variable spacer length (n = 3, 5, and 11), and with constant spacer length (n = 5) and variable DP (45, 72, 127, and 198). The form factor P(q) at high q was analyzed using the wormlike chain model with finite cross‐sectional thickness (R_c) and taking into account the molecular weight polydispersity. The analysis generated values of persistence length in the range l_p = 28–32 Å, considerably larger than that of the unsubstituted polysiloxane chain (l_p = 5.8 Å), with contour lengths per monomer comparable to the fully‐extended polysiloxane backbone (l_m = 2.9 Å). This indicates a relatively rigid SCLCP chain due to the influence of the densely attached mesogenic groups. The SCLCP with n = 11 is more flexible (l_p = 28 Å) than those with n = 3 and n = 5 (l_p = 32 Å). The cross‐sectional thickness increases with spacer length, R_c ～ n^0.21±0.02 (3 ≤ n ≤ 11), and the contour length per monomer decreases with increasing spacer length, l_m ～ n^?0.35±0.01. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2412–2424, 2006     

Glass transition and its characteristic length for thin crosslinked polystyrene shells of rodlike capsules

Rodlike capsules consisting of a calcium carbonate core and a crosslinked polystyrene shell were synthesized, and the glass transition temperature (T_g) and characteristic length of the glass transition ξ(T_g) for the thin outer shells were investigated by temperature‐modulated differential scanning calorimetry. The shell thickness ranged from 20 to 129 nm. The ratio of the T_g for the outer shell to the bulk T_g increases with decreasing shell thickness d. The d‐dependence of T_g is interpreted in terms of a simple two‐layer model which assumes that an immobile layer exists near the core‐shell interface. Shells of hollow capsules unexpectedly exhibit a similar d‐dependence of T_g to that for the filled capsules. This is characteristic of the crosslinked polymeric shells, and is attributed to certain spatial heterogeneity of crosslink distribution, and/or to the unstable configuration in the ultrathin shell that does not undergo relaxation due to the crosslink. The latter idea is based on the assumption that unstable configurational state is responsible for the T_g shift from the bulk value observed for nanosized polymeric materials. The ratio of the characteristic length for the shell of the filled capsule to that of the bulk ξ_f(T_g)/ξ_b(T_g) decreases with decreasing d. The results are interpreted in terms of the configurational entropy, and it is also suggested that the configurational state of network polymer chains in the shell affects the characteristic length. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 2116–2125, 2008     

Unusual finite size effects in the Monte Carlo simulation of microphase formation of block copolymer melts

Extensive Monte Carlo simulations are presented for the Fried-Binder model of block copolymer melts, where polymer chains are represented as self and mutually avoiding walks on a simple cubic lattice, and monomer units of different kind (A, B) repel each other if they are nearest neighbors (ε_AB > 0). Choosing a chain length N = 20, vacancy concentration Φ_v = 0,2, composition ƒ = 3/4, and a L × L × L geometry with periodic boundary conditions and 8 ≤ L ≤ 32, finite size effects on the collective structure factor S(q) and the gyration radii are investigated. It is shown that already above the microphase separation transition, namely when the correlation length ξ(T) of concentration fluctuations becomes comparable with L, a nonmonotonic variation of both S(q) and the radii with L sets in. This variation is due to the fact that the wavelength λ^*(T) of the ordering (defined from the wavenumber q^* where S(q) is maximal at λ^* = 2 π/q^*) in general is incommensurable with the box. The competition of two nontrivial lengths ξ(T), λ^* (T) with L makes the straigthforward application of finite size scaling techniques impossible, unlike the case of polymer blends. Since also the specific heat is found to have a broad rounded peak near the transition only, locating the transition accurately from Monte Carlo simulations remains an unsolved problem.     

Kinetic and Mechanisms of the Homogeneous,Unimolecular Elimination of Phenyl Chloroformate and p‐Tolyl Chloroformate in the Gas Phase

The gas‐phase elimination of phenyl chloroformate gives chlorobenzene, 2‐chlorophenol, CO₂, and CO, whereasp‐tolyl chloroformate produces p‐chlorotoluene and 2‐chloro‐4‐methylphenol CO₂ and CO. The kinetic determination of phenyl chloroformate (440–480^oC, 60–110 Torr) and p‐tolyl chloroformate (430–480°C, 60–137 Torr) carried out in a deactivated static vessel, with the free radical inhibitor toluene always present, is homogeneous, unimolecular and follows a first‐order rate law. The rate coefficient is expressed by the following Arrhenius equations: Phenyl chloroformate: Formation of chlorobenzene, log k_I = (14.85 ± 0.38) – (260.4 ± 5.4) kJ mol^?1 (2.303RT)^?1; r = 0.9993 Formation of 2‐chlorophenol, log k_II = (12.76 ± 0.40) – (237.4 ± 5.6) kJ mol^?1(2.303RT)^?1; r = 0.9993 p‐Tolyl chloroformate: Formation of p‐chlorotoluene: log k_I = (14.35 ± 0.28) – (252.0 ± 1.5) kJ mol^–1 (2.303RT)^?1; r = 0.9993 Formation of 2‐chloro‐4‐methylphenol, log k_II = (12.81 ± 0.16) – (222.2 ± 0.9) kJ mol^?1(2.303RT)^–1; r = 0.9995 The estimation of the k_I values, which is the decarboxylation process in both substrates, suggests a mechanism involving an intramolecular nucleophilic displacement of the chlorine atom through a semipolar, concerted four‐membered cyclic transition state structure; whereas the k_II values, the decarbonylation in both substrates, imply an unusual migration of the chlorine atom to the aromatic ring through a semipolar, concerted five‐membered cyclic transition state type of mechanism. The bond polarization of the C–Cl, in the sense C^{δ+ …} Cl^δ?, appears to be the rate‐determining step of these elimination reactions.     

Crystal Structure of the Mixed‐Valent Basic Mercury Nitrate HgI2(NO3)2·HgII(OH)(NO3)·HgII(NO3)2·4HgIIO [= Hg8O4(OH)(NO3)5]

Light‐yellow single crystals of the mixed‐valent mercury‐rich basic nitrate Hg₈O₄(OH)(NO₃)₅ were obtained as a by‐product at 85 °C from a melt consisting of stoichiometric amounts of (Hg^I₂)(NO₃)₂·2H₂O and Hg^II(OH)(NO₃). The title compound, represented by the more detailed formula Hg^I₂(NO₃)₂·Hg^II(OH)(NO₃)·Hg^II(NO₃)₂·4Hg^IIO, exhibits a new structure type (monoclinic, C2/c, Z = 4, a = 6.7708(7), b = 11.6692(11), c = 24.492(2) Å, β = 96.851(2)°, 2920 structure factors, 178 parameters, R1[F² > 2σ(F²)] = 0.0316) and is made up of almost linear [O‐Hg^II‐O] and [O‐Hg^I‐Hg^I‐O] building blocks with typical Hg^II‐O distances around 2.06Å and a Hg^I‐O distance of 2.13Å. The Hg₂²⁺ dumbbell exhibits a characteristic Hg‐Hg distance of 2.5079(7) Å. The different types of mercury‐oxygen units form a complex three‐dimensional network exhibiting large cavities which are occupied by the nitrate groups. The NO₃^? anions show only weak interactions between the nitrate oxygen atoms and the mercury atoms which are at distances > 2.6Å from one another. One of the three crystallographically independent nitrate groups is disordered.     

Synthesis,characterization and oxygen‐sensing properties of a novel luminescent Cu(I) complex

A novel luminescent copper(I) complex with formula [Cu(PPh₃)₂(PIP)]BF₄ (PPh₃ = triphenyl phosphine, PIP = 2‐phenyl‐1H‐imidazo[4,5‐f][1,10]phenanthroline) has been synthesized and characterized by ¹H NMR, IR, elemental analysis and X‐ray crystal structure analysis. In solid state, it displays broad band emission upon excitation at λ = 420 nm with the emission maximum locates at 551 nm. Its excited‐state lifetime is in the microsecond time scale (3.02 µs); as a result, its emission intensity is sensitive to oxygen concentration and shows oxygen‐sensing properties after being encapsulated into mesoporous silica MCM‐41. For the system with 60 mg/g loading level, a sensitivity (I₀/I) of 4.35, a fluorescence quenching time (t_Q) of 5 s and a recovery time (t_R) of 36 s were achieved. Even after aging for 5 months, the sensitivities of the three loading level systems can be retained, ignoring the measurement error, which indicates that they possess long‐term stability. Copyright © 2009 John Wiley & Sons, Ltd.     

Syntheses,Crystal Structures,and Properties of Lead(II), ­Zinc(II), and Manganese(II) Complexes Constructed from 2, 3, 5, 6‐Tetraiodo‐1, 4‐benzenedicarboxylic Acid

Three new coordination compounds, [Pb(HBDC‐I₄)₂(DMF)₄]( 1 ) and [M(BDC‐I₄)(MeOH)₂(DMF)₂]_n (M = Zn^II for 2 and Mn^II for ( 3 ) (H₂BDC‐I₄ = 2, 3, 5, 6‐tetraiodo‐1, 4‐benzenedicarboxylic acid), were synthesized and characterized by elemental analysis, IR spectroscopy, thermogravimetric (TG) analysis, and X‐ray single crystal structure analysis. Single‐crystal X‐ray diffraction reveals that 1 crystallizes in the monoclinic space group C2/c and has a discrete mononuclear structure, which is further assembled to form a two‐dimensional (2D) layer through intermolecular O–H ··· O and C–H ··· O hydrogen bonding interactions. The isostructural compounds 2 and 3 crystallize in the space group P2₁/c and have similar one‐dimensional (1D) chain structures that are extended into three‐dimensional (3D) supramolecular networks by interchain C–H ··· π interactions. The Pb^II and Zn^II complexes 1 and 2 display similar emissions at 472 nm in the solid state, which essentially are intraligand transitions.     

Structure of cellulose in cuoxam

Cuoxam ([Cu^II(NH₃)₄](OH)₂) is a well known solvent for cellulose. Because of its deep blue colour, it has been used so far only for viscosity measurements. Direct light scattering measurements have not yet been reported in the literature. We carried out static and dynamic light scattering measurements in cuoxam using the blue wavelength of λ₀ = 457.9 nm from an Argon ion laser. The measurements were involved with some difficulties mainly caused by colloidal particles of CuO and Cu(OH)₂ which could be removed by direct centrifugation of the cells. Furthermore, the scattering intensity had to be corrected for extinction. The refractive index increment was taken from the literature. 12 samples of different molecular weight and different origin were measured, and common power law behavior was found in a region up to about DP_w = 1000 for both, the radius of gyration R_g and the hydrodynamic radius R_h, derived from the diffusion coefficient D_z. At higher degrees of polymerization characteristic deviations to lower radii occurred.These deviations are not caused by aggregation since the DP_w's agreed with those from the cellulose tricarbanilates. The quantitative analysis of the radii and the angular dependence of the scattered light allowed determination of the chain stiffness. A Kuhn segment length of I_k = 25.6 (±6.2) nm and a characteristic ratio C_∞ = 49.6 (±12.0) were derived. These values are close to those for cellulose-tri-carbanilate in dioxane.The reason for the increased stiffening is discussed on the basis of a special H-bond model.     

Two polymorphs of 5‐cyclohexyl‐5‐ethylbarbituric acid and their packing relationships with other barbiturates

Polymorph (Ia) (m.p. 474 K) of the title compound, C₁₂H₁₈N₂O₃, displays an N—H...O=C hydrogen‐bonded layer structure which contains R₆⁶(28) rings connecting six molecules, as well as R₂²(8) rings linking two molecules. The 3‐connected hydrogen‐bonded net resulting from these interactions has the hcb topology. Form (Ib) (m.p. 471 K) displays N—H...O=C hydrogen‐bonded looped chains in which neighbouring molecules are linked to one another by two different R₂²(8) rings. Polymorph (Ia) is isostructural with the previously reported form II of 5‐(2‐bromoallyl)‐5‐isopropylbarbituric acid (noctal) and polymorph (Ib) is isostructural with the known crystal structures of four other barbiturates.     

Synthesis,Structure, and Photoluminescence Properties of an Organically‐Templated Uranyl Selenite

The organically‐templated uranyl selenite, (H₂en)[(UO₂)(SeO₃)(HSeO₃)](NO₃) · 0.5H₂O ( 1 ) (en = 1,2‐ethylenediamine) was synthesized and characterized by elemental analyses, IR spectroscopy, TG, and single‐crystal X‐ray diffraction. Compound 1 crystallizes in the orthorhombic system, space group Pbca, with a = 13.170(3) Å, b = 11.055(2) Å, c = 18.009(4) Å, V = 2621.8(9) ų, M = 1316.19, Z = 4, D_cal = 3.334 g · cm^–3, μ(Mo‐K_α) = 17.998 mm^–1, GOF = 1.059, R₁ = 0.0263, wR₂ = 0.0532 [I>2σ(I)]. The X‐ray diffraction analysis reveals that compound 1 has a three‐dimensional (3D) supramolecular structure. It contains negatively charged [UO₂(HSeO₃)(SeO₃)]^– inorganic anion layers and is balanced by [H₂en]²⁺ cations and NO₃^– anions located in the interlayers. Furthermore, the photoluminescence properties of 1 were investigated.     

An Unusual Mixed‐Anionic Iodine‐Rich Polyiodide: [Rb(crypt‐2,2,2)]4(I5)2(I8)

Black crystals of [Rb(crypt‐2,2,2)]₄(I₅)₂(I₈) were obtained from a dichloromethane/ethanol solution of RbI, I₂ and Kryptofix‐2,2,2®. The crystal structure (monoclinic, P2₁/c (no. 14), a = 1250.1(1), b = 2555.2(2), c = 2313.4(3) pm, β = 121.45(1)°, V = 6309.9(11)·10⁶ pm³, Z = 2) consists of [Rb(crypt‐2,2,2)]⁺ cations leaving three‐dimensional channels for the V‐shaped (I₅)^? and Z‐shaped (I₈)^2? anions which are isolated from each other.     

Coordination Chemistry of Diiodine and Implications for the Oxidation Capacity of the Synergistic Ag+/X2 (X=Cl,Br, I) System

The synergistic Ag⁺/X₂ system (X=Cl, Br, I) is a very strong, but ill‐defined oxidant—more powerful than X₂ or Ag⁺ alone. Intermediates for its action may include [Ag_m(X₂)_n]^m+ complexes. Here, we report on an unexpectedly variable coordination chemistry of diiodine towards this direction: ( A )Ag‐I₂‐Ag( A ), [Ag₂(I₂)₄]²⁺( A ^?)₂ and [Ag₂(I₂)₆]²⁺( A ^?)₂?(I₂)_x≈0.65 form by reaction of Ag( A ) ( A =Al(OR^F)₄; R^F=C(CF₃)₃) with diiodine (single crystal/powder XRD, Raman spectra and quantum‐mechanical calculations). The molecular ( A )Ag‐I₂‐Ag( A ) is ideally set up to act as a 2 e^? oxidant with stoichiometric formation of 2 AgI and 2 A ^?. Preliminary reactivity tests proved this ( A )Ag‐I₂‐Ag( A ) starting material to oxidize n‐C₅H₁₂, C₃H₈, CH₂Cl₂, P₄ or S₈ at room temperature. A rough estimate of its electron affinity places it amongst very strong oxidizers like MF₆ (M=4d metals). This suggests that ( A )Ag‐I₂‐Ag( A ) will serve as an easily in bulk accessible, well‐defined, and very potent oxidant with multiple applications.     

Ag9I3(SeO4)2(IO3)2 – Synthesis,Crystal Structure,and Ionic Conductivity

Ag₉I₃(SeO₄)₂(IO₃)₂ was obtained for the first time by reacting a stoichiometric mixture of Ag₂O, AgI and SeO₂ at elevated oxygen pressure (255 MPa) and at a temperature of 500 °C. Ag₉I₃(SeO₄)₂(IO₃)₂ was characterized by X‐ray powder diffraction, differential scanning calorimetry, impedance spectroscopy and single crystal structure analysis. The crystal structure was solved by direct methods (I23, Z = 8, a = 12.9584(6) Å, V = 2175.9(2) ų and R₁ = 2.70 %). The crystal structure consists of isolated SeO₄ tetrahedra and trigonal IO₃ pyramids separated by Ag⁺ and I^– ions. Each four of the SeO₄^2– and IO₃^– anions aggregate, forming a novel supramolecular building block, showing a hetero‐cubane like structure. According to the results of impedance measurements, Ag₉I₃(SeO₄)₂(IO₃)₂ is a good silver ion conductor. The compound shows an abrupt increase in the ionic conductivity in the temperature range of 115 to 147 °C, and has a silver ion conductivity of 7.1 × 10^–5 Ω^–1 cm^–1 at 25 °C. The activation energy for silver ion conduction is 0.45 eV, in the temperature range from 25 to 115°.     

Coordination Chemistry of Diiodine and Implications for the Oxidation Capacity of the Synergistic Ag+/X2 (X=Cl,Br, I) System

The synergistic Ag⁺/X₂ system (X=Cl, Br, I) is a very strong, but ill‐defined oxidant—more powerful than X₂ or Ag⁺ alone. Intermediates for its action may include [Ag_m(X₂)_n]^m+ complexes. Here, we report on an unexpectedly variable coordination chemistry of diiodine towards this direction: ( A )Ag‐I₂‐Ag( A ), [Ag₂(I₂)₄]²⁺( A ⁻)₂ and [Ag₂(I₂)₆]²⁺( A ⁻)₂⋅(I₂)_x≈0.65 form by reaction of Ag( A ) ( A =Al(OR^F)₄; R^F=C(CF₃)₃) with diiodine (single crystal/powder XRD, Raman spectra and quantum‐mechanical calculations). The molecular ( A )Ag‐I₂‐Ag( A ) is ideally set up to act as a 2 e⁻ oxidant with stoichiometric formation of 2 AgI and 2 A ⁻. Preliminary reactivity tests proved this ( A )Ag‐I₂‐Ag( A ) starting material to oxidize n‐C₅H₁₂, C₃H₈, CH₂Cl₂, P₄ or S₈ at room temperature. A rough estimate of its electron affinity places it amongst very strong oxidizers like MF₆ (M=4d metals). This suggests that ( A )Ag‐I₂‐Ag( A ) will serve as an easily in bulk accessible, well‐defined, and very potent oxidant with multiple applications.     

Binuclear Iron(I) Complex Containing Bridging Phenanthrene‐4,5‐dithiolate Ligand: Preparation,Spectroscopy, Crystal Structure,and Electrochemistry

A diiron hexacarbonyl complex containing bridging phenanthrene‐4,5‐dithiolate ligand is prepared by oxidative addition of Phenanthro[4,5‐cde][1,2]dithiin to Fe₂(CO)₉. The complex is investigated as a model for the active site of the [Fe–Fe] hydrogenase enzyme. The compound, [(μ‐PNT)Fe₂(CO)₆]; (PNT = phenanthrene‐4,5‐dithiolate), was characterized by spectroscopic methods (IR, UV/Vis and NMR) and X‐ray crystallography. The IR and proton NMR spectra of [(μ‐PNT)Fe₂(CO)₆] ( 4 ) are in agreement with a PNT ligand attached to a Fe₂(CO)₆ core. The infrared spectrum of 4 recorded in dichloromethane contains three peaks at 2001, 2040, and 2075 cm^–1 corresponding to the stretching frequency of terminal metal carbonyls. X‐ray crystallographic study unequivocally confirms the structure of the complex having a butterfly shape with an Fe–Fe bond length of 2.5365 Å close to that of the enzyme (2.6 Å). Electrochemical properties of [(μ‐PNT)Fe₂(CO)₆] have been investigated by cyclic voltammetry. The cyclic voltammogram of [(μ‐PNT)Fe₂(CO)₆] recorded in acetonitrile contains one quasi‐irreversible reduction (E_1/2 = –0.84 V vs. Ag/AgCl, I_pc/I_pa = 0.6, ΔE_p = 131 V at 0.1 V · s^–1) and one irreversible oxidation (E_pa = 0.86 V vs. Ag/AgCl). The redox of [(μ‐PNT)Fe₂(CO)₆] at E_1/2 = –0.84 V can be assigned to the one‐electron transfer processes; [Fe^I–Fe^I] → [Fe^I–Fe⁰] and [Fe^I–Fe⁰] → [Fe^I–Fe^I].     

Photoinduced Degradation of the Herbicide Clomazone Model Reactions for Natural and Technical Systems

The photodegradation of the herbicide clomazone in the presence of S₂O₈^2? or of humic substances of different origin was investigated. A value of (9.4 ± 0.4) × 10⁸ m ^?1 s^?1 was measured for the bimolecular rate constant for the reaction of sulfate radicals with clomazone in flash‐photolysis experiments. Steady state photolysis of peroxydisulfate, leading to the formation of the sulfate radicals, in the presence of clomazone was shown to be an efficient photodegradation method of the herbicide. This is a relevant result regarding the in situ chemical oxidation procedures involving peroxydisulfate as the oxidant. The main reaction products are 2‐chlorobenzylalcohol and 2‐chlorobenzaldehyde. The degradation kinetics of clomazone was also studied under steady state conditions induced by photolysis of Aldrich humic acid or a vermicompost extract (VCE). The results indicate that singlet oxygen is the main species responsible for clomazone degradation. The quantum yield of O₂(a¹Δ_g) generation (λ = 400 nm) for the VCE in D₂O, Φ_Δ = (1.3 ± 0.1) × 10^?3, was determined by measuring the O₂(a¹Δ_g) phosphorescence at 1270 nm. The value of the overall quenching constant of O₂(a¹Δ_g) by clomazone was found to be (5.7 ± 0.3) × 10⁷ m ^?1 s^?1 in D₂O. The bimolecular rate constant for the reaction of clomazone with singlet oxygen was k_r = (5.4 ± 0.1) × 10⁷ m ^?1 s^?1, which means that the quenching process is mainly reactive.     

Synthesis,Structures, and Photophysics of Polynuclear Silver(I) Thiolate and Silver(I) Thiocarboxylate Complexes with Dppm Ligands

Trinuclear silver(I) thiolate and silver(I) thiocarboxylate complexes [Ag₃(μ‐dppm)₃(μ_n‐SR)₂](ClO₄) [n = 2, R = C₆H₄Cl‐4 ( 1 ) and C{O}Ph ( 2 ); n = 3, R = tBu ( 3 )], pentanuclear silver(I) thiolate complex [Ag₅(μ‐dppm)₄(μ₃‐SC₆H₄NO₂‐4)₄](PF₆) ( 4 ), and hexanuclear silver(I) thiolate complexes [Ag₆(μ‐dppm)₄(μ₃‐SR)₄]Y₂ [Y = ClO₄, R =C₆H₄CH₃‐4 ( 5 ) and C₁₀H₇ (2‐naphthyl) ( 7 ); Y = PF₆, R = C₆H₄OCH₃‐4( 6 )], were synthesized [dppm = bis(diphenylphosphanyl)methane] and their crystal structures as well as photophysical properties were studied. In the solid state at 77 K, trinuclear silver(I) thiolate and silver(I) thiocarboxylate complexes 1 and 2 exhibit luminescence at 470–523 nm, tentatively attributed to originate from the ³IL (intraligand) of thiolate or thiocarboxylate ligands, whereas hexanuclaer silver(I) thiolate complexes 5 and 7 produce dual emission, in which high‐energy emission is tentatively attributed to come from the ³IL of thiolate ligands and low‐energy emission is tentatively assigned to come from the admixture of metal ··· metal bond‐to‐ligand charge‐transfer (MMLCT) and metal‐centered (MC) excited states.     

Channel‐forming solvate crystals and isostructural solvent‐free powder of 5‐hydroxy‐6‐methyl‐2‐pyridone

Crystals of 5‐hydroxy‐6‐methyl‐2‐pyridone, (I), grown from a variety of solvents, are invariably trigonal (space group R); these are 5‐hydroxy‐6‐methyl‐2‐pyridone acetone 0.1667‐solvate, C₆H₇NO₂·0.1667C₃H₆O, (Ia), and 6‐methyl‐5‐hydroxy‐2‐pyridone propan‐2‐ol 0.1667‐solvate, C₆H₇NO₂·0.1667C₃H₈O, (Ib), and the forms from methanol, (Ic), water, (Id), benzonitrile, (Ie), and benzyl alcohol, (If). They incorporate channels running the length of the c axis that contain extensively disordered solvent molecules. A solvent‐free sublimed powder of 5‐hydroxy‐6‐methyl‐2‐pyridone microcrystals is essentially isostructural. Inversion‐related host molecules interact via pairs of N—H...O hydrogen bonds to form R₂²(8) dimers. Six of these dimers form large R₁₂⁶(42) puckered rings, in which the O atom of each N—H...O hydrogen bond is also the acceptor in an O—H...O hydrogen bond that involves the 5‐hydroxy group. The large R₁₂⁶(42) rings straddle the axes and form stacked columns viaπ–π interactions between inversion‐related molecules of (I) [mean interplanar spacing = 3.254 Å and ring centroid–centroid distance = 3.688 (2) Å]. The channels are lined by methyl groups, which all point inwards to the centre of the channels.