Isolation and Crystallographic Characterization of Two,Nonisolated Pentagon Endohedral Fullerenes: Ho3N@C2(22010)-C78 and Tb3N@C2(22010)-C78

Purified samples of Ho₃N@C₂(22010)-C₇₈ and Tb₃N@C₂(22010)-C₇₈ have been isolated by two distinct processes from the rich array of fullerenes and endohedral fullerenes present in carbon soot from graphite rods doped with Ho₂O₃ or Tb₄O₇. Crystallographic analysis of the endohedral fullerenes as cocrystals with Ni(OEP) (in which OEP is the dianion of octaethylporphyrin) shows that both molecules contain the chiral C₂(22010)-C₇₈ cage. This cage does not obey the isolated pentagon rule (IPR) but has two sites where two pentagons share a common C−C bond. These pentalene units bind two of the metal ions, whereas the third metal resides near a hexagon of the cage. Inside the cages, the Ho₃N or Tb₃N unit is planar. Ho₃N@C₂(22010)-C₇₈ and Tb₃N@C₂(22010)-C₇₈ use the same cage previously found for Gd₃N@C₂(22010)-C₇₈ rather than the IPR-obeying cage found in Sc₃N@D_3h-C₇₈.     

Syntheses and crystal structures of polymeric ionic triorganotin esters of 3,5-pyridinedicarboxylic acid and 5-nitroisophthalic acid

The triethylammonium dicarboxylatotriorganostannates, [(C₂H₅)₃NH][R₃Sn(3,5-pdc)]?·?mH₂O (3,5-pdc?=?3,5-pyridinedicarboxylate) (m?=?1, R?=?Me 1; m?=?0, R?=?Ph 2, PhCH₂ 3, n-Bu 4), [(C₂H₅)₃NH][R₃Sn(5-nip)] (5-nip?=?5-nitroisophthalate) (R?=?Me 5, Ph 6, PhCH₂ 7, n-Bu 8) have been prepared from triethylamine, 3,5-pyridinedicarboxylic acid, 5-nitroisophthalic acid and triorganotin chloride. Complexes 1–8 have been characterized by elemental, IR, ¹H, ¹³C and ¹¹⁹Sn NMR analyses. Complexes 1, 2, 5 and 6 are also determined by single crystal X-ray diffraction. For 1, 2, 5 and 6, each carboxylate moiety is involved in coordination to a tin center via only one O atom showing that the Sn atoms are five-coordinate and exist in trigonal bipyramidal geometries. Moreover, for 2, 5 and 6, the nitrogen atoms of ammonium are hydrogen bonded to the pendant carboxyl oxygen. In 1, adjacent polymeric chains and triethylammonium are linked by hydrogen bonds through the co-crystallized water molecule, thus a 2D network is formed.     

Thiadiazolo-Azaacenes

This work reports the synthesis and characterization of bis- and tetrakis(thiadiazolo)-appended di- and tetraazaacenes, displaying up to seven catenated benzene/pyrazine rings. The targets are obtained by condensation of benzo-bis(thiadiazole)-4,5-dione with aromatic di- and tetraamines. The condensation products—up to a heptacene-like species—are stable but can be insoluble. Soluble derivatives are readily processible, but do not show enhanced electron affinities, as the two or four attached benzothiadiazole units are effectively resonance-separated from the acene body, maximizing the number of Clar-sextets.     

Synthesis,characterization, and electrochemistry of monophosphine‐containing diiron propane‐1,2‐dithiolate complexes related to the active site of [FeFe]‐hydrogenases

Five monophosphine‐substituted diiron propane‐1,2‐dithiolate complexes as the active site models of [FeFe]‐hydrogenases have been synthesized and characterized. Reactions of complex [Fe₂(CO)₆{μ‐SCH₂CH(CH₃)S}] ( 1 ) with a monophosphine ligand tris(4‐methylphenyl)phosphine, diphenyl‐2‐pyridylphosphine, tris(4‐chlorophenyl)phosphine, triphenylphosphine, or tris(4‐fluorophenyl)phosphine in the presence of the oxidative agent Me₃NO·2H₂O gave the monophosphine‐substituted diiron complexes [Fe₂(CO)₅(L){μ‐SCH₂CH(CH₃)S}] [L = P(4‐C₆H₄CH₃)₃, 2 ; Ph₂P(2‐C₅H₄N), 3 ; P(4‐C₆H₄Cl)₃, 4 ; PPh₃, 5 ; P(4‐C₆H₄F)₃, 6 ] in 81%–94% yields. Complexes 2 – 6 have been characterized by elemental analysis, spectroscopy, and X‐ray crystallography. In addition, electrochemical studies revealed that these complexes can catalyze the reduction of protons to H₂ in the presence of HOAc.     

Reducing the computational cost of NMR crystallography of organic powders at natural isotopic abundance with the help of 13C-13C dipolar couplings

Structure determination of functional organic compounds remains a formidable challenge when the sample exists as a powder. Nuclear magnetic resonance crystallography approaches based on the comparison of experimental and Density Functional Theory (DFT)-computed ¹H chemical shifts have already demonstrated great potential for structure determination of organic powders, but limitations still persist. In this study, we discuss the possibility of using ¹³C-¹³C dipolar couplings quantified on powdered theophylline at natural isotopic abundance with the help of dynamic nuclear polarization, to realize a DFT-free, rapid screening of a pool of structures predicted by ab initio random structure search. We show that although ¹³C-¹³C dipolar couplings can identify structures possessing long range structural motifs and unit cell parameters close to those of the true structure, it must be complemented with other data to recover information about the presence and the chemical nature of the supramolecular interactions.     

The Impact of pH on Catalytically Critical Protein Conformational Changes: The Case of the Urease,a Nickel Enzyme

Urease uses a cluster of two Ni^II ions to activate a water molecule for urea hydrolysis. The key to this unsurpassed enzyme is a change in the conformation of a flexible structural motif, the mobile flap, which must be able to move from an open to a closed conformation to stabilize the chelating interaction of urea with the Ni^II cluster. This conformational change brings the imidazole side chain functionality of a critical histidine residue, αHis323, in close proximity to the site that holds the transition state structure of the reaction, facilitating its evolution to the products. Herein, we describe the influence of the solution pH in modulating the conformation of the mobile flap. High-resolution crystal structures of urease inhibited in the presence of N-(n-butyl)phosphoric triamide (NBPTO) at pH 6.5 and pH 7.5 are described and compared to the analogous structure obtained at pH 7.0. The kinetics of urease in the absence and presence of NBPTO are investigated by a calorimetric assay in the pH 6.0–8.0 range. The results indicate that pH modulates the protonation state of αHis323, which was revealed to have pK_a=6.6, and consequently the conformation of the mobile flap. Two additional residues (αAsp224 and αArg339) are shown to be key factors for the conformational change. The role of pH in modulating the catalysis of urea hydrolysis is clarified through the molecular and structural details of the interplay between protein conformation and solution acidity in the paradigmatic case of a metalloenzyme.     

Single determinant N‐representability and the kernel energy method applied to water clusters

The Kernel energy method (KEM) is a quantum chemical calculation method that has been shown to provide accurate energies for large molecules. KEM performs calculations on subsets of a molecule (called kernels) and so the computational difficulty of KEM calculations scales more softly than full molecule methods. Although KEM provides accurate energies those energies are not required to satisfy the variational theorem. In this article, KEM is extended to provide a full molecule single‐determinant N‐representable one‐body density matrix. A kernel expansion for the one‐body density matrix analogous to the kernel expansion for energy is defined. This matrix is converted to a normalized projector by an algorithm due to Clinton. The resulting single‐determinant N‐representable density matrix maps to a quantum mechanically valid wavefunction which satisfies the variational theorem. The process is demonstrated on clusters of three to twenty water molecules. The resulting energies are more accurate than the straightforward KEM energy results and all violations of the variational theorem are resolved. The N‐representability studied in this article is applicable to the study of quantum crystallography. © 2017 Wiley Periodicals, Inc.