Cooperative C–H…O H-bonds in ‘Bay Area’and Crystal Structure of 1-(4-Methylphenyl)-3-(4-methoxyphenyl)-2-propene-1-one

1 INTRODUCTION Chalcones possessing -C=C–C=O group are res-ponsible for the photoreaction[1], biological activity[2]and non-linear optical properties[3]. During our sys-tematic searches for organic functional materials forwhich the mode of molecular self-assembling (crys-tal packing) is important, the title compound wassynthesized. Presented herein are the studies on crystalpacking of the title complex and a brief study on theC–H…O H-bonds in “bay area” (Fig. 3) of this crys-tal a…     

Synthesis and Spectroscopic Characterization of Organophosphoryl Polyoxotungstates α-A-[RP(O)]_2PW_9O_(34)~(5-)

Derivatized polyoxometalates (POMs ), especially those including organic andorganometallic components, have received current attention due to their potential applicationin catalysis, medicine and material sciences~[1]. For these reasons, several research groupshave devoted their efforts to the synthesis of organic and organometallic derivatives of heteropolyanions~[2]. However, the studies on organophosphorus-substituted heteropolyanionshave been reported rarely. Recently, a unique study on …     

Synthesis and Crystal Structure of a New Mononuclear Nickel（Ⅱ） Mixed Complex Derived from 2-Aminoethyl-bi（3-bi-aminopropyl）amine with 1,10-Phenanthroline

1 INTRODUCTION The research on organic polyamines is currently of great interest because of their potential applica- tions as useful organic ligands, in which the amine nitrogen atoms have strong coordination ability to the transition metal ions and recognition function[1~4]. Their transition metal complexes play an excellent role in catalysis and mimic studies on dismutase and chlorophyll[5~7]. Therefore much attention has been focused on their syntheses and applications[8~11]. Our group…     

On the Crystal Structure of [Cu(OH)_2(H_2O)_2(4-C_5H_4NCOOH)_2]

In their report of the crystal structure of the compound claimed to be [Cu(OH)2(H2O)2(4- C5H4NCOOH)2], the authors did not give any experimental details on the location and refinement of the water and hydroxyl hydrogen atoms[1]; they had assumed the presence of the carboxylic -CO2H unit on the basis of the infrared stretching frequency at 1700 cm-1 that is only of medium intensity. The cell constants for the compound are, in fact, identical, with those documented for tetraaquabis(isonicot…     

Synthesis and Structure of the Manganese Complex with 2-Aminopyridine N-oxide

1 INTRODUCTIONMany complexes of 2-aminopyridine N-oxide (apo) have been characterized by infrared spectra, X-ray powder diffraction spectra, and by magnetic measurements and electronic spectra to liquid nitrogen temperature, but very few are on their crystal X-ray studies[1~3]. We have been studying complexes of pyridine N-oxide ligands containing a donor substitutes at the 2-position, in an attempt to broaden the range of N-oxide ligands complexes[4,5]. As continuing work of research on…     

Synthesis, Crystal Structure and Antimicrobial Study of N, N,N＇-Tris（3- aminopropyl）ethylenediamine Copper（Ⅱ） Diperchlorate

1 INTRODUCTION The researches on organic polyamines are currently of great interest because of their potential applications as useful organic ligands, in which the amine nitrogen atoms have strong coordination ability to the transition metal ions. Their transition metal complexes play an excellent role in catalysis and the mimic studies on superoxide dismutase and chlorophyll[1～6]. N,N,N?,N?-Tetrakis(3-ami- nopropyl) ethylenediamine has been extensively stu- died[7～9], but few new ineq…     

澄清溶液中NaA型分子筛膜的合成及气体渗透性能

The use of zeolite membranes in separation or combined reaction and separation processes is very attractive. Advantages of using such a type of membranes include their ability to discriminate molecules based on the molecular size and their stability[1]. In the past ten years, most efforts were involved in the synthesis and permeation studies of MFI zeolite membrane[2, 3]. Recently, NaA zeolite membrane has attracted much attention because of its high potential in the dehydration of organic liquids[4]. However, few gas permeation results were reported[5]. Furthermore, most of the NaA zeolite membrane was synthesized from gel[4]. In this letter, the synthesis of NaA zeolite membrane from clear solution and its gas permeation properties are reported.     

A Density Functional Study on the Geometries of Compounds Fe(HCN)_n~+ (n = 1～6)

1 INTRODUCTION The solvation of metal ion by different types ofsolvents is of great interest for a wide variety of app-lications[1]. In the experimental and theoretical inve-stigations, most of such studies are focused on ion-ligand systems complexed by…     

Low-temperature catalytic preparation of multi-wall MoS_2 nanotubes

Since the first report on inorganic fullerene-like WS2 polyhedra and nanotubes by Tenne et al.[1] in 1992, this kind of nanostructural materials have become extensive research topics owing to their unique electronic structures. WS2 and MoS2 nanomaterials have shown potential applications in the fields of scanning probe microscopy[2], solid-state lubrication[3], heterogeneous catalysis[4], and electrochemical hydrogen storage[5]. Up to now, a great deal of progress has been achieved in the st…     

Synthesis and Crystal Structure of a New Imidazole Coordinated Octamolybdate Compound

1 INTRODUCTION Polyoxometallates are of great interest not only for their structural variety but also for their un- expected properties[1, 2]. These inorganic anions had been widely investigated in catalysis, biology, me- dicine, magnetochemistry and materials science[3～6]. Especially, the studies on the organic ligands coor- dinated by polyoxometallates might help to under- stand the catalytic mechanism of polyoxometallates. In recent years, several octamolybdates containing organic l…     

Further test of the isolated pentagon rule: Thermodynamic and kinetic stabilities of C84 fullerene isomers

Thermodynamic and kinetic stabilities of 73 C₈₄ fullerene isomers were estimated from the MM3 heats of formation and the recently defined bond resonance energies (BREs), respectively. The BRE represents the contribution of a given π bond in a molecule to the topological resonance energy (TRE). All π bonds shared by two pentagons turned out to be highly reactive without exceptions. C₈₄ fullerene isomers with such π bonds must be incapable of survival during harsh synthetic processes. Thus, the isolated pentagon rule (IPR) proved to be applicable to such large fullerene cages. For sufficiently large fullerenes like C₈₄, some isolated-pentagon isomers are also predicted to be very unstable with highly antiaromatic π bonds. © 1996 by John Wiley & Sons, Inc.     

Nonclassical fullerenes with a heptagon violating the pentagon adjacency penalty rule

Nonclassical fullerenes with heptagon(s) and their derivatives have attracted increasing attention, and the studies on them are performing to enrich the chemistry of carbon. Density functional theory calculations are performed on nonclassical fullerenes C_n (n = 46, 48, 50, and 52) to give insight into their structures and stability. The calculated results demonstrate that the classical isomers generally satisfy the pentagon adjacency penalty rule. However, the nonclassical isomers with a heptagon are more energetically favorable than the classical ones with the same number of pentagon–pentagon bonds (B₅₅ bonds), and many of them are even more stable than some classical isomers with fewer B₅₅ bonds. The nonclassical isomers with the lowest energy are higher in energy than the classical ones with the lowest energy, because they have more B₅₅ bonds. Generally, the HOMO–LUMO gaps of the former are larger than those of the latter. The sphericity and asphericity are unable to rationalize the unique stability of the nonclassical fullerenes with a heptagon. The pyramidization angles of the vertices shared by two pentagons and one heptagon are smaller than those of the vertices shared by two pentagons and one hexagon. It is concluded that the strain in the fused pentagons can be released by the adjacent heptagons partly, and consequently, it is a common phenomenon for nonclassical fullerenes to violate the pentagon adjacent penalty rule. These findings are heuristic and conducive to search energetically favorable isomers of C_n, especially as n is 62, 64, 66, and 68, respectively. © 2010 Wiley Periodicals, Inc. J Comput Chem, 2010     

Fused five-membered rings determine the stability of C60F60

The structure and stability of a set of (CF)60 isomers have been computed at the B3LYP/6-31G(d) density functional theory level. The most stable isomer (6, F4@C60F56) has tube-like structure with four endo C-F bonds and fused five-membered rings at the end of the tube, while the reported most stable cage structure (2, F8@C60F52) with eight endo C-F bonds is higher in energy by 22.6 kcal/mol. This is in contrast to the isolated pentagon rule for the stability of fullerenes. The mean bond dissociation energy of 6 is larger than those of the experimental known C60F36, C60F48, and graphite fluoride. The relative energy per CF unit of 6 to graphite fluoride (CF)n is 3.7 kcal/mol, which is smaller than that of C60 fullerene per carbon to graphite (about 9-10 kcal/mol).     

Structure and reactivity of C54q+ (q = 0, 1, 2 and 4) fullerenes

Using density functional theory we have studied the structural properties of eleven C54 isomers that appear in the C60 fragmentation. We have evaluated the relative stability of the different isomers with respect the most stable one, which corresponds to the structure with the minimum number (four) of adjacent pentagons. On average, the length of a bond shared by pentagons and/or hexagons increases in the order hexagon-hexagon, hexagon-pentagon and pentagon-pentagon. However, we have found that the central bond in the confluence of four hexagons, i.e. a pyrene substructure, is anomalously large, becoming in some cases the largest one. We have also evaluated the nucleus-independent chemical shifts (NICS) at the center of every individual ring in the most stable isomers. For the chlorine derivatives, our calculations show that the favorite position for chlorine addition are the bonds shared by pentagons.     

The way of stabilizing non-IPR fullerenes and structural elucidation of C(54)Cl(8)

Recently, a new non-IPR chlorofullerene C(54)Cl(8) was isolated experimentally (Science 2004, 304, 699). To explore the ways to stabilize non-IPR fullerenes, the authors studied all of the possible isomers of C(54) fullerene and some of the C(54)Cl(8) isomers at PM3, B3LYP/3-21G, and B3LYP/6-31G* levels. Combined with analysis of pentagon distributions, bond resonance energies, and steric strains, C(54):540 with the least number of 5/5 bonds was determined to be the thermodynamically best isomer for the C(54)Cl(8). Based on C(54):540, the most probable structure of the experimental C(54)Cl(8) was elucidated. The results suggested one of the necessary conditions of stabilizing non-IPR fullerenes: chemical derivatizations of either endohedral complexation or exohedral addition need to sufficiently stabilize all of the kinetically unstable 5/5 bonds of the cages.     

DFT Studies on Non-IPR C68 and Endohedral Fullerene Sc3N@C68

The structures and spectra of 20 possible isomers of C78(CH2)3 have been studied by using AM1,INDO/CIS and DFT methods. The results show that the most stable isomer is 1,2,3,4,5,6-C78(CH2)3 (A) with annulene structures,where three -CH2 groups are added to the 6/6 bonds located at the same hexagon passed by the shortest axis of C78 (C2v). Compared with that of C78 (C2v),the first absorption in the electronic spectrum of C78(CH2)3 (A) is blue-shifted because of its wider LUMO-HOMO energy gap. While the IR frequencies of the C–C bonds on the carbon cage are red-shifted owing to the formation of annulene structures and the extension of the conjugated system. The chemical shifts of the carbon atoms in 13C NMR spectra are moved upfield upon the addition.     

Stability of small fullerenes C n (n=36,40 and 60): A topological and molecular orbital approach

Summary By semi-empirical molecular orbital calculations stability of fullerenes was analyzed in terms of topological parameters, such as the number of special fragments and the number of three types of abutting bonds between two 5-membered rings. Relative stability was compared by AM1 method for all spectrally distinct closed-shell isomers of C₃₆ and C₄₀ fullerenes, and for some closed-shell isomers of C₆₀ fullerene. Molecular geometries of these fullerenes were also optimized. Their relative stabilities were well explained by the instability of abutting bonds.     

On the structure and relative stability of C50 fullerenes

The complete set of 271 classical fullerene isomers of C50 has been studied by full geometry optimizations at the SAM1, PM3, AM1, and MNDO quantum-chemical levels, and their lower energy structures have also been partially computed at the ab initio levels of theory. A D(5h) species, with the least number of pentagon adjacency, is predicted by all semiempirical methods and the HF/4-31G calculations as the lowest energy structure, but the B3LYP/6-31G* geometry optimizations favor a D3 structure (with the largest HOMO-LUMO gap and the second least number of adjacent pentagons) energetically lower (-2 kcal/mol) than the D(5h) isomer. To clarify the relative stabilities at elevated temperatures, the entropy contributions are taken into account on the basis of the Gibbs energy at the HF/4-31G level for the first time. The computed relative-stability interchanges show that the D3 isomer behaves more thermodynamically stable than the D(5h) species within a wide temperature interval related to fullerene formation. According to a newly reported experimental observation, the structural/energetic properties and relative stabilities of both critical isomers (D(5h) and D3) are analyzed along with the experimentally identified decachlorofullerene C50Cl10 of D(5h) symmetry. Some features of higher symmetry C50 nanotube-type isomers are also discussed.     

Structure and Electronic Properties of Fullerenes C52q+: Is C522+ an Exception to the Pentagon Adjacency Penalty Rule?

The structure, vibrational spectra and electronic properties of the neutral, singly and doubly charged C52 fullerenes were studied by means of the Hartree-Fock method and density functional theory. Different isomers were considered, in particular those with the lowest possible number (five or six) of adjacent pentagons, and an isomer with a four-atom ring. For neutral and singly charged species, the most stable isomer is that with the lowest number of adjacent pentagons, namely five. However, for C(52)2+, the most stable structure has six adjacent pentagons. This finding, which contradicts the pentagon adjacency penalty rule, is a consequence of complete filling of the HOMO pi shell and the near-perfect sphericity of the most stable isomer. The simulated vibrational spectra show important differences in the positions and intensities of the vibrations for the different isomers.     

Isolated pentagon rule in buckybowls: a computational study on thermodynamic stabilities and bowl-to-bowl inversion barriers

Computations on a series of sumanene and pinakene isomers reveal that the isolated pentagon species are found to be more stable than non-isolated pentagon structures. However, the present study indicates that there is no correlation between the bowl-to-bowl inversion barrier and the relative stability. Unexpectedly, the least stable isomer has the lowest bowl-to-bowl inversion barrier in pinakene isomers. Thus, curvature cannot be taken as a measure to evaluate the stability of buckybowls. The relative energy ordering and HOMO-LUMO gap correlate well in the series of pinakene isomers considered.