A dendrimeric silane containing 162 allylic end groups is prepared via a divergent growing approach. The reaction process of the repetitive alkenylation and hydrosilylation cycles was monitored by NMR spectroscopic attachments. Both steps provided almost quantitative yields of pure silane dendrimers.

TlCl2(TCNQ)2.5 and Tl(TCNQ)3 were obtained from the reaction of LiTCNQ (TCNQ=tetracyanoquinodimethane) and TlX3 (X=Cl and NO3). These compounds were characterized by spectroscopic(IR, UV, EPR), electrochemical methods, and electrical conductivity measurements. Thermal analysis (TG, DSC) was also conducted. The room temperature electrical conductivities of these compounds are in the range of semiconductors. Spectroscopic studies indicate that Tl(TCNQ)3 has fully ionized TCNQ- ions in a form of simple salt, whereas TlCl2(TCNQ)2.5 is consisted of TCNQ- and TCNQ0 as a complex salt. EPR values of TCNQ- radical anion are 1.999 in both compounds and the signal attributable to metal ion is not observed, suggesting that any unpaired electrons are localized on TCNQ radicals, and metal atoms have diamagnetic state. Ligand decomposition and reduction process are simultaneously progressed in both compounds above at 200 ℃. The endothermic activation energy of TlCl2(TCNQ)2.5 is shown somewhat larger than that of Tl(TCNQ)3, it may be due to Tl-Cl bond strength. The mid-peak potentials of these compounds are very similar to those of TCNQ and the values of Epa and Epc are almost equal to 1. The wave of thallium ion is not detected in cyclic voltammogram, hence the redox processes of the complexes might be mainly localized to the TCNQ ligand rather than thallium ion.

Amino acid cobalt(Ⅲ) complexes of 1,3-diminopropane-N,N'-di-α-(β-methyl)-pentanoic acid (H2dpdmp), uns-cis-[Co(dpdmp)(aa)] (aa=glycine, S-alanine, R-aspartic acid, sarcosine) have been prepared from the reaction between the uns-cis-[Co(dpdmp)Cl2]- complex and the corresponding amino acid. In the reaction with the uns-cis-[Co(dpdmp)Cl2]- complex, glycine and S-alanine have yielded both merridional and facial isomers, while R-aspartic acid and sarcosine, only merridional isomers. The stereospecific substitution reaction of R-aspartic acid to racemic uns-cis-[Co(dpdmp)Cl2]- complex has yielded two merridional diastereomers; ΛR-uns-cis- and ΛR-uns-cis-[Co(dpdmp)(R-asp)]. It is of interest to note that this is one of the few CoⅢ(ONNO)(aa) type complex preparations, which gives only one isomer with stereospecificity. On the other hand, two merridional products obtained from the reaction of sarcosine with racemic uns-cis-[Co(dpdmp)Cl2]- are turned out to be mixtures of optical isomers.

Cobalt(Ⅲ) complexes of trifunctional amino acid and N,N'-diethylethylenediamine-N,N'-di-α-butyrate(deedba), s-cis-[Co(deedba)(L-aa)] (L-aa=S-methyl-L-cysteine, L-aspartic acid, L-glutamic acid) have been prepared from the reaction between the s-cis-[Co(deedba)(Cl2)]- complex and the corresponding amino acid. The amino acids have been found to coordinate through the amine and carboxylate groups. The S-methyl-L-cystene is coordinated not by the sulfur donor atom, but by the nitrogen and oxgen donor atoms, and the L-aspartic and L-glutamic acids are coordinated to the cobalt(Ⅲ) ion via formation of the five-membered glycinate chelate ring. Relatively small optical activity shown by the complexes is due to the chiral center present in the amino acids.

Electrocyclic ring-closure of 6-vinylcyclohepta-1,3,5-isocyanate has been carried out in the presence of triphenylphosphine to examine a catalyzing effect of the triphenylphosphine. The preparation of 10-(1-carboalkoxyalkyl)-2,7-methanoaza[10]annulenes by the electrocyclic ring-closure of ketenimine intermediates, which are formed by the reaction of triphenylalkylidenephosphorane and 6-vinylcyclo-hepta-1,3,5-isocyanate, is described. 10-Alkyl-2,7-methanoaza[10]annulenes were prepared by basic hydrolysis of the carboalkoxyaza[10]annulenes and decarboxylation of the acid intermediates. In the same manner, 10-(N-alkyl(or aryl))-2,7-methanoaza[10]annulenes were prepared from the reaction of the isocyanate and N-alkyl(or aryl)iminotriphenylphosphorane via electrocylic ring-closure of carbodiimide intermediate.

Several polysilanes with sterically bulky substituents such as poly(2-phenylpropyl)(n-hexyl)silane were prepared by Wurtz-type coupling. The polysilane products were mixtures of low-molecular-weight polymers (&bar{M};w~103) as major and high-molecular-weight polymers (&bar{M};w~106) as minor. Overall yields for polysilanes were in the range of 81-99%. λmax of liquid low MW polymers appeared at around 280 nm. Formations of solid high MW polymers were decreased by a longer reaction time and increased steric bulkiness of substituents. High MW polymers with λmax at 327 nm except crosslinked polymers were soluble in common organic solvents and found to be light sensitive. Crosslinked high MW polymer gave 21% TGA ceramic yield, compared with linear high polymer giving zero ceramic yield.

Three conformational isomers of calix[4]arene butanoate were isolated from the reaction of calix[4]arene and butanoyl chloride in the presence of NaH and their structures were determined by NMR spectra as 1,2-alternate 2a, partial cone 2b and 1,3-alternate conformer 2c, respectively. The crystal structure of 2a has been determined by X-ray diffraction method. The crystals are monoclinic, space group C2/c, a=18.435 (4), b=13.774 (2), c=16.941 (3) Å, β=116.23 (1)°, Z=4, V=3858.8 (12)Å3, Dc=1.21 g cm-3, Dm=1.21 g cm-3. The molecule is in the 1,2-alternate conformation. It has two-fold symmetry axis along the line connecting between C (7AA') and C (7BB') parallel to the b axis of crystal lattice.

The effects caused by the ionization on the electronic structure and geometry on C60 are studied by the modified Su-Schriffer-Heeger (SSH) model Hamiltonian. After the ionization of C60, the bond structure of the singly charged C60 cation is deformed from Ih symmetry of the neutral C60 to D5d, C1, and C2, which is dependent upon the change of the electron-phonon coupling strength. The electronic structure of the C60+ cation ground state undergoes Jahn-Teller distortion in the weak electron-phonon coupling region, while self-localized states occur in the intermediate electron-phonon region, but delocalized electronic states appear again in the strong electron-phonon region. In the realistic strength of the electron-phonon coupling in C60, the bond structure of C60+ shows the layer structure of the bond distortion and a polaron-like state is formed.

The principal elements of the 31P NMR chemical shielding tensors have been determined for three binuclear platinum diphosphite complexes, K4[Pt2(P2O5H2)4·2H2O ("Pt2"), K4[Pt2(P2O5H2)4Cl2]·2H2O ("Pt2Cl2"), and K4[Pt2(P2O5H2)4Br2]·2H2O ("Pt2Br2"), by using a Herzfeld-Berger graphical method for interpreting the 31P MAS spectrum. The orientations of 31P chemical shielding tensor relative to the molecular axis system are partially assigned with combination of the longitudinal relaxation study of HPO32- and the reference to known tensor orientations of related sites; the most chemical shielding component, δ33, is directed along the P-Pt bond axis. A discussion is given in which the experimental principal elements of the 31P chemical shielding tensor are related with the Pt-Pt bond distances in binuclear platinum diphosphite complexes.

The laser-induced fluorescence excitation spectrum of 7-amino-4-(trifluoromethyl)coumarin in a supersonic jet has been recorded in the 340-352 nm region. The electronic band origin was observed at 28622.8 cm-1. Vibrational assignments for the three fundamental low-frequency modes and eight combination bands have been made for the S1 electronic excited state. The out-of-plane vibrations of this molecule have been characterized from the low-frequency assignments of the spectrum. The periodic potential energy function for the CF3 torsion, which satisfactorily fits the observed data, were also determined to be V(Φ)=95X(1-cos3Φ)-32X(1-cos6Φ) where Φ is the torsional angle. The relatively low torsional barrier of 99 cm-1 in S1 state could be explained by the small steric interactions between the functional groups attached to a bicyclic ring.