Synthesis of π-Extended Carbazole Dimers Via Oxidative Cyclization Using DDQ and Sulfonic Acid and Elucidation of the Reaction Mechanism.

This paper describes the synthesis of various π-extended carbazole dimers via intramolecular oxidative cyclization using a chain precursor consisting of two carbazole units bridged by a nitrogen atom. A careful selection of the reaction conditions using 2,3-dichloro-5,6-dicyano-p-benzoquinone/sulfonic acid enabled the selective synthesis of a π-extended analogue with an angular (L-shape) structure in moderate yield. The preferential positions for the bonding of the two carbazole units in this π-extended derivative were determined by performing density functional theory calculations.

Synthesis, Structures, and Electronic Properties of 2,7-Anthrylene-Based Azacyclophanes Bearing o-, m-, and p-Phenylenediamine Linkers.

A series of novel azacyclophanes consisting of 2,7-anthrylene and phenylene units were designed and synthesized by the Buchwald-Hartwig coupling reaction to investigate their unique electronic properties in multiple oxidized states. Cyclic voltammetry showed that the p-phenylene derivative exhibited three reversible oxidation waves, whereas the o- and m-phenylene derivatives showed two quasi-reversible oxidation waves due to the complicated intramolecular interaction between the oxidized units and neutral units. Moreover, the absorption spectra of the p-phenylene derivative in different oxidation states showed absorption bands at 865 and 1025 nm, which were attributed to intramolecular charge-transfer interactions. The photophysical and electrochemical properties of the p-phenylene analog were also compared with those of the o- and m-phenylene derivatives based on theoretical calculations for further evaluation of the intramolecular electronic interactions.

Donor-Donor'-Acceptor Triads Based on [3.3]Paracyclophane with a 1,4-Dithiafulvene Donor and a Cyanomethylene Acceptor: Synthesis, Structure, and Electrochemical and Photophysical Properties.

Donor-donor'-acceptor triads (1, 2), based on [3.3]paracyclophane ([3.3]PCP) as a bridge, with electron-donating properties (D') using 1,4-dithiafulvene (DTF; TTF half unit) as a donor and dicyanomethylene (DCM; TCNE half unit) or an ethoxycarbonyl-cyanomethylene (ECM) as an acceptor were designed and synthesized. The pulse radiolysis study of 1 a in 1,2-dichloroethane allowed the clear assignment of the absorption bands of the DTF radical cation (1 a.+ ), whereas the absorption bands due to the DCM radical anion could not be observed by γ-ray radiolysis in 2-methyltetrahydrofuran rigid glass at 77 K. Electrochemical oxidation of 1 a first generates the DTF radical cation (1 a.+ ), the absorption bands of which are in agreement with those observed by a pulse radiolysis study, followed by dication (1 a2+ ). The ESR spectrum of 1 a.+ showed a symmetrical signal with fine structure and an ESR simulation predicted that the spin of 1 a.+ is delocalized over S and C atoms of the DTF moiety and the central C atom of the trimethylene bridge bearing the DTF moiety. Pulse radiolysis, ESR, and electrochemical studies indicate that the DTF radical cation of 1 a.+ is more stable than that of 6.+ , and the latter shows a strong tendency to dimerize. This result indicates that the [3.3]PCP moiety as a bridge can stabilize the DTF radical cation more than the 1,3-diphenylpropane moiety because of kinetic stability due to its rigid structure and the weak electronic interaction of DTF and DCM moieties through [3.3]PCP.

Synthesis and Electronic Properties of Length-Defined 9,10-Anthrylene-Butadiynylene Oligomers.

Linear π-conjugated oligomers consisting of anthracene and diacetylene units were readily synthesized by a one-pot process that involved desilylation and oxidative coupling from appropriate building units. We were able to isolate length-defined oligomers ranging from 2-mer to 6-mer as stable and soluble solids. The bathochromic shifts in the UV-vis spectra suggested that the π-conjugation was extended with elongation of the linear chain. Cyclic voltammetric measurements showed characteristic reversible oxidation waves that were dependent on the number of anthracene units.

Oxidation State-Dependent Intramolecular Electronic Interaction of Carbazole-Based Azacyclophanes with 9,10-Anthrylene Units.

We designed an azacyclophane comprising 3,6-substituted carbazole and 9,10-anthrylene units to investigate the unique electronic properties of the oxidation states arising from the presence of multiple oxidizable azacyclophane. This compound and its analogue containing 1,4-phenylene in substitution of 9,10-anthrylene units were synthesized by Buchwald-Hartwig coupling reactions. Cyclic voltammograms of both the 9,10-anthrylene and 1,4-phenylene derivatives exhibited four quasi-reversible oxidation processes. The absorption spectra of the oxidation states of the 9,10-anthrylene derivative exhibited broad absorption bands in the near-infrared region arising from charge-resonance and intramolecular charge-transfer interactions. The photophysical and electrochemical properties of the 9,10-anthrylene derivative were compared with those of the corresponding 1,4-phenylene derivative on the basis of theoretical calculations to evaluate the intramolecular electronic interactions.

Synthesis of 1,2-Bis(2-aryl-1H-indol-3-yl)ethynes via 5-exo-Digonal Double Cyclization Reactions of 1,4-Bis(2-isocyanophenyl)buta-1,3-diyne with Aryl Grignard Reagents.

New π-conjugated 1,2-bis(2-aryl-1H-indol-3-yl)ethynes 1a-j having various substituents on the two aryl groups were efficiently synthesized via unusual 5-exo-digonal double isocyanide-acetylene cyclization reactions of 1,4-bis(2-isocyanophenyl)buta-1,3-diyne 3 and aryl Grignard reagents (R-MgBr, R = C6H5 (1a), 4-H3CC6H4 (1b), 2-H3CC6H4 (1c), 3-MeOC6H4 (1d), 3-(CH3)2NC6H4 (1e), 4-F3CC6H4 (1f), 4-FC6H4 (1g), 3-FC6H4 (1h), 4-PhOC6H4 (1i), and 2-Naph (1j)) in 19-85% yields. The UV-vis spectra were rationalized in detail using time-dependent DFT and single point calculations. The fluorescence emission peaks for 1a-j were observed at around 450 nm. Especially for 1f and 1j, those spectra displayed broad emission bands and relatively large Stokes shifts (3977-4503 cm-1), indicating the contribution of an intramolecular charge transfer. The absolute quantum yields (0.50-0.62) of 1a-j were higher than those of parent 8 (0.19) and 2-phenyl-1H-indole (0.11). The electrochemical features for 1a-j were investigated by cyclic voltammetry. The frontier molecular orbital levels for 1a-j were estimated based on the combination of oxidation potentials, UV-vis, and DFT calculated data. The structural property of 1,2-bis(2-phenyl-1H-indol-3-yl)ethyne 1a was characterized by several spectroscopic methods and finally determined by X-ray analysis of a single crystal of 1a recrystallized from ethyl acetate. The structural features of 1a-j were also supported by DFT calculations.

Intramolecular Charge-Transfer Interaction of Donor-Acceptor-Donor Arrays Based on Anthracene Bisimide.

We designed anthracene bisimide (ABI) derivatives having two triphenylamine (TPA) groups as donor units at the 9,10-positions to form a novel π-conjugated donor-acceptor system. These compounds and their analogues with ethynylene linkers were synthesized by Suzuki-Miyaura and Sonogashira coupling reactions, respectively. In UV-vis spectra, the linker-free derivatives showed broad absorption bands arising from intramolecular charge-transfer interactions. Introducing ethynylene linkers resulted in a considerable red shift of the absorption bands. In fluorescence spectra, the ethynylene derivatives showed intense emission bands at 600-650 nm. Their photophysical and electrochemical properties were compared with those of the corresponding mono TPA derivatives on the basis of theoretical calculations and cyclic voltammetry to evaluate the intramolecular electronic interactions between the donor and acceptor units.

Chemistry of anthracene-acetylene oligomers XXV: on-surface chirality of a self-assembled molecular network of a fan-blade-shaped anthracene-acetylene macrocycle with a long alkyl chain.

An anthracene cyclic dimer with two different linkers and a dodecyl group was synthesized by means of coupling reactions. The calculated structure had a planar macrocyclic π core and a linear alkyl chain. Scanning tunneling microscopy observations at the 1-phenyloctane/graphite interface revealed that the molecules formed a self-assembled monolayer that consisted of linear striped bright and dark bands. In each domain, the molecular network consisted of either Re or Si molecules that differed in the two-dimensional chirality about the macrocyclic faces, which led to a unique conglomerate-type self-assembly. The molecular packing mode and the conformation of the alkyl chains are discussed in terms of the intermolecular interactions and the interactions between the molecules and the graphite surface with the aid of MM3 simulations of a model system.

Three-dimensional aromatic networks.

Three-dimensional (3D) networks consisting of aromatic units and linkers are reviewed from various aspects. To understand principles for the construction of such compounds, we generalize the roles of building units, the synthetic approaches, and the classification of networks. As fundamental compounds, cyclophanes with large aromatic units and aromatic macrocycles with linear acetylene linkers are highlighted in terms of transannular interactions between aromatic units, conformational preference, and resolution of chiral derivatives. Polycyclic cage compounds are constructed from building units by linkages via covalent bonds, metal-coordination bonds, or hydrogen bonds. Large cage networks often include a wide range of guest species in their cavity to afford novel inclusion compounds. Topological isomers consisting of two or more macrocycles are formed by cyclization of preorganized species. Some complicated topological networks are constructed by self-assembly of simple building units.

Chemistry of anthracene-acetylene oligomers. XVII. Synthesis, structure, and dynamic behavior of 1,8-anthrylene pentamers and hexamers with acetylene linkers.

Three types of cyclic oligomers consisting of five or six 1,8-anthrylene units with acetylene linkers were synthesized by macrocyclization of the corresponding acyclic precursors with coupling reactions. DFT calculations at the M05/3-21G level revealed that the pentamers had a relatively rigid structure with strained alkyne carbons. Meanwhile, out of several possible conformers the hexamers preferred to take parallelogram-prism structures due to transannular π···π interactions, and conformational interconversions via rotation about the acetylene axes took place rapidly at room temperature. NMR spectra and electronic spectra are discussed on the basis of molecular structures. The enantiomers of the chiral hexamer with one diacetylene linker were resolved by chiral HPLC, and showed optical activity.

Chemistry of Anthracene-Acetylene Oligomers XXVII. Iterative Synthesis, Structures, and Properties of Anthracene-Diacetylene Cyclic Oligomers with 10-Mesitylanthracene-1,8-diyl Units.

A series of cyclic oligomers consisting of 10-mesitylanthracene-1,8-diyl units and diacetylene linkers were synthesized as soluble π-conjugated compounds. Macrocyclic frameworks from dimer to octamer except heptamer were constructed from 1,8-diethynylanthracene derivatives by iterative coupling reactions. The rigid structure of the dimer, the strained structures of the trimer and the pentamer, and the belt-shaped structures of the other even-numbered oligomers were revealed by X-ray analysis and DFT calculations. The dynamic behavior of the cyclic oligomers was analyzed by observing variable-temperature 1 H NMR spectra. The UV/Vis and fluorescence spectra of these emissive cyclic compounds are discussed on the basis of the molecular structures.

Molecular folding screen: folding and unfolding of 1,8-anthrylene-ethynylene oligomers by photochemical cycloaddition and thermal cycloreversion.

Molecular folding screens consisting of anthracene plates and acetylene linkers stereoselectively fold into a zigzag form by [4 + 4]photocycloaddition, and unfold by thermal cycloreversion.

New pi-conjugated system with a rigid framework of 1,8-anthrylene-ethynylene cyclic dimer and its monoanthraquinone analogue.

Two types of pi-conjugated compounds were synthesized by Sonogashira coupling, and their structures and properties were investigated by X-ray analysis and spectroscopic measurements. The monoanthraquinone compound features an out-of-plane deformation of the inner carbonyl moiety and dimer formation in crystals and solution.

Planar Anthracene-Acetylene Frameworks as a Stereogenic Motif.

Planar and rigid frameworks that consist of two 1,8-substituted anthracene units and two acetylene linkers were utilized as key structures for the generation of stereoisomers through the introduction of extra substituents. These compounds were synthesized from 1,8-substituted anthracene building units by a combination of coupling reactions. We designed diastereomers, enantiomers, and topomers by modifying the combination of the two linkers and the number of substituents at sterically crowded intraannular positions. The molecular structures, stereochemistry, and properties of these compounds were investigated by means of spectroscopic techniques and theoretical calculations. A prochiral cyclic dimer with one extraannular substituent was designed to generate a stereochemical phenomenon in two dimensions. Scanning tunneling microscopy measurements revealed that the molecules formed a self-assembled monolayer at the liquid-solid interface in a conglomerate-type manner. The scope and potential of the macrocyclic frameworks in studies of π-conjugated compounds are presented.

Isolable Triradical Trication of Hexaaza[16]paracyclophane with Embedded 9,10-Anthrylenes: A Frustrated Three-Spin System.

A new derivative of hexaaza[16]paracyclophane in which p-phenylenes are alternately replaced by 9,10-anthrylenes was prepared to investigate the impact on overall π-conjugation as well as conformational change of the macrocycle. The charge and spin distribution for one-electron and three-electron oxidation of the macrocycle was elucidated by means of electrochemical, spectroelectrochemical, EPR spectroscopic, and SQUID magnetometric methods. In particular, the triradical trication was successfully isolated as an air-stable salt, and moreover, its structure was disclosed by X-ray analysis. The triradical trication was characterized as a spin-frustrated three-spin system with the antiferromagnetic exchange interaction (J/kB ≃ - 74 K).

Macrocyclic 2,7-Anthrylene Oligomers.

A macrocyclic compound consisting of six 2,7-anthrylene units was successfully synthesized by Ni-mediated coupling of the corresponding dibromo precursor as a novel π-conjugated compound. This compound was sufficiently stable and soluble in organic solvents due to the presence of mesityl groups. X-ray analysis showed that the molecule had a nonplanar and hexagonal wheel-shaped framework of approximately S6 symmetry. The dynamic process between two S6 structures was observed by using the dynamic NMR technique, the barrier being 58 kJ mol(-1) . The spectroscopic properties of the hexamer were compared with those of analogous linear oligomers.

[A questionnaire about radiation safety management of the draining-water system at nuclear medicine facilities].

We conducted a questionnaire survey about radiation-safety management condition in Japanese nuclear medicine facilities to make materials of proposition for more reasonable management of medical radioactive waste. We distributed a questionnaire to institutions equipped with Nuclear Medicine facilities. Of 1,125 institutions, 642 institutes (52.8%) returned effective answers. The questionnaire covered the following areas: 1) scale of an institution, 2) presence of enforcement of radiotherapy, 3) system of a tank, 4) size and number of each tank, 5) a form of draining-water system, 6) a displacement in a radioactive rays management area, 7) a measurement method of the concentration of medical radioactive waste in draining water system, 8) planned and used quantity of radioisotopes for medical examination and treatment, 9) an average displacement of hospital for one month. In most institutions, a ratio of dose limitation of radioisotope in draining-water system was less than 1.0, defined as an upper limitation in ordinance. In 499 hospitals without facilities of hospitalization for unsealed radioisotope therapy, 473 hospitals reported that sum of ratios of dose limits in a draining-water system was less than 1.0. It was calculated by used dose of radioisotope and monthly displacement from hospital, on the premise that all used radioisotope entered in the general draining-water system. When a drainage including radioactivity from a controlled area join with that from other area before it flows out of a institution, it may be diluted and its radioactive concentration should be less than its upper limitation defined in the rule. Especially, in all institutions with a monthly displacement of more than 25,000 m3, the sum of ratio of the concentration of each radionuclide to the concentration limit dose calculated by used dose of radioisotope, indicated less than 1.0.

[Investigation of radioactivity measurement of medical radioactive waste].

To explore the possibility of which medical radioactive wastes could be disposed as general wastes after keeping them a certain period of time and confirming that their radioactivity reach a background level (BGL), we made a survey of these wastes in several nuclear medicine facilities. The radioactive wastes were collected for one week, packed in a box according to its half-life, and measured its radioactivity by scintillation survey meter with time. Some wastes could reach a BGL within 10 times of half-life, but 19% of the short half-life group (group 1) including 99mTc and 123I, and 8% of the middle half-life group (group 2) including 67Ga, (111)In, and 201Tl did not reach a BGL within 20 times of half-life. A reason for delaying the time of reaching a BGL might be partially attributed to high initial radiation dose rate or heavy package weight. However, mixing with the nuclides of longer half-life was estimated to be the biggest factor affecting this result. When disposing medical radioactive wastes as general wastes, it is necessary to avoid mixing with radionuclide of longer half-life and confirm that it reaches a BGL by actual measurement.

Chemistry of anthracene-acetylene oligomers XX: synthesis, structures, and self-association of anthracene-anthraquinone cyclic compounds with ethynylene linkers.

We have synthesized anthracene-acetylene oligomers, which contained one 10-substituted anthracene unit and one anthraquinone unit, by cyclization with Sonogashira coupling. X-ray analysis revealed an almost-planar framework and significant out-of-plane deformation around the inner carbonyl moiety because of steric hindrance. These compounds underwent self-association in solution and their association constants for monomer-dimer exchange were determined by variable-concentration (1)H NMR measurements in CDCl(3): 8 mol(-1) L (10-substituent: isopropyl), <5 mol(-1) L (methoxy), and 19 mol(-1) L (octyloxy). These results were discussed on the basis of spectroscopic and molecular-orbital analysis. A linear molecular assembly of the octyloxy compound at a liquid/graphite interface was observed by STM measurements.