Synthesis,Structure, Optical,and Electrochemical Properties of Triple‐ and Quadruple‐Decker Co‐facial Tetrathiafulvalene Arrays

Understanding the details of the electronic structure in face‐to‐face arranged tetrathiafulvalenes (TTFs) is very important for the design of supramolecular functional materials and superior conductive organic materials. This article is a comprehensive study of the interactions among columnar stacked TTFs using trimeric (trimer) and tetrameric (tetramer) TTFs linked by alkylenedithio groups (‐S(CH₂)_nS‐, n=1–4) as models of triple‐ and quadruple‐decker TTF arrays. Single‐crystal X‐ray analyses of neutral trimeric TTFs revealed that the three TTF moieties are oriented in a zigzag arrangement. Cyclic voltammetry measurements (CV) reveal that the trimer and tetramer exhibited diverse reversible redox processes with multi‐electron transfers, depending on the length of the ‐S(CH₂)_nS‐ units and substituents. The electronic spectra of the radical cations, prepared by electrochemical oxidation, showed charge resonance (CR) bands in the NIR/IR region (1630–1850 nm), attributed to a mixed valence (MV) state of the triple‐ and quadruple‐decker TTF arrays. In the trimeric systems, the dicationic state (+2; 0.66 cation per TTF unit) was found to be a stable state, whereas the monocationic state (+1) was not observed in the electronic spectra. In the tetrameric system, substituent‐dependent redox processes were observed. Moreover, π‐trimers and π‐tetramers, which show a significant Davydov blueshift in the spectra, are formed in the tricationic (trimer) and tetracationic (tetramer) state. In addition, these attractive interactions are strongly dependent on the length of the linkage unit.     

Humidity-responsive thermal conduction properties of bacterial cellulose films

Cellulose - High hygroscopicity is an unavoidable feature of cellulose materials, and it is important for clarifying the humidity dependence of the target function toward precise utilization....     

Improvement of TiO2/Dye/Electrolyte Interface Conditions by Positional Change of Alkyl Chains in Modified Panchromatic Ru Complex Dyes

A series of panchromatic ruthenium sensitizers ( MJ sensitizers) with attached thiophene and phenyl units bearing alkyl chains was synthesized. A new synthetic route was used to examine all possible positions for the alkyl chains. The absorption spectra showed the sum of a ruthenium complex and peripheral organic chromophore units. The hypochromic effect and blueshift of the metal‐to‐ligand charge‐transfer band observed in the modified ruthenium sensitizers were suppressed by changing the positions of the alkyl chains on the attached thiophene ring. Changing only one alkyl chain also influenced the performance of dye‐sensitized solar cells. Ruthenium sensitizer MJ‐10 with bulky substituent harvests visible and near‐infrared light, and solar cells sensitized by MJ‐10 exhibit an efficiency of 9.1 % under 1 sun irradiation.     

The Microwave Spectrum of Methyl Formate (HCOOCH3) in the Frequency Range from 7 to 200 GHz

The rotational spectrum of methyl formate (HCOOCH₃) has been observed in the frequency range from 7 to 200 GHz. We newly assigned 1612 lines in the ground torsional state and simultaneously analyzed both A- and E-species data including previously reported lines on the basis of the internal axis method. A total of 3077 lines were fitted to a 1σ standard deviation of 139 kHz, and molecular parameters were determined.     

Rotational Spectra of XeH and Its Isotopic Species

Frequencies of rotational transitions of XeH⁺ and its isotopic species were measured in the 1–5 THz region with a highprecision far-infrared spectrometer using a tunable radiation source. Measured frequencies were analyzed together with previous microwave and infrared measurements to refine mass-independent Dunham parameters.     

On the strength of marriage theorems and uniformity

Kierstead showed that every computable marriage problem has a computable matching under the assumption of computable expanding Hall condition and computable local finiteness for boys and girls. The strength of the marriage theorem reaches or if computable expanding Hall condition or computable local finiteness for girls is weakened. In contrast, the provability of the marriage theorem is maintained in even if local finiteness for boys is completely removed. Using these conditions, we classify the strength of variants of marriage theorems in the context of reverse mathematics. Furthermore, we introduce another condition that also makes the marriage theorem provable in , and investigate the sequential and Weihrauch strength of marriage theorems under that condition.     

Extraction behavior and separation of lanthanides with a diglycol amic acid derivative and a nitrogen-donor ligand.

The extraction and separation of lanthanides have been investigated using CHON-type extractants, which are composed of only C, H, O, and N atoms. N,N-Dioctyldiglycol amic acid (DODGAA) showed high extraction and separation performances for heavier lanthanides compared with typical CHON-type extractants. On the other hand, N,N,N',N'-tetrakis(2-pyridylmethyl)ethylenediamine (TPEN) provided an unprecedentedly high selectivity for lighter lanthanides. Furthermore, it was found that the combination of DODGAA and TPEN under suitable conditions enabled the mutual separation of light, middle, and heavy lanthanides.     

Behaviour of 4-(4-chlorophenyl)-6-(4-tolyl)-4,5-dihydro pyrimidine-2(1H) thione and 2-hydrazino derivative toward carbon electrophiles

The reaction of thiourea with p-methyl-β-p-chlorophenyl acrylophenone ( 1 ) is, in principle, an attractive [3 + 3]-fragment approach to the synthesis of dihydropyrimidine bearing aryl groups.     

Structural properties of an artificial protein that regulates the nucleation of inorganic and organic crystals

Technological advances have facilitated the generation of artificial proteins that possess the capabilities of recognizing and binding to inorganic solids and/or controlling nucleation processes that form inorganic solids. However, very little is known regarding the structure of these interesting polypeptides and how their structure contributes to functionality. To address this deficiency, we report structural investigations of an artificial protein, p288, that self-assembles and controls the nucleation of simple salts and organic compounds into dendrite-like crystals. Under aqueous conditions at low pH and in the presence of high salt, p288 is conformationally labile and exists primarily as a random coil conformer in equilibrium with other undefined secondary structures, including polyproline type II and beta turn. We note that p288 can fold into either a partial beta strand (at neutral pH) or a predominantly alpha helical (in the presence of TFE) conformation. Solid-state 13C-15N NMR experiments also reveal that p288 in the lyophilized, hydrated state possesses some degree of nonrandom coil structure. These results indicate that p288 is conformationally labile but can undergo conformational transitions to a more stable structure when water solvent loss/displacement occurs and protein concentrations increase. We believe that conformational instability and the ability to adopt different structures as a function of different environmental conditions represent important molecular features that impact p288 supramolecular assembly and crystal nucleation processes.