Construction of porphyrin-cyclodextrin self-assembly with molecular wedge

A new host porphyrin bearing four permethyl-beta-cyclodextrin moieties for multi-porphyrin assembly forms a unique 2 : 2 assembly with the tetra-anion of tetrakis(p-sulfonylphenyl)porphyrin (TPPS) in aqueous solution.     

2H NMR study of phase transition and hydrogen dynamics in hydrogen bonded organic antiferroelectric 55DMBP-H2ca

Hydrogen dynamics in one-dimensional hydrogen bonded organic antiferroelectric, co-crystal of 5,5’-dimethyl-2,2’-bipyridine (55DMBP) and chloranilic acid (H₂ca), was investigated by use of ²H high resolution solid-state NMR. The two types of hydrogen bonds O-H …N and N⁺-H …O^? in the antiferroelectric phase were clearly observed as the splitting of the side band of the ²H MAS NMR spectra of the acid-proton deuterated compound 55DMBP-D ₂ca. The temperature dependence of the spin-lattice relaxation time was measured of the N⁺-H and O-H deuterons, respectively. It was suggested that the motion of the O-H deuteron is already in the antiferroelectric phase in the fast-motion regime in the NMR time scale, while that of the N⁺-H deuteron is a slow motion. In the high-temperature paraelectric phase, the both deuterons become equivalent and the fast motion of the deuterons in the NMR time scale is taking place with the activation energy of 7.9 kJ mol^?1.     

RhI‐Catalyzed Intramolecular Carbonylative C−H/C−I Coupling of 2‐Iodobiphenyls Using Furfural as a Carbonyl Source

Synthesis of fluoren‐9‐ones by a Rh‐catalyzed intramolecular C?H/C?I carbonylative coupling of 2‐iodobiphenyls using furfural as a carbonyl source is presented. The findings indicate that the rate‐determining step is not a C?H bond cleavage but, rather, the oxidative addition of the C?I bond to a Rh^I center.     

Organocatalytic Enantioselective Nucleophilic Alkynylation of Allyl Fluorides Affording Chiral Skipped Ene‐ynes

Asymmetric methods for preparation of chiral alkynyl‐containing compounds are in extremely high demand in many sectors of chemical research. In this work, we report the discovery of a general organocatalytic enantioselective alkynylation based on the idea of Si/F activation of the allylic C?F bond. This approach features reasonably broad substrate scope, functional group tolerance, and relatively neutral, mild, and operationally convenient reaction conditions; all of which bode well for the synthetic value of the discovered method. In particular, this method provides unique chiral skipped 1,4‐ene‐ynes having two kinds of versatile functional groups.     

Visualizing the “heartbeat” of a city with tweets

Describing the dynamics of a city is a crucial step to both understanding the human activity in urban environments and to planning and designing cities accordingly. Here, we describe the collective dynamics of New York City (NYC) and surrounding areas as seen through the lens of Twitter usage. In particular, we observe and quantify the patterns that emerge naturally from the hourly activities in different areas of NYC, and discuss how they can be used to understand the urban areas. Using a dataset that includes more than 6 million geolocated Twitter messages we construct a movie of the geographic density of tweets. We observe the diurnal “heartbeat” of the NYC area. The largest scale dynamics are the waking and sleeping cycle and commuting from residential communities to office areas in Manhattan. Hourly dynamics reflect the interplay of commuting, work and leisure, including whether people are preoccupied with other activities or actively using Twitter. Differences between weekday and weekend dynamics point to changes in when people wake and sleep, and engage in social activities. We show that by measuring the average distances to a central location one can quantify the weekly differences and the shift in behavior during weekends. We also identify locations and times of high Twitter activity that occur because of specific activities. These include early morning high levels of traffic as people arrive and wait at air transportation hubs, and on Sunday at the Meadowlands Sports Complex and Statue of Liberty. We analyze the role of particular individuals where they have large impacts on overall Twitter activity. Our analysis points to the opportunity to develop insight into both geographic social dynamics and attention through social media analysis. © 2015 Wiley Periodicals, Inc. Complexity 21: 280–287, 2016     

Crystal plane dependent growth of aligned single-walled carbon nanotubes on sapphire

On single-crystal substrates, such as sapphire (alpha-Al 2O 3) and quartz (SiO 2), single-walled carbon nanotubes (SWNTs) align along specific crystallographic axes of the crystal, indicating that the SWNT growth is influenced by the crystal surface. Here, we show that not only the orientation, but also the diameter and chirality of SWNTs are affected by the crystal plane of the sapphire substrate. The aligned SWNTs grown on the A- and R-planes of sapphire have narrower diameter distributions than randomly oriented tubes produced on the C-plane sapphire and amorphous SiO 2. Photoluminescence measurements reveal a striking difference between the aligned SWNTs: near-zigzag tubes are observed on the A-plane and near-armchair tubes on the R-plane. This study shows the route for the diameter and chirality control of SWNTs by surface atomic arrangements of a single-crystal substrate.     

Synthesis of Bicyclo[1.1.1]pentane (BCP)-Based Straight-Shaped Diphosphine Ligands**

[1.1.1]Propellane, which is structurally simple and compact, exhibits promising potential for the synthesis of disubstituted straight-shaped bicyclo[1.1.1]pentane (BCP) compounds by manipulation of its highly reactive internal C−C bond. BCPs are considered to be isosteres of 1,4-disubstituted benzenes, which have found broad applications in the areas of functional molecules and drug discovery. The internal C−C single bond of [1.1.1]propellane is regarded as a charge-shift bond, which can be readily cleaved by radical means to construct BCPs. We herein report a novel synthetic method for (un)symmetric diphosphines based on the BCP motif, which can be interpreted as isosteres of 1,4-bis(diphenylphosphino)benzenes. The obtained BCP-diphosphine derivatives were used to generate a straight-shaped Au complex and an Eu-based coordination polymer.     

Excitation energy flow control in {Ru(2,2'-bipyridine)2}-{pyridylporphyrin}2 systems

The direction of excitation energy migration is reversed in a system composed of {Ru(bpy)(2)}-{pyridylporphyrin}(2) by the addition of a Zn(2+) ion. The Zn(2+) system shows an excitation-wavelength dependent emission.     

Intermolecular radical addition of alkylthio- and arylthiodiphenylphosphines to terminal alkynes

Intermolecular radical thiophosphination of terminal alkynes with alkylthio- and arylthiophosphines affords 1-thio-2-phosphino-1-alkenes in good yields. The addition reaction proceeds predominantly in an anti fashion to yield E isomers.