An official website of the United States government
Abstract Coordination complexes of general formulatrans‐[MX2(R2ECH2CH2ER2)2] (MII=Ti, V, Cr, Mn; E=N or P; R=alkyl or aryl) are a cornerstone of coordination and organometallic chemistry. We investigate the electronic properties of two such complexes,trans‐[VCl2(tmeda)2] andtrans‐[VCl2(dmpe)2], which thus representtrans‐[MX2(R2ECH2CH2ER2)2] where M=V, X=Cl, R=Me and E=N (tmeda) and P (dmpe). These VIIcomplexes haveS=3/2 ground states, as expected for octahedral d3. Their tetragonal distortion leads to zero‐field splitting (zfs) that is modest in magnitude (D≈0.3 cm−1) relative to analogousS=1 TiIIand CrIIcomplexes. This parameter was determined from conventional EPR spectroscopy, but more effectively from high‐frequency and ‐field EPR (HFEPR) that determined the sign ofDas negative for the diamine complex, but positive for the diphosphine, which information had not been known for anytrans‐[VX2(R2ECH2CH2ER2)2] systems. The ligand‐field parameters oftrans‐[VCl2(tmeda)2] andtrans‐[VCl2(dmpe)2] are obtained using both classical theory andab initioquantum chemical theory. The results shed light not only on the electronic structure of VIIin this environment, but also on differences between N and P donor ligands, a key comparison in coordination chemistry.
more »
« less
Visible-light TiO 2 -catalyzed synthesis of dihydrobenzofurans by oxidative [3 + 2] annulation of phenols with alkenyl phenols
An oxidative strategy for the preparation of dihydrobenzofuransviaheterogeneous photocatalysis is reported.
more »
« less
- Award ID(s):
- 2102626
- PAR ID:
- 10585483
- Publisher / Repository:
- Royal Society of Chemistry
- Date Published:
- Journal Name:
- Chemical Science
- Volume:
- 15
- Issue:
- 19
- ISSN:
- 2041-6520
- Page Range / eLocation ID:
- 7150 to 7159
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Abstract Bi2SeO2is a promisingn‐type semiconductor to pair withp‐type BiCuSeO in a thermoelectric (TE) device. The TE figure of meritzTand, therefore, the device efficiency must be optimized by tuning the carrier concentration. However, electron concentrations in self‐dopedn‐type Bi2SeO2span several orders of magnitude, even in samples with the same nominal compositions. Such unsystematic variations in the electron concentration have a thermodynamic origin related to the variations in native defect concentrations. In this study, first‐principles calculations are used to show that the selenium vacancy, which is the source ofn‐type conductivity in Bi2SeO2, varies by 1–2 orders of magnitude depending on the thermodynamic conditions. It is predicted that the electron concentration can be enhanced by synthesizing under more Se‐poor conditions and/or at higher solid‐state reaction temperatures (TSSR), which promote the formation of selenium vacancies without introducing extrinsic dopants. The computational predictions are validated through solid‐state synthesis of Bi2SeO2. More than two orders of magnitude increase are observed in the electron concentration simply by adjusting the synthesis conditions. Additionally, a significant effect of grain boundary scattering on the electron mobility in Bi2SeO2is revealed, which can also be controlled by adjusting TSSR. By simultaneously optimizing the electron concentration and mobility, azTof ≈0.2 is achieved at 773 K for self‐dopedn‐type Bi2SeO2. The study highlights the need for careful control of thermodynamic growth conditions and demonstrates TE performance improvement by varying synthesis parameters according to thermodynamic guidelines.more » « less
-
Abstract Synthesizing solids in molten fluxes enables the rapid diffusion of soluble species at temperatures lower than in solid‐state reactions, leading to crystal formation of kinetically stable compounds. In this study, we demonstrate the effectiveness of mixed hydroxide and halide fluxes in synthesizing complex Sr/Ag/Se in mixed LiOH/LiCl. We have accessed a series of two‐dimensional Sr(Ag1−xLix)2Se2layered phases. With increased LiOH/LiCl ratio or reaction temperature, Li partially substituted Ag to form solid solutions of Sr(Ag1−xLix)2Se2withxup to 0.45. In addition, a new type of intergrowth compound [Sr3Se2][(Ag1−xLix)2Se2] was synthesized upon further reaction of Sr(Ag1−xLix)2Se2with SrSe. Both Sr(Ag1−xLix)2Se2and [Sr3Se2][(Ag1−xLix)2Se2] exhibit a direct band gap, which increases with increasing Li substitution (x). Therefore, the band gap of Sr(Ag1−xLix)2Se2can be precisely tuned via fine‐tuningxthat is controlled by only the flux ratio and temperature.more » « less
-
Abstract The preparation of 0.58 Li2S + 0.315 SiS2+ 0.105 LiPO3glass, and the impacts of polysulfide and P1Pdefect structure impurities on the glass transition temperature (Tg), crystallization temperature (Tc), working range (ΔT≡ Tc‐ Tg), fragility index, and the Raman spectra were evaluated using statistical analysis. In this study, 33 samples of this glass composition were synthesized through melt‐quenching. Thermal analysis was conducted to determine the glass transition temperature, crystallization temperature, working range, and fragility index through differential scanning calorimetry. The quantity of the impurities described above was determined through Raman spectroscopy peak analysis. Elemental sulfur was doped into a glass to quantify the wt% sulfur content in the glasses. Linear regression analysis was conducted to determine the impact of polysulfide impurities and P1Pdefect impurities on the thermal properties. Polysulfide impurities were found to decrease theTgat rate of nearly 12°C per 1 wt% increase in sulfur concentration. The sulfur concentration does not have a statistically significant impact on the other properties (α = 0.05). The P1Pdefect structure appears to decrease the resistance to crystallization of the glass by measurably decreasing the working range of the glasses, but further study is necessary to fully quantify and determine this.more » « less
-
Abstract The overarching goal of this study is to effect the elimination of platinum from adducts withcis–C≡C−Pt−C≡C‐ linkages, thereby generating novel conjugated polyynes. Thus, the bis(hexatriynyl) complextrans‐(p‐tol3P)2Pt((C≡C)3H)2is treated with 1,3‐diphosphines R2C(CH2PPh2)2to generate (R2C(CH2PPh2)2)2Pt((C≡C)3H)2(14; R=c,n‐Bu;e,p‐tolCH2). These condense with the diiodide complexes R2C(CH2PPh2)2PtI2(9 a,c) in the presence of CuI (cat.) and excess HNEt2to give the title macrocycles [(R2C(CH2PPh2)2)Pt(C≡C)3]4(16 c,e) as adducts of the byproduct [H2NEt2]+I−(30–66 %). DOSY NMR experiments establish that this association is maintained in solution, but NaOAc removes the ammonium salt. The bis(triethylsilylpolyynyl) complexes (n‐Bu2C(CH2PPh2)2)Pt((C≡C)nSiEt3)2(n=2, 3) are synthesized analogously to14 c. They react with I2at rt to give mainly the diiodide complex9 cand the coupling product Et3Si(C≡CC≡C)nSiEt3. The possibility of competing reactions giving IC≡C species is investigated. Analogous reactions of the Pt4C24macrocycle16 calso give9 c, but no sp13C NMR signals or mass spectrometric Cxz+ions (x=24–100) could be detected. It is proposed that some cyclo[24]carbon is generated, but then rapidly converts to other forms of elemental carbon. No cyclotetracosane (C24H48) is detected when this sequence is carried out in the presence of PtO2and H2.more » « less
- Free Publicly Accessible Full Text
-
Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/D4SC00723A
